Sample records for biomass fast pyrolysis

  1. Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

    DOE PAGES

    Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.; ...

    2016-09-05

    Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, heremore » we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective

  2. Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.

    Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, heremore » we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg -1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg -1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective

  3. Catalytic fast pyrolysis of lignocellulosic biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, Changjun; Wang, Huamin; Karim, Ayman M.

    2014-11-21

    Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy Q3 carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectivelymore » convert lignocellulose into a liquid fuel—bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating values, high corrosiveness, high viscosity, and instability; they also greatly Q4 limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.« less

  4. Acidity of biomass fast pyrolysis bio-oils

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Oasmaa, Anja; Elliott, Douglas C.; Korhonen, Jaana

    2010-12-17

    The use of the TAN method for measuring the acidity of biomass fast pyrolysis bio-oil was evaluated. Suggestions for carrying out the analysis have been made. The TAN method by ASTM D664 or D3339 can be used for measuring the acidity of fast pyrolysis bio-oils and their hydrotreating products. The main difference between the methods is that ASTM D664 is specified for higher TAN values than ASTM D3339. Special focus should be placed on the interpretation of the TAN curves because they differ significantly from those of mineral oils. The curve for bio-oils is so gentle that the automatic detectionmore » may not observe the end point properly and derivatization should be used. The acidity of fast pyrolysis bio-oils is mainly derived (60-70%) from volatile acids. Other groups of compounds in fast pyrolysis bio-oils that influence acidity include phenolics, fatty and resin acids, and hydroxy acids.« less

  5. Simulating Biomass Fast Pyrolysis at the Single Particle Scale

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ciesielski, Peter; Wiggins, Gavin; Daw, C Stuart

    2017-07-01

    Simulating fast pyrolysis at the scale of single particles allows for the investigation of the impacts of feedstock-specific parameters such as particle size, shape, and species of origin. For this reason particle-scale modeling has emerged as an important tool for understanding how variations in feedstock properties affect the outcomes of pyrolysis processes. The origins of feedstock properties are largely dictated by the composition and hierarchical structure of biomass, from the microstructural porosity to the external morphology of milled particles. These properties may be accounted for in simulations of fast pyrolysis by several different computational approaches depending on the level ofmore » structural and chemical complexity included in the model. The predictive utility of particle-scale simulations of fast pyrolysis can still be enhanced substantially by advancements in several areas. Most notably, considerable progress would be facilitated by the development of pyrolysis kinetic schemes that are decoupled from transport phenomena, predict product evolution from whole-biomass with increased chemical speciation, and are still tractable with present-day computational resources.« less

  6. Specialists' workshop on fast pyrolysis of biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Not Available

    1980-01-01

    This workshop brought together most of those who are currently working in or have published significant findings in the area of fast pyrolysis of biomass or biomass-derived materials, with the goal of attaining a better understanding of the dominant mechanisms which produce olefins, oxygenated liquids, char, and tars. In addition, background papers were given in hydrocarbon pyrolysis, slow pyrolysis of biomass, and techniques for powdered-feedstock preparation in order that the other papers did not need to introduce in depth these concepts in their presentations for continuity. In general, the authors were requested to present summaries of experimental data with asmore » much interpretation of that data as possible with regard to mechanisms and process variables such as heat flux, temperatures, partial pressure, feedstock, particle size, heating rates, residence time, etc. Separate abstracts have been prepared of each presentation for inclusion in the Energy Data Base. (DMC)« less

  7. Pyrolysis of fast-growing aquatic biomass -Lemna minor (duckweed): Characterization of pyrolysis products.

    PubMed

    Muradov, Nazim; Fidalgo, Beatriz; Gujar, Amit C; T-Raissi, Ali

    2010-11-01

    The aim of this work was to conduct the experimental study of pyrolysis of fast-growing aquatic biomass -Lemna minor (commonly known as duckweed) with the emphasis on the characterization of main products of pyrolysis. The yields of pyrolysis gas, pyrolytic oil (bio-oil) and char were determined as a function of pyrolysis temperature and the sweep gas (Ar) flow rate. Thermogravimetric/differential thermogravimetric (TG/DTG) analyses of duckweed samples in inert (helium gas) and oxidative (air) atmosphere revealed differences in the TG/DTG patterns obtained for duckweed and typical plant biomass. The bio-oil samples produced by duckweed pyrolysis at different reaction conditions were analyzed using GC-MS technique. It was found that pyrolysis temperature had minor effect on the bio-oil product slate, but exerted major influence on the relative quantities of the individual pyrolysis products obtained. While, the residence time of the pyrolysis vapors had negligible effect on the yield and composition of the duckweed pyrolysis products. Copyright 2010 Elsevier Ltd. All rights reserved.

  8. Fast Pyrolysis of Biomass Residues in a Twin-screw Mixing Reactor

    PubMed Central

    Funke, Axel; Richter, Daniel; Niebel, Andreas; Dahmen, Nicolaus; Sauer, Jörg

    2016-01-01

    Fast pyrolysis is being increasingly applied in commercial plants worldwide. They run exclusively on woody biomass, which has favorable properties for conversion with fast pyrolysis. In order to increase the synergies of food production and the energetic and/or material use of biomass, it is desirable to utilize residues from agricultural production, e.g., straw. The presented method is suitable for converting such a material on an industrial scale. The main features are presented and an example of mass balances from the conversion of several biomass residues is given. After conversion, fractionated condensation is applied in order to retrieve two condensates — an organic-rich and an aqueous-rich one. This design prevents the production of fast pyrolysis bio-oil that exhibits phase separation. A two phase bio-oil is to be expected because of the typically high ash content of straw biomass, which promotes the production of water of reaction during conversion. Both fractionated condensation and the use of biomass with high ash content demand a careful approach for establishing balances. Not all kind of balances are both meaningful and comparable to other results from the literature. Different balancing methods are presented, and the information that can be derived from them is discussed. PMID:27684439

  9. Screening acidic zeolites for catalytic fast pyrolysis of biomass and its components

    USDA-ARS?s Scientific Manuscript database

    Zeolites have been shown to effectively promote cracking reactions during pyrolysis resulting in highly deoxygenated and hydrocarbon-rich compounds and stable pyrolysis oil product. Py/GC-MS was employed to study the catalytic fast pyrolysis of lignocellulosic biomass samples comprising oak, corn...

  10. Production of hydrogen from biomass by catalytic steam reforming of fast pyrolysis oil

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Czernik, S.; Wang, D.; Chornet, E.

    1998-08-01

    Hydrogen is the prototype of the environmentally cleanest fuel of interest for power generation using fuel cells and for transportation. The thermochemical conversion of biomass to hydrogen can be carried out through two distinct strategies: (a) gasification followed by water-gas shift conversion, and (b) catalytic steam reforming of specific fractions derived from fast pyrolysis and aqueous/steam processes of biomass. This paper presents the latter route that begins with fast pyrolysis of biomass to produce bio-oil. This oil (as a whole or its selected fractions) can be converted to hydrogen via catalytic steam reforming followed by a water-gas shift conversion step.more » Such a process has been demonstrated at the bench scale using model compounds, poplar oil aqueous fraction, and the whole pyrolysis oil with commercial Ni-based steam reforming catalysts. Hydrogen yields as high as 85% have been obtained. Catalyst initial activity can be recovered through regeneration cycles by steam or CO{sub 2} gasification of carbonaceous deposits.« less

  11. Dual fluidized bed design for the fast pyrolysis of biomass

    USDA-ARS?s Scientific Manuscript database

    A mechanism for the transport of solids between fluidised beds in dual fluidised bed systems for the fast pyrolysis of biomass process was selected. This mechanism makes use of an overflow standpipe to transport solids from the fluidised bed used for the combustion reactions to a second fluidised be...

  12. Biomass Conversion to Produce Hydrocarbon Liquid Fuel Via Hot-vapor Filtered Fast Pyrolysis and Catalytic Hydrotreating.

    PubMed

    Wang, Huamin; Elliott, Douglas C; French, Richard J; Deutch, Steve; Iisa, Kristiina

    2016-12-25

    Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. The protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.

  13. Biomass Conversion to Produce Hydrocarbon Liquid Fuel Via Hot-vapor Filtered Fast Pyrolysis and Catalytic Hydrotreating

    PubMed Central

    Wang, Huamin; Elliott, Douglas C.; French, Richard J.; Deutch, Steve; Iisa, Kristiina

    2016-01-01

    Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. The protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research. PMID:28060311

  14. Catalytic hydroprocessing of fast pyrolysis oils: Impact of biomass feedstock on process efficiency

    DOE PAGES

    Carpenter, Daniel; Westover, Tyler; Howe, Daniel; ...

    2016-12-01

    Here, we report here on an experimental study to produce refinery-ready fuel blendstocks via catalytic hydrodeoxygenation (upgrading) of pyrolysis oil using several biomass feedstocks and various blends. Blends were tested along with the pure materials to determine the effect of blending on product yields and qualities. Within experimental error, oil yields from fast pyrolysis and upgrading are shown to be linear functions of the blend components. Switchgrass exhibited lower fast pyrolysis and upgrading yields than the woody samples, which included clean pine, oriented strand board (OSB), and a mix of pinon and juniper (PJ). The notable exception was PJ, formore » which the poor upgrading yield of 18% was likely associated with the very high viscosity of the PJ fast pyrolysis oil (947 cp). The highest fast pyrolysis yield (54% dry basis) was obtained from clean pine, while the highest upgrading yield (50%) was obtained from a blend of 80% clean pine and 20% OSB (CP 8OSB 2). For switchgrass, reducing the fast pyrolysis temperature to 450 degrees C resulted in a significant increase to the pyrolysis oil yield and reduced hydrogen consumption during hydrotreating, but did not directly affect the hydrotreating oil yield. The water content of fast pyrolysis oils was also observed to increase linearly with the summed content of potassium and sodium, ranging from 21% for clean pine to 37% for switchgrass. Multiple linear regression models demonstrate that fast pyrolysis is strongly dependent upon the contents lignin and volatile matter as well as the sum of potassium and sodium.« less

  15. A CFD model for biomass fast pyrolysis in fluidized-bed reactors

    NASA Astrophysics Data System (ADS)

    Xue, Qingluan; Heindel, T. J.; Fox, R. O.

    2010-11-01

    A numerical study is conducted to evaluate the performance and optimal operating conditions of fluidized-bed reactors for fast pyrolysis of biomass to bio-oil. A comprehensive CFD model, coupling a pyrolysis kinetic model with a detailed hydrodynamics model, is developed. A lumped kinetic model is applied to describe the pyrolysis of biomass particles. Variable particle porosity is used to account for the evolution of particle physical properties. The kinetic scheme includes primary decomposition and secondary cracking of tar. Biomass is composed of reference components: cellulose, hemicellulose, and lignin. Products are categorized into groups: gaseous, tar vapor, and solid char. The particle kinetic processes and their interaction with the reactive gas phase are modeled with a multi-fluid model derived from the kinetic theory of granular flow. The gas, sand and biomass constitute three continuum phases coupled by the interphase source terms. The model is applied to investigate the effect of operating conditions on the tar yield in a fluidized-bed reactor. The influence of various parameters on tar yield, including operating temperature and others are investigated. Predicted optimal conditions for tar yield and scale-up of the reactor are discussed.

  16. Biomass conversion to produce hydrocarbon liquid fuel via hot-vapor filtered fast pyrolysis and catalytic hydrotreating

    DOE PAGES

    Wang, Huamin; Elliott, Douglas C.; French, Richard J.; ...

    2016-12-25

    Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and themore » processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. As a result, the protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.« less

  17. Biomass conversion to produce hydrocarbon liquid fuel via hot-vapor filtered fast pyrolysis and catalytic hydrotreating

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Huamin; Elliott, Douglas C.; French, Richard J.

    Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and themore » processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. As a result, the protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.« less

  18. Effect of torrefaction on biomass structure and hydrocarbon production from fast pyrolysis

    DOE PAGES

    Neupane, Sneha; Adhikari, Sushil; Wang, Zhouhong; ...

    2015-01-27

    Torrefaction has been shown to improve the chemical composition of bio-oils produced from fast pyrolysis by lowering its oxygen content and enhancing the aromatic yield. A Py-GC/MS study was employed to investigate the effect of torrefaction temperatures (225, 250 and 275 °C) and residence times (15, 30 and 45 min) on product distribution from non-catalytic and H +ZSM-5 catalyzed pyrolysis of pinewood. During torrefaction, structural transformations in biomass constitutive polymers: hemicellulose, cellulose and lignin took place, which were evaluated using component analysis, solid state CP/MAS 13C NMR and XRD techniques. Torrefaction caused deacetylation and decomposition of hemicellulose, cleavage of arylmore » ether linkages and demethoxylation of lignin, degradation of cellulose and an overall increase in aromaticity of biomass, all of which affected the product yield from pyrolysis of torrefied biomass. For non-catalytic pyrolysis, selectivity of phenolic compounds increased with an increase in torrefaction severity while that of furan compounds decreased. In the case of catalytic pyrolysis, the sample torrefied at 225 °C-30 min and 250 °C-15 min resulted in a significant increase in aromatic hydrocarbon (HC) and also total carbon yield (approx. 1.6 times higher) as compared to catalytic pyrolysis of non-torrefied pine. Cleavage of aryl ether linkages and demethoxylation in lignin due to torrefaction caused increased yield of phenolic compounds, which in the presence of a catalyst were dehydrated to form aromatic HC.« less

  19. Fast microwave assisted pyrolysis of biomass using microwave absorbent.

    PubMed

    Borges, Fernanda Cabral; Du, Zhenyi; Xie, Qinglong; Trierweiler, Jorge Otávio; Cheng, Yanling; Wan, Yiqin; Liu, Yuhuan; Zhu, Rongbi; Lin, Xiangyang; Chen, Paul; Ruan, Roger

    2014-03-01

    A novel concept of fast microwave assisted pyrolysis (fMAP) in the presence of microwave absorbents was presented and examined. Wood sawdust and corn stover were pyrolyzed by means of microwave heating and silicon carbide (SiC) as microwave absorbent. The bio-oil was characterized, and the effects of temperature, feedstock loading, particle sizes, and vacuum degree were analyzed. For wood sawdust, a temperature of 480°C, 50 grit SiC, with 2g/min of biomass feeding, were the optimal conditions, with a maximum bio-oil yield of 65 wt.%. For corn stover, temperatures ranging from 490°C to 560°C, biomass particle sizes from 0.9mm to 1.9mm, and vacuum degree lower than 100mmHg obtained a maximum bio-oil yield of 64 wt.%. This study shows that the use of microwave absorbents for fMAP is feasible and a promising technology to improve the practical values and commercial application outlook of microwave based pyrolysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Optimizing biomass feedstock blends with respect to cost, supply, and quality for catalyzed and uncatalyzed fast pyrolysis applications

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Thompson, Vicki S.; Aston, John E.; Lacey, Jeffrey A.

    Here, biomass cost, quality and quantity are important parameters to consider when choosing feedstocks and locations for biorefineries. Biomass cost is dependent upon type, location, quantities available in a given area and logistics costs as well the quality needed for the biorefinery. Biomass quality depends upon type, growth conditions, weather, harvesting methods, storage conditions as well as any preprocessing methods used to improve quality. Biomass quantity depends heavily on location as well as growth conditions, weather, harvesting methods and storage conditions. This study examines how all three of these parameters affect the biomass mixture that is needed in a biomassmore » depot or biorefinery to achieve the lowest cost with the highest quality and at the quantities needed for biorefinery operation. Four biomass depots were proposed in South Carolina that would each process the predominant type of biomass available in that area and each produce 200,000 tons of feedstock per year. These depots would then feed a centrally located 800,000 ton biorefinery that would convert the feedstocks to pyrolysis oil using either catalyzed or uncatalyzed fast pyrolysis. The four depots each needed to produce different blends of biomass based upon the quantities available to them but still meet the minimum quality requirements for the biorefinery. Costs were minimized by using waste biomass resources such as construction and demolition waste, logging residues and forest residuals. Depending upon the quality specification required by the biorefinery, it was necessary to utilize preprocessing methods such as air classification and acid leaching to upgrade biomass quality. In the case of uncatalyzed fast pyrolysis, all four depots could produce biomass blends that were lower cost than the the preferred pyrolysis feedstock, clean pine, and meet quality and quantity specifications. For catalyzed fast pyrolysis, three of the four depots were able to produce blends that met

  1. Optimizing biomass feedstock blends with respect to cost, supply, and quality for catalyzed and uncatalyzed fast pyrolysis applications

    DOE PAGES

    Thompson, Vicki S.; Aston, John E.; Lacey, Jeffrey A.; ...

    2017-05-24

    Here, biomass cost, quality and quantity are important parameters to consider when choosing feedstocks and locations for biorefineries. Biomass cost is dependent upon type, location, quantities available in a given area and logistics costs as well the quality needed for the biorefinery. Biomass quality depends upon type, growth conditions, weather, harvesting methods, storage conditions as well as any preprocessing methods used to improve quality. Biomass quantity depends heavily on location as well as growth conditions, weather, harvesting methods and storage conditions. This study examines how all three of these parameters affect the biomass mixture that is needed in a biomassmore » depot or biorefinery to achieve the lowest cost with the highest quality and at the quantities needed for biorefinery operation. Four biomass depots were proposed in South Carolina that would each process the predominant type of biomass available in that area and each produce 200,000 tons of feedstock per year. These depots would then feed a centrally located 800,000 ton biorefinery that would convert the feedstocks to pyrolysis oil using either catalyzed or uncatalyzed fast pyrolysis. The four depots each needed to produce different blends of biomass based upon the quantities available to them but still meet the minimum quality requirements for the biorefinery. Costs were minimized by using waste biomass resources such as construction and demolition waste, logging residues and forest residuals. Depending upon the quality specification required by the biorefinery, it was necessary to utilize preprocessing methods such as air classification and acid leaching to upgrade biomass quality. In the case of uncatalyzed fast pyrolysis, all four depots could produce biomass blends that were lower cost than the the preferred pyrolysis feedstock, clean pine, and meet quality and quantity specifications. For catalyzed fast pyrolysis, three of the four depots were able to produce blends that met

  2. Estimating the Temperature Experienced by Biomass Particles during Fast Pyrolysis Using Microscopic Analysis of Biochars

    DOE PAGES

    Thompson, Logan C.; Ciesielski, Peter N.; Jarvis, Mark W.; ...

    2017-07-12

    Here, biomass particles can experience variable thermal conditions during fast pyrolysis due to differences in their size and morphology, and from local temperature variations within a reactor. These differences lead to increased heterogeneity of the chemical products obtained in the pyrolysis vapors and bio-oil. Here we present a simple, high-throughput method to investigate the thermal history experienced by large ensembles of particles during fast pyrolysis by imaging and quantitative image analysis. We present a correlation between the surface luminance (darkness) of the biochar particle and the highest temperature that it experienced during pyrolysis. Next, we apply this correlation to large,more » heterogeneous ensembles of char particles produced in a laminar entrained flow reactor (LEFR). The results are used to interpret the actual temperature distributions delivered by the reactor over a range of operating conditions.« less

  3. Development of bio-fuel from palm frond via fast pyrolysis

    NASA Astrophysics Data System (ADS)

    Solikhah, M. D.; Raksodewanto, A. A.; Kismanto, A.; Karuana, F.; Heryana, Y.; Riza; Pratiwi, F. T.

    2017-05-01

    In order to fulfill the fuel demand in the future, Indonesia has to find a sustainable alternative for its energy. Energy source in the form of biomass is a promising alternative since its availability is abundance in this tropical country. Biomass can be converted into liquid fuel via fast pyrolysis by contacting the solid biomass into hot medium in the absence of oxygen. Hot sand is the common heat carrier for fast pyrolysis purposes but it is very abrasive and required high pyrolysis temperature (450-600 °C). This paper will discuss on the equipment design and experiment of fast pyrolysis of palm frond using high boiling point thermal oil as heat carrier. Experiments show that by using thermal oil as heat carrier, bio-oil can be produced at lower pyrolysis temperature of 350 °C, compared to the one using hot sand as heating carrier. The yield of bio-oil production is 36.4 % of biomass feeding. The water content of bio-oil is 52.77 % mass while heating value is 10.25 MJ/kg.

  4. Upgrading biomass pyrolysis bio-oil to renewable fuels.

    DOT National Transportation Integrated Search

    2015-01-01

    Fast pyrolysis is a process that can convert woody biomass to a crude bio-oil (pyrolysis oil). However, some of these compounds : contribute to bio-oil shelf life instability and difficulty in refining. Catalytic hydrodeoxygenation (HDO) of the bio-o...

  5. Quantitative Insights into the Fast Pyrolysis of Extracted Cellulose, Hemicelluloses, and Lignin

    PubMed Central

    Windt, Michael; Ziegler, Bernhard; Appelt, Jörn; Saake, Bodo; Meier, Dietrich; Bridgwater, Anthony

    2017-01-01

    Abstract The transformation of lignocellulosic biomass into bio‐based commodity chemicals is technically possible. Among thermochemical processes, fast pyrolysis, a relatively mature technology that has now reached a commercial level, produces a high yield of an organic‐rich liquid stream. Despite recent efforts to elucidate the degradation paths of biomass during pyrolysis, the selectivity and recovery rates of bio‐compounds remain low. In an attempt to clarify the general degradation scheme of biomass fast pyrolysis and provide a quantitative insight, the use of fast pyrolysis microreactors is combined with spectroscopic techniques (i.e., mass spectrometry and NMR spectroscopy) and mixtures of unlabeled and 13C‐enriched materials. The first stage of the work aimed to select the type of reactor to use to ensure control of the pyrolysis regime. A comparison of the chemical fragmentation patterns of “primary” fast pyrolysis volatiles detected by using GC‐MS between two small‐scale microreactors showed the inevitable occurrence of secondary reactions. In the second stage, liquid fractions that are also made of primary fast pyrolysis condensates were analyzed by using quantitative liquid‐state 13C NMR spectroscopy to provide a quantitative distribution of functional groups. The compilation of these results into a map that displays the distribution of functional groups according to the individual and main constituents of biomass (i.e., hemicelluloses, cellulose and lignin) confirmed the origin of individual chemicals within the fast pyrolysis liquids. PMID:28644517

  6. Quantitative Insights into the Fast Pyrolysis of Extracted Cellulose, Hemicelluloses, and Lignin.

    PubMed

    Carrier, Marion; Windt, Michael; Ziegler, Bernhard; Appelt, Jörn; Saake, Bodo; Meier, Dietrich; Bridgwater, Anthony

    2017-08-24

    The transformation of lignocellulosic biomass into bio-based commodity chemicals is technically possible. Among thermochemical processes, fast pyrolysis, a relatively mature technology that has now reached a commercial level, produces a high yield of an organic-rich liquid stream. Despite recent efforts to elucidate the degradation paths of biomass during pyrolysis, the selectivity and recovery rates of bio-compounds remain low. In an attempt to clarify the general degradation scheme of biomass fast pyrolysis and provide a quantitative insight, the use of fast pyrolysis microreactors is combined with spectroscopic techniques (i.e., mass spectrometry and NMR spectroscopy) and mixtures of unlabeled and 13 C-enriched materials. The first stage of the work aimed to select the type of reactor to use to ensure control of the pyrolysis regime. A comparison of the chemical fragmentation patterns of "primary" fast pyrolysis volatiles detected by using GC-MS between two small-scale microreactors showed the inevitable occurrence of secondary reactions. In the second stage, liquid fractions that are also made of primary fast pyrolysis condensates were analyzed by using quantitative liquid-state 13 C NMR spectroscopy to provide a quantitative distribution of functional groups. The compilation of these results into a map that displays the distribution of functional groups according to the individual and main constituents of biomass (i.e., hemicelluloses, cellulose and lignin) confirmed the origin of individual chemicals within the fast pyrolysis liquids. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  7. Biomass fast pyrolysis in a fluidized bed reactor under N2, CO2, CO, CH4 and H2 atmospheres.

    PubMed

    Zhang, Huiyan; Xiao, Rui; Wang, Denghui; He, Guangying; Shao, Shanshan; Zhang, Jubing; Zhong, Zhaoping

    2011-03-01

    Biomass fast pyrolysis is one of the most promising technologies for biomass utilization. In order to increase its economic potential, pyrolysis gas is usually recycled to serve as carrier gas. In this study, biomass fast pyrolysis was carried out in a fluidized bed reactor using various main pyrolysis gas components, namely N(2), CO(2), CO, CH(4) and H(2), as carrier gases. The atmosphere effects on product yields and oil fraction compositions were investigated. Results show that CO atmosphere gave the lowest liquid yield (49.6%) compared to highest 58.7% obtained with CH(4). CO and H(2) atmospheres converted more oxygen into CO(2) and H(2)O, respectively. GC/MS analysis of the liquid products shows that CO and CO(2) atmospheres produced less methoxy-containing compounds and more monofunctional phenols. The higher heating value of the obtained bio-oil under N(2) atmosphere is only 17.8 MJ/kg, while that under CO and H(2) atmospheres increased to 23.7 and 24.4 MJ/kg, respectively. Copyright © 2010 Elsevier Ltd. All rights reserved.

  8. Norms, Standards, and Legislation for Fast Pyrolysis Bio-oils from Lignocellulosic Biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Oasmaa, Anja; van de Beld, Bert; Saari, Pia

    2015-04-16

    Fast pyrolysis of woody biomass is close to full maturity, with first-of-its-kind commercial size installations for fuel production being commissioned in Finland (Fortum) and in The Netherlands (Empyro), and in the design phase in Brazil (Ensyn). In the industrial-scale combustion tests, the use of fast pyrolysis bio-oil (FPBO) has been demonstrated to be a viable option to replace heavy fuel oil in district heating applications. Commercially usable district heating boilers and burners suitable for FPBO are available. There is research on diesel-engine and gas-turbine applications but, so far, no proven demonstrations. FPBO is completely different from mineral oils; hence, standardsmore » are needed. Analytical methods have been systematically validated and modifications to the standards as well as completely new methods have been made. Two ASTM burner fuel standards already exist and European boiler fuel grades are being developed under CEN. The focus on CEN standardization is on boiler use, because of its commercial readiness.« less

  9. Catalytic fast pyrolysis of biomass impregnated with potassium phosphate in a hydrogen atmosphere for the production of phenol and activated carbon

    NASA Astrophysics Data System (ADS)

    Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

    2018-02-01

    A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550 oC in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1605 m2/g.

  10. Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon.

    PubMed

    Lu, Qiang; Zhang, Zhen-Xi; Wang, Xin; Guo, Hao-Qiang; Cui, Min-Shu; Yang, Yong-Ping

    2018-01-01

    A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K 3 PO 4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K 3 PO 4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K 3 PO 4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO 2 activation method, the specific surface area was as high as 1,605 m 2 /g.

  11. One-dimensional biomass fast pyrolysis model with reaction kinetics integrated in an Aspen Plus Biorefinery Process Model

    DOE PAGES

    Humbird, David; Trendewicz, Anna; Braun, Robert; ...

    2017-01-12

    A biomass fast pyrolysis reactor model with detailed reaction kinetics and one-dimensional fluid dynamics was implemented in an equation-oriented modeling environment (Aspen Custom Modeler). Portions of this work were detailed in previous publications; further modifications have been made here to improve stability and reduce execution time of the model to make it compatible for use in large process flowsheets. The detailed reactor model was integrated into a larger process simulation in Aspen Plus and was stable for different feedstocks over a range of reactor temperatures. Sample results are presented that indicate general agreement with experimental results, but with higher gasmore » losses caused by stripping of the bio-oil by the fluidizing gas in the simulated absorber/condenser. Lastly, this integrated modeling approach can be extended to other well-defined, predictive reactor models for fast pyrolysis, catalytic fast pyrolysis, as well as other processes.« less

  12. One-dimensional biomass fast pyrolysis model with reaction kinetics integrated in an Aspen Plus Biorefinery Process Model

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Humbird, David; Trendewicz, Anna; Braun, Robert

    A biomass fast pyrolysis reactor model with detailed reaction kinetics and one-dimensional fluid dynamics was implemented in an equation-oriented modeling environment (Aspen Custom Modeler). Portions of this work were detailed in previous publications; further modifications have been made here to improve stability and reduce execution time of the model to make it compatible for use in large process flowsheets. The detailed reactor model was integrated into a larger process simulation in Aspen Plus and was stable for different feedstocks over a range of reactor temperatures. Sample results are presented that indicate general agreement with experimental results, but with higher gasmore » losses caused by stripping of the bio-oil by the fluidizing gas in the simulated absorber/condenser. Lastly, this integrated modeling approach can be extended to other well-defined, predictive reactor models for fast pyrolysis, catalytic fast pyrolysis, as well as other processes.« less

  13. Selectively improving the bio-oil quality by catalytic fast pyrolysis of heavy-metal-polluted biomass: take copper (Cu) as an example.

    PubMed

    Liu, Wu-Jun; Tian, Ke; Jiang, Hong; Zhang, Xue-Song; Ding, Hong-Sheng; Yu, Han-Qing

    2012-07-17

    Heavy-metal-polluted biomass derived from phytoremediation or biosorption is widespread and difficult to be disposed of. In this work, simultaneous conversion of the waste woody biomass into bio-oil and recovery of Cu in a fast pyrolysis reactor were investigated. The results show that Cu can effectively catalyze the thermo-decomposition of biomass. Both the yield and high heating value (HHV) of the Cu-polluted fir sawdust biomass (Cu-FSD) derived bio-oil are significantly improved compared with those of the fir sawdust (FSD) derived bio-oil. The results of UV-vis and (1)H NMR spectra of bio-oil indicate pyrolytic lignin is further decomposed into small-molecular aromatic compounds by the catalysis of Cu, which is in agreement with the GC-MS results that the fractions of C7-C10 compounds in the bio-oil significantly increase. Inductively coupled plasma-atomic emission spectrometry, X-ray diffraction, and X-ray photoelectron spectroscopy analyses of the migration and transformation of Cu in the fast pyrolysis process show that more than 91% of the total Cu in the Cu-FSD is enriched in the char in the form of zerovalent Cu with a face-centered cubic crystalline phase. This study gives insight into catalytic fast pyrolysis of heavy metals, and demonstrates the technical feasibility of an eco-friendly process for disposal of heavy-metal-polluted biomass.

  14. Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

    PubMed Central

    Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

    2018-01-01

    A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g. PMID:29515994

  15. Two-step fast microwave-assisted pyrolysis of biomass for bio-oil production using microwave absorbent and HZSM-5 catalyst.

    PubMed

    Zhang, Bo; Zhong, Zhaoping; Xie, Qinglong; Liu, Shiyu; Ruan, Roger

    2016-07-01

    A novel technology of two-step fast microwave-assisted pyrolysis (fMAP) of corn stover for bio-oil production was investigated in the presence of microwave absorbent (SiC) and HZSM-5 catalyst. Effects of fMAP temperature and catalyst-to-biomass ratio on bio-oil yield and chemical components were examined. The results showed that this technology, employing microwave, microwave absorbent and HZSM-5 catalyst, was effective and promising for biomass fast pyrolysis. The fMAP temperature of 500°C was considered the optimum condition for maximum yield and best quality of bio-oil. Besides, the bio-oil yield decreased linearly and the chemical components in bio-oil were improved sequentially with the increase of catalyst-to-biomass ratio from 1:100 to 1:20. The elemental compositions of bio-char were also determined. Additionally, compared to one-step fMAP process, two-step fMAP could promote the bio-oil quality with a smaller catalyst-to-biomass ratio. Copyright © 2016. Published by Elsevier B.V.

  16. Improving the conversion of biomass in catalytic fast pyrolysis via white-rot fungal pretreatment.

    PubMed

    Yu, Yanqing; Zeng, Yelin; Zuo, Jiane; Ma, Fuying; Yang, Xuewei; Zhang, Xiaoyu; Wang, Yujue

    2013-04-01

    This study investigated the effect of white-rot fungal pretreatment on corn stover conversion in catalytic fast pyrolysis (CFP). Corn stover pretreated by white-rot fungus Irpex lacteus CD2 was fast pyrolyzed alone (non-CFP) and with ZSM-5 zeolite (CFP) in a semi-batch pyroprobe reactor. The fungal pretreatment considerably increased the volatile product yields (predominantly oxygenated compounds) in non-CFP, indicating that fungal pretreatment enhances the corn stover conversion in fast pyrolysis. In the presence of ZSM-5 zeolite, these oxygenated volatiles were further catalytically converted to aromatic hydrocarbons, whose yield increased from 10.03 wt.% for the untreated corn stover to 11.49 wt.% for the pretreated sample. In contrast, the coke yield decreased from 14.29 to 11.93 wt.% in CFP following the fungal pretreatment. These results indicate that fungal pretreatment can enhance the production of valuable aromatics and decrease the amount of undesired coke, and thus has a beneficial effect on biomass conversion in CFP. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. Life cycle analysis of fuel production from fast pyrolysis of biomass.

    PubMed

    Han, Jeongwoo; Elgowainy, Amgad; Dunn, Jennifer B; Wang, Michael Q

    2013-04-01

    A well-to-wheels (WTW) analysis of pyrolysis-based gasoline was conducted and compared with petroleum gasoline. To address the variation and uncertainty in the pyrolysis pathways, probability distributions for key parameters were developed with data from literature. The impacts of two different hydrogen sources for pyrolysis oil upgrading and of two bio-char co-product applications were investigated. Reforming fuel gas/natural gas for H2 reduces WTW GHG emissions by 60% (range of 55-64%) compared to the mean of petroleum fuels. Reforming pyrolysis oil for H2 increases the WTW GHG emissions reduction up to 112% (range of 97-126%), but reduces petroleum savings per unit of biomass used due to the dramatic decline in the liquid fuel yield. Thus, the hydrogen source causes a trade-off between GHG reduction per unit fuel output and petroleum displacement per unit biomass used. Soil application of biochar could provide significant carbon sequestration with large uncertainty. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Catalytic biomass pyrolysis process

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dayton, David C.; Gupta, Raghubir P.; Turk, Brian S.

    Described herein are processes for converting a biomass starting material (such as lignocellulosic materials) into a low oxygen containing, stable liquid intermediate that can be refined to make liquid hydrocarbon fuels. More specifically, the process can be a catalytic biomass pyrolysis process wherein an oxygen removing catalyst is employed in the reactor while the biomass is subjected to pyrolysis conditions. The stream exiting the pyrolysis reactor comprises bio-oil having a low oxygen content, and such stream may be subjected to further steps, such as separation and/or condensation to isolate the bio-oil.

  19. Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading

    DOE PAGES

    Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.; ...

    2017-11-24

    Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less

  20. Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.

    Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less

  1. Pyrolysis characteristics of typical biomass thermoplastic composites

    NASA Astrophysics Data System (ADS)

    Cai, Hongzhen; Ba, Ziyu; Yang, Keyan; Zhang, Qingfa; Zhao, Kunpeng; Gu, Shiyan

    The biomass thermoplastic composites were prepared by extrusion molding method with poplar flour, rice husk, cotton stalk and corn stalk. The thermo gravimetric analyzer (TGA) has also been used for evaluating the pyrolysis process of the composites. The results showed that the pyrolysis process mainly consists of two stages: biomass pyrolysis and the plastic pyrolysis. The increase of biomass content in the composite raised the first stage pyrolysis peak temperature. However, the carbon residue was reduced and the pyrolysis efficiency was better because of synergistic effect of biomass and plastic. The composite with different kinds of biomass have similar pyrolysis process, and the pyrolysis efficiency of the composite with corn stalk was best. The calcium carbonate could inhibit pyrolysis process and increase the first stage pyrolysis peak temperature and carbon residue as a filling material of the composite.

  2. Resole resin products derived from fractionated organic and aqueous condensates made by fast-pyrolysis of biomass materials

    DOEpatents

    Chum, Helena L.; Black, Stuart K.; Diebold, James P.; Kreibich, Roland E.

    1993-01-01

    A process for preparing phenol-formaldehyde resole resins by fractionating organic and aqueous condensates made by fast-pyrolysis of biomass materials while using a carrier gas to move feed into a reactor to produce phenolic-containing/neutrals in which portions of the phenol normally contained in said resins are replaced by a phenolic/neutral fractions extract obtained by fractionation.

  3. Resole resin products derived from fractionated organic and aqueous condensates made by fast-pyrolysis of biomass materials

    DOEpatents

    Chum, H.L.; Black, S.K.; Diebold, J.P.; Kreibich, R.E.

    1993-08-10

    A process for preparing phenol-formaldehyde resole resins by fractionating organic and aqueous condensates made by fast-pyrolysis of biomass materials while using a carrier gas to move feed into a reactor to produce phenolic-containing/neutrals in which portions of the phenol normally contained in said resins are replaced by a phenolic/neutral fractions extract obtained by fractionation.

  4. From biomass to advanced bio-fuel by catalytic pyrolysis/hydro-processing: hydrodeoxygenation of bio-oil derived from biomass catalytic pyrolysis.

    PubMed

    Wang, Yuxin; He, Tao; Liu, Kaituo; Wu, Jinhu; Fang, Yunming

    2012-03-01

    Compared hydrodeoxygenation experimental studies of both model compounds and real bio-oil derived from biomass fast pyrolysis and catalytic pyrolysis was carried out over two different supported Pt catalysts. For the model compounds, the deoxygenation degree of dibenzofuran was higher than that of cresol and guaiacol over both Pt/Al(2)O(3) and the newly developed Pt supported on mesoporous zeolite (Pt/MZ-5) catalyst, and the deoxygenation degree of cresol over Pt/MZ-5 was higher than that over Pt/Al(2)O(3). The results indicated that hydrodeoxygenation become much easier upon oxygen reduction. Similar to model compounds study, the hydrodeoxygenation of the real bio-oil derived from catalytic pyrolysis was much easier than that from fast pyrolysis over both Pt catalysts, and the Pt/MZ-5 again shows much higher deoxygenation ability than Pt/Al(2)O(3). Clearly synergy between catalytic pyrolysis and bio-oil hydro-processing was found in this paper and this finding will lead an advanced biofuel production pathway in the future. Copyright © 2012 Elsevier Ltd. All rights reserved.

  5. Low-order modeling of internal heat transfer in biomass particle pyrolysis

    DOE PAGES

    Wiggins, Gavin M.; Daw, C. Stuart; Ciesielski, Peter N.

    2016-05-11

    We present a computationally efficient, one-dimensional simulation methodology for biomass particle heating under conditions typical of fast pyrolysis. Our methodology is based on identifying the rate limiting geometric and structural factors for conductive heat transport in biomass particle models with realistic morphology to develop low-order approximations that behave appropriately. Comparisons of transient temperature trends predicted by our one-dimensional method with three-dimensional simulations of woody biomass particles reveal good agreement, if the appropriate equivalent spherical diameter and bulk thermal properties are used. Here, we conclude that, for particle sizes and heating regimes typical of fast pyrolysis, it is possible to simulatemore » biomass particle heating with reasonable accuracy and minimal computational overhead, even when variable size, aspherical shape, anisotropic conductivity, and complex, species-specific internal pore geometry are incorporated.« less

  6. Expanding the biomass resource: sustainable oil production via fast pyrolysis of low input high diversity biomass and the potential integration of thermochemical and biological conversion routes.

    PubMed

    Corton, J; Donnison, I S; Patel, M; Bühle, L; Hodgson, E; Wachendorf, M; Bridgwater, A; Allison, G; Fraser, M D

    2016-09-01

    Waste biomass is generated during the conservation management of semi-natural habitats, and represents an unused resource and potential bioenergy feedstock that does not compete with food production. Thermogravimetric analysis was used to characterise a representative range of biomass generated during conservation management in Wales. Of the biomass types assessed, those dominated by rush ( Juncus effuses ) and bracken ( Pteridium aquilinum ) exhibited the highest and lowest volatile compositions respectively and were selected for bench scale conversion via fast pyrolysis. Each biomass type was ensiled and a sub-sample of silage was washed and pressed. Demineralization of conservation biomass through washing and pressing was associated with higher oil yields following fast pyrolysis. The oil yields were within the published range established for the dedicated energy crops miscanthus and willow. In order to examine the potential a multiple output energy system was developed with gross power production estimates following valorisation of the press fluid, char and oil. If used in multi fuel industrial burners the char and oil alone would displace 3.9 × 10 5  tonnes per year of No. 2 light oil using Welsh biomass from conservation management. Bioenergy and product development using these feedstocks could simultaneously support biodiversity management and displace fossil fuels, thereby reducing GHG emissions. Gross power generation predictions show good potential.

  7. Low-Order Modeling of Internal Heat Transfer in Biomass Particle Pyrolysis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wiggins, Gavin M.; Ciesielski, Peter N.; Daw, C. Stuart

    2016-06-16

    We present a computationally efficient, one-dimensional simulation methodology for biomass particle heating under conditions typical of fast pyrolysis. Our methodology is based on identifying the rate limiting geometric and structural factors for conductive heat transport in biomass particle models with realistic morphology to develop low-order approximations that behave appropriately. Comparisons of transient temperature trends predicted by our one-dimensional method with three-dimensional simulations of woody biomass particles reveal good agreement, if the appropriate equivalent spherical diameter and bulk thermal properties are used. We conclude that, for particle sizes and heating regimes typical of fast pyrolysis, it is possible to simulate biomassmore » particle heating with reasonable accuracy and minimal computational overhead, even when variable size, aspherical shape, anisotropic conductivity, and complex, species-specific internal pore geometry are incorporated.« less

  8. Fast pyrolysis of oil palm shell (OPS)

    NASA Astrophysics Data System (ADS)

    Abdullah, Nurhayati; Sulaiman, Fauziah; Aliasak, Zalila

    2015-04-01

    Biomass is an important renewable source of energy. Residues that are obtained from harvesting and agricultural products can be utilised as fuel for energy generation by conducting any thermal energy conversion technology. The conversion of biomass to bio oil is one of the prospective alternative energy resources. Therefore, in this study fast pyrolysis of oil palm shell was conducted. The main objective of this study was to find the optimum condition for high yield bio-oil production. The experiment was conducted using fixed-bed fluidizing pyrolysis system. The biomass sample was pyrolysed at variation temperature of 450°C - 650°C and at variation residence time of 0.9s - 1.35s. The results obtained were further discussed in this paper. The basic characteristic of the biomass sample was also presented here. The experiment shows that the optimum bio-oil yield was obtained at temperature of 500°C at residence time 1.15s.

  9. Fast Pyrolysis of Poplar Using a Captive Sample Reactor: Effects of Inorganic Salts on Primary Pyrolysis Products

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mukarakate, C.; Robichaud, D.; Donohoe, B.

    2012-01-01

    We have constructed a captive sample reactor (CSR) to study fast pyrolysis of biomass. The reactor uses a stainless steel wire mesh to surround biomass materials with an isothermal environment by independent controlling of heating rates and pyrolysis temperatures. The vapors produced during pyrolysis are immediately entrained and transported in He carrier gas to a molecular beam mass spectrometer (MBMS). Formation of secondary products is minimized by rapidly quenching the sample support with liquid nitrogen. A range of alkali and alkaline earth metal (AAEM) and transition metal salts were tested to study their effect on composition of primary pyrolysis products.more » Multivariate curve resolution (MCR) analysis of the MBMS data shows that transition metal salts enhance pyrolysis of carbohydrates and AAEM salts enhances pyrolysis of lignin. This was supported by performing similar separate studies on cellulose, hemicellulose and extracted lignin. The effect of salts on char formation is also discussed.« less

  10. Physicochemical and adsorptive properties of fast-pyrolysis bio-chars and their steam activated counterparts

    USDA-ARS?s Scientific Manuscript database

    Fast pyrolysis is rapid heating in the absence of oxygen resulting in decomposition of organic material. When applied to biomass, it produces bio-oil, bio-char and gas. The Agricultural Research Service (ARS) of the USDA has studied fluidized-bed fast pyrolysis of several bimoass including perenni...

  11. Methods for deoxygenating biomass-derived pyrolysis oil

    DOEpatents

    Baird, Lance Awender; Brandvold, Timothy A.

    2015-06-30

    Methods for deoxygenating a biomass-derived pyrolysis oil are provided. A method for deoxygenating a biomass-derived pyrolysis oil comprising the steps of combining a biomass-derived pyrolysis oil stream with a heated low-oxygen-pyoil diluent recycle stream to form a heated diluted pyoil feed stream is provided. The heated diluted pyoil feed stream has a feed temperature of about 150.degree. C. or greater. The heated diluted pyoil feed stream is contacted with a first deoxygenating catalyst in the presence of hydrogen at first hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent.

  12. Integrated biomass pyrolysis with organic Rankine cycle for power generation

    NASA Astrophysics Data System (ADS)

    Nur, T. B.; Syahputra, A. W.

    2018-02-01

    The growing interest on Organic Rankine Cycle (ORC) application to produce electricity by utilizing biomass energy sources are increasingly due to its successfully used to generate power from waste heat available in industrial processes. Biomass pyrolysis is one of the thermochemical technologies for converting biomass into energy and chemical products consisting of liquid bio-oil, solid biochar, and pyrolytic gas. In the application, biomass pyrolysis can be divided into three main categories; slow, fast and flash pyrolysis mainly aiming at maximizing the products of bio-oil or biochar. The temperature of synthesis gas generated during processes can be used for Organic Rankine Cycle to generate power. The heat from synthesis gas during pyrolysis processes was transfer by thermal oil heater to evaporate ORC working fluid in the evaporator unit. In this study, the potential of the palm oil empty fruit bunch, palm oil shell, and tree bark have been used as fuel from biomass to generate electricity by integrated with ORC. The Syltherm-XLT thermal oil was used as the heat carrier from combustion burner, while R245fa was used as the working fluid for ORC system. Through Aspen Plus, this study analyses the influences on performance of main thermodynamic parameters, showing the possibilities of reaching an optimum performance for different working conditions that are characteristics of different design parameters.

  13. Catalytic and non-catalytic pyrolysis of biomass in non-inert environments for production of deoxygenated bio-oil and chemicals

    USDA-ARS?s Scientific Manuscript database

    Fast pyrolysis processes are among the most effective methods for liquefaction of lignocellulosic biomass. Catalytic fast pyrolysis (CFP) over HZSM-5 or other zeolites and/or utilization of reactive atmospheres such as in the non-catalytic Tail Gas Reactive Pyrolysis (TRGP) process, a recent patent...

  14. Catalytic fast co-pyrolysis of biomass and food waste to produce aromatics: Analytical Py-GC/MS study.

    PubMed

    Zhang, Bo; Zhong, Zhaoping; Min, Min; Ding, Kuan; Xie, Qinglong; Ruan, Roger

    2015-01-01

    In this study, catalytic fast co-pyrolysis (co-CFP) of corn stalk and food waste (FW) was carried out to produce aromatics using quantitative pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and ZSM-5 zeolite in the hydrogen form was employed as the catalyst. Co-CFP temperature and a parameter called hydrogen to carbon effective ratio (H/C(eff) ratio) were examined for their effects on the relative content of aromatics. Experimental results showed that co-CFP temperature of 600 °C was optimal for the formation of aromatics and other organic pyrolysis products. Besides, H/C(eff) ratio had an important influence on product distribution. The yield of total organic pyrolysis products and relative content of aromatics increased non-linearly with increasing H/C(eff) ratio. There was an apparent synergistic effect between corn stalk and FW during co-CFP process, which promoted the production of aromatics significantly. Co-CFP of biomass and FW was an effective method to produce aromatics and other petrochemicals. Copyright © 2015. Published by Elsevier Ltd.

  15. Methods for deoxygenating biomass-derived pyrolysis oil

    DOEpatents

    Brandvold, Timothy A.

    2015-07-14

    Methods for deoxygenating a biomass-derived pyrolysis oil are provided. A method comprising the steps of diluting the biomass-derived pyrolysis oil with a phenolic-containing diluent to form a diluted pyoil-phenolic feed is provided. The diluted pyoil-phenolic feed is contacted with a deoxygenating catalyst in the presence of hydrogen at hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent.

  16. The integration of dilute acid hydrolysis of xylan and fast pyrolysis of glucan to obtain fermentable sugars.

    PubMed

    Jiang, Liqun; Wu, Nannan; Zheng, Anqing; Zhao, Zengli; He, Fang; Li, Haibin

    2016-01-01

    Fermentable sugars are important intermediates in the biological conversion of biomass. Hemicellulose and amorphous cellulose are easily hydrolyzed to fermentable sugars in dilute acid, whereas crystalline cellulose is more difficult to be hydrolyzed. Cellulose fast pyrolysis is an alternative method to liberate valuable fermentable sugars from biomass. The amount of levoglucosan generated from lignocellulose by fast pyrolysis is usually lower than the theoretical yield based on the cellulose fraction. Pretreatment is a promising route to improve the yield of levoglucosan from lignocellulose. The integration of dilute sulfuric acid hydrolysis and fast pyrolysis to obtain fermentable sugars was evaluated in this study. Dilute sulfuric acid hydrolysis could remove more than 95.1 and 93.4 % of xylan (the main component of hemicellulose) from sugarcane bagasse and corncob with high yield of xylose. On the other hand, dilute sulfuric acid hydrolysis was also an effective pretreatment to enhance levoglucosan yield from lignocellulose. Dilute acid hydrolysis could accumulate glucan (the component of cellulose) and remove most of the alkali and alkaline earth metals which were powerful catalysts during fast pyrolysis. Further increase in dilute acid concentration (from 0 to 2 %) in pretreatment could promote the yield of levoglucosan in fast pyrolysis. The acid pretreated sugarcane bagasse and corncob gave levoglucosan yields of 43.8 and 35.2 % which were obvious higher than those of raw sugarcane bagasse (12.0 %) and corncob (7.0 %). Obtaining fermentable sugars by combination dilute acid hydrolysis of xylan and fast pyrolysis of glucan could make full utilization of biomass, and get fermentable sugars economically from biomass for bio-refinery.

  17. Fast Pyrolysis of Tropical Biomass Species and Influence of Water Pretreatment on Product Distributions

    PubMed Central

    Morgan, Trevor James; Turn, Scott Q.; Sun, Ning; George, Anthe

    2016-01-01

    The fast pyrolysis behaviour of pretreated banagrass was examined at four temperatures (between 400 and 600 C) and four residence times (between ~1.2 and 12 s). The pretreatment used water washing/leaching to reduce the inorganic content of the banagrass. Yields of bio-oil, permanent gases and char were determined at each reaction condition and compared to previously published results from untreated banagrass. Comparing the bio-oil yields from the untreated and pretreated banagrass shows that the yields were greater from the pretreated banagrass by 4 to 11 wt% (absolute) at all reaction conditions. The effect of pretreatment (i.e. reducing the amount of ash, and alkali and alkali earth metals) on pyrolysis products is: 1) to increase the dry bio-oil yield, 2) to decrease the amount of undetected material, 3) to produce a slight increase in CO yield or no change, 4) to slightly decrease CO2 yield or no change, and 5) to produce a more stable bio-oil (less aging). Char yield and total gas yield were unaffected by feedstock pretreatment. Four other tropical biomass species were also pyrolyzed under one condition (450°C and 1.4 s residence time) for comparison to the banagrass results. The samples include two hardwoods: leucaena and eucalyptus, and two grasses: sugarcane bagasse and energy-cane. A sample of pretreated energy-cane was also pyrolyzed. Of the materials tested, the best feedstocks for fast pyrolysis were sugarcane bagasse, pretreated energy cane and eucalyptus based on the yields of 'dry bio-oil', CO and CO2. On the same basis, the least productive feedstocks are untreated banagrass followed by pretreated banagrass and leucaena. PMID:26978265

  18. Fast Pyrolysis of Tropical Biomass Species and Influence of Water Pretreatment on Product Distributions.

    PubMed

    Morgan, Trevor James; Turn, Scott Q; Sun, Ning; George, Anthe

    2016-01-01

    The fast pyrolysis behaviour of pretreated banagrass was examined at four temperatures (between 400 and 600 C) and four residence times (between ~1.2 and 12 s). The pretreatment used water washing/leaching to reduce the inorganic content of the banagrass. Yields of bio-oil, permanent gases and char were determined at each reaction condition and compared to previously published results from untreated banagrass. Comparing the bio-oil yields from the untreated and pretreated banagrass shows that the yields were greater from the pretreated banagrass by 4 to 11 wt% (absolute) at all reaction conditions. The effect of pretreatment (i.e. reducing the amount of ash, and alkali and alkali earth metals) on pyrolysis products is: 1) to increase the dry bio-oil yield, 2) to decrease the amount of undetected material, 3) to produce a slight increase in CO yield or no change, 4) to slightly decrease CO2 yield or no change, and 5) to produce a more stable bio-oil (less aging). Char yield and total gas yield were unaffected by feedstock pretreatment. Four other tropical biomass species were also pyrolyzed under one condition (450°C and 1.4 s residence time) for comparison to the banagrass results. The samples include two hardwoods: leucaena and eucalyptus, and two grasses: sugarcane bagasse and energy-cane. A sample of pretreated energy-cane was also pyrolyzed. Of the materials tested, the best feedstocks for fast pyrolysis were sugarcane bagasse, pretreated energy cane and eucalyptus based on the yields of 'dry bio-oil', CO and CO2. On the same basis, the least productive feedstocks are untreated banagrass followed by pretreated banagrass and leucaena.

  19. The impacts of biomass properties on pyrolysis yields, economic and environmental performance of the pyrolysis-bioenergy-biochar platform to carbon negative energy.

    PubMed

    Li, Wenqin; Dang, Qi; Brown, Robert C; Laird, David; Wright, Mark M

    2017-10-01

    This study evaluated the impact of biomass properties on the pyrolysis product yields, economic and environmental performance for the pyrolysis-biochar-bioenergy platform. We developed and applied a fast pyrolysis, feedstock-sensitive, regression-based chemical process model to 346 different feedstocks, which were grouped into five types: woody, stalk/cob/ear, grass/plant, organic residue/product and husk/shell/pit. The results show that biomass ash content of 0.3-7.7wt% increases biochar yield from 0.13 to 0.16kg/kg of biomass, and decreases biofuel yields from 87.3 to 40.7 gallons per tonne. Higher O/C ratio (0.88-1.12) in biomass decreases biochar yield and increases biofuel yields within the same ash content level. Higher ash content of biomass increases minimum fuel selling price (MFSP), while higher O/C ratio of biomass decreases MFSP within the same ash content level. The impact of ash and O/C ratio of biomass on GHG emissions are not consistent for all feedstocks. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. A review of the toxicity of biomass pyrolysis liquids formed at low temperatures

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Diebold, J P

    1997-04-01

    The scaleup of biomass fast pyrolysis systems to large pilot and commercial scales will expose an increasingly large number of personnel to potential health hazards, especially during the evaluation of the commercial use of the pyrolysis condensates. Although the concept of fast pyrolysis to optimize liquid products is relatively new, low-temperature pyrolysis processes have been used over the aeons to produce charcoal and liquid by-products, e.g., smoky food flavors, food preservatives, and aerosols containing narcotics, e.g., nicotine. There are a number of studies in the historical literature that concern the hazards of acute and long-term exposure to smoke and tomore » the historical pyrolysis liquids formed at low temperatures. The reported toxicity of smoke, smoke food flavors, and fast pyrolysis oils is reviewed. The data found for these complex mixtures suggest that the toxicity may be less than that of the individual components. It is speculated that there may be chemical reactions that take place that serve to reduce the toxicity during aging. 81 refs.« less

  1. Investigation on the fast co-pyrolysis of sewage sludge with biomass and the combustion reactivity of residual char.

    PubMed

    Deng, Shuanghui; Tan, Houzhang; Wang, Xuebin; Yang, Fuxin; Cao, Ruijie; Wang, Zhao; Ruan, Renhui

    2017-09-01

    Gaining the valuable fuels from sewage sludge is a promising method. In this work, the fast pyrolysis characteristics of sewage sludge (SS), wheat straw (WS) and their mixtures in different proportions were carried out in a drop-tube reactor. The combustion reactivity of the residual char obtained was investigated in a thermogravimetric analyzer (TGA). Results indicate that SS and WS at different pyrolysis temperatures yielded different characteristic gas compositions and product distributions. The co-pyrolysis of SS with WS showed that there existed a synergistic effect in terms of higher gas and bio-oil yields and lower char yield, especially at the WS adding percentage of 80wt%. The addition of WS to SS increased the carbon content in the SS char and improved char porous structures, resulting in an improvement in the combustion reactivity of the SS char. The research results can be used to promote co-utilization of sewage sludge and biomass. Copyright © 2017. Published by Elsevier Ltd.

  2. Co-generated fast pyrolysis biochar mitigates green-house gas emissions and increases carbon sequestration in temperate soils

    USDA-ARS?s Scientific Manuscript database

    Biochar (BC) is a product of thermochemical conversion of biomass via pyrolysis, together with gas (syngas), liquid (bio-oil), and heat. Fast pyrolysis is a promising process for bio-oil generation, which leaves 10-30% of the original biomass as char. When applied to soils, BC may increase soil C s...

  3. Fates of Chemical Elements in Biomass during Its Pyrolysis.

    PubMed

    Liu, Wu-Jun; Li, Wen-Wei; Jiang, Hong; Yu, Han-Qing

    2017-05-10

    Biomass is increasingly perceived as a renewable resource rather than as an organic solid waste today, as it can be converted to various chemicals, biofuels, and solid biochar using modern processes. In the past few years, pyrolysis has attracted growing interest as a promising versatile platform to convert biomass into valuable resources. However, an efficient and selective conversion process is still difficult to be realized due to the complex nature of biomass, which usually makes the products complicated. Furthermore, various contaminants and inorganic elements (e.g., heavy metals, nitrogen, phosphorus, sulfur, and chlorine) embodied in biomass may be transferred into pyrolysis products or released into the environment, arousing environmental pollution concerns. Understanding their behaviors in biomass pyrolysis is essential to optimizing the pyrolysis process for efficient resource recovery and less environmental pollution. However, there is no comprehensive review so far about the fates of chemical elements in biomass during its pyrolysis. Here, we provide a critical review about the fates of main chemical elements (C, H, O, N, P, Cl, S, and metals) in biomass during its pyrolysis. We overview the research advances about the emission, transformation, and distribution of elements in biomass pyrolysis, discuss the present challenges for resource-oriented conversion and pollution abatement, highlight the importance and significance of understanding the fate of elements during pyrolysis, and outlook the future development directions for process control. The review provides useful information for developing sustainable biomass pyrolysis processes with an improved efficiency and selectivity as well as minimized environmental impacts, and encourages more research efforts from the scientific communities of chemistry, the environment, and energy.

  4. Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve

    Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the non-catalytic process separates into a non-polar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon presentmore » in this stream. Our work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical micro-reactor coupled to a molecular beam mass spectrometer (MBMS). Furthermore, the MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction to fuels comprising small olefins and aromatic hydrocarbons. During processing the aqueous bio-oil fraction the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt% of the carbon in the feed stream is recovered as hydrocarbons.« less

  5. Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels

    DOE PAGES

    Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve; ...

    2017-01-07

    Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the non-catalytic process separates into a non-polar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon presentmore » in this stream. Our work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical micro-reactor coupled to a molecular beam mass spectrometer (MBMS). Furthermore, the MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction to fuels comprising small olefins and aromatic hydrocarbons. During processing the aqueous bio-oil fraction the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt% of the carbon in the feed stream is recovered as hydrocarbons.« less

  6. Modeling the impact of bubbling bed hydrodynamics on tar yield and its fluctuations during biomass fast pyrolysis

    DOE PAGES

    Xiong, Qingang; Ramirez, Emilio; Pannala, Sreekanth; ...

    2015-10-09

    The impact of bubbling bed hydrodynamics on temporal variations in the exit tar yield for biomass fast pyrolysis was investigated using computational simulations of an experimental laboratory-scale reactor. A multi-fluid computational fluid dynamics model was employed to simulate the differential conservation equations in the reactor, and this was combined with a multi-component, multi-step pyrolysis kinetics scheme for biomass to account for chemical reactions. The predicted mean tar yields at the reactor exit appear to match corresponding experimental observations. Parametric studies predicted that increasing the fluidization velocity should improve the mean tar yield but increase its temporal variations. Increases in themore » mean tar yield coincide with reducing the diameter of sand particles or increasing the initial sand bed height. However, trends in tar yield variability are more complex than the trends in mean yield. The standard deviation in tar yield reaches a maximum with changes in sand particle size. As a result, the standard deviation in tar yield increases with the increases in initial bed height in freely bubbling state, while reaches a maximum in slugging state.« less

  7. Fast pyrolysis of tropical biomass species and influence of water pretreatment on product distributions

    DOE PAGES

    Morgan, Trevor James; Turn, Scott Q.; Sun, Ning; ...

    2016-03-15

    Here, the fast pyrolysis behaviour of pretreated banagrass was examined at four temperatures (between 400 and 600 C) and four residence times (between ~1.2 and 12 s). The pretreatment used water washing/leaching to reduce the inorganic content of the banagrass. Yields of bio-oil, permanent gases and char were determined at each reaction condition and compared to previously published results from untreated banagrass. Comparing the bio-oil yields from the untreated and pretreated banagrass shows that the yields were greater from the pretreated banagrass by 4 to 11 wt% (absolute) at all reaction conditions. The effect of pretreatment (i.e. reducing the amountmore » of ash, and alkali and alkali earth metals) on pyrolysis products is: 1) to increase the dry bio-oil yield, 2) to decrease the amount of undetected material, 3) to produce a slight increase in CO yield or no change, 4) to slightly decrease CO 2 yield or no change, and 5) to produce a more stable bio-oil (less aging). Char yield and total gas yield were unaffected by feedstock pretreatment. Four other tropical biomass species were also pyrolyzed under one condition (450°C and 1.4 s residence time) for comparison to the banagrass results. The samples include two hardwoods: leucaena and eucalyptus, and two grasses: sugarcane bagasse and energy-cane. A sample of pretreated energy-cane was also pyrolyzed. Of the materials tested, the best feedstocks for fast pyrolysis were sugarcane bagasse, pretreated energy cane and eucalyptus based on the yields of 'dry bio-oil', CO and CO 2. On the same basis, the least productive feedstocks are untreated banagrass followed by pretreated banagrass and leucaena.« less

  8. Fast pyrolysis of tropical biomass species and influence of water pretreatment on product distributions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Morgan, Trevor James; Turn, Scott Q.; Sun, Ning

    Here, the fast pyrolysis behaviour of pretreated banagrass was examined at four temperatures (between 400 and 600 C) and four residence times (between ~1.2 and 12 s). The pretreatment used water washing/leaching to reduce the inorganic content of the banagrass. Yields of bio-oil, permanent gases and char were determined at each reaction condition and compared to previously published results from untreated banagrass. Comparing the bio-oil yields from the untreated and pretreated banagrass shows that the yields were greater from the pretreated banagrass by 4 to 11 wt% (absolute) at all reaction conditions. The effect of pretreatment (i.e. reducing the amountmore » of ash, and alkali and alkali earth metals) on pyrolysis products is: 1) to increase the dry bio-oil yield, 2) to decrease the amount of undetected material, 3) to produce a slight increase in CO yield or no change, 4) to slightly decrease CO 2 yield or no change, and 5) to produce a more stable bio-oil (less aging). Char yield and total gas yield were unaffected by feedstock pretreatment. Four other tropical biomass species were also pyrolyzed under one condition (450°C and 1.4 s residence time) for comparison to the banagrass results. The samples include two hardwoods: leucaena and eucalyptus, and two grasses: sugarcane bagasse and energy-cane. A sample of pretreated energy-cane was also pyrolyzed. Of the materials tested, the best feedstocks for fast pyrolysis were sugarcane bagasse, pretreated energy cane and eucalyptus based on the yields of 'dry bio-oil', CO and CO 2. On the same basis, the least productive feedstocks are untreated banagrass followed by pretreated banagrass and leucaena.« less

  9. Coupling DAEM and CFD for simulating biomass fast pyrolysis in fluidized beds

    DOE PAGES

    Xiong, Qingang; Zhang, Jingchao; Wiggins, Gavin; ...

    2015-12-03

    We report results from computational simulations of an experimental, lab-scale bubbling bed biomass pyrolysis reactor that include a distributed activation energy model (DAEM) for the kinetics. In this study, we utilized multiphase computational fluid dynamics (CFD) to account for the turbulent hydrodynamics, and this was combined with the DAEM kinetics in a multi-component, multi-step reaction network. Our results indicate that it is possible to numerically integrate the coupled CFD–DAEM system without significantly increasing computational overhead. It is also clear, however, that reactor operating conditions, reaction kinetics, and multiphase flow dynamics all have major impacts on the pyrolysis products exiting themore » reactor. We find that, with the same pre-exponential factors and mean activation energies, inclusion of distributed activation energies in the kinetics can shift the predicted average value of the exit vapor-phase tar flux and its statistical distribution, compared to single-valued activation-energy kinetics. Perhaps the most interesting observed trend is that increasing the diversity of the DAEM activation energies appears to increase the mean tar yield, all else being equal. As a result, these findings imply that accurate resolution of the reaction activation energy distributions will be important for optimizing biomass pyrolysis processes.« less

  10. Integrated supply chain design for commodity chemicals production via woody biomass fast pyrolysis and upgrading.

    PubMed

    Zhang, Yanan; Hu, Guiping; Brown, Robert C

    2014-04-01

    This study investigates the optimal supply chain design for commodity chemicals (BTX, etc.) production via woody biomass fast pyrolysis and hydroprocessing pathway. The locations and capacities of distributed preprocessing hubs and integrated biorefinery facilities are optimized with a mixed integer linear programming model. In this integrated supply chain system, decisions on the biomass chipping methods (roadside chipping vs. facility chipping) are also explored. The economic objective of the supply chain model is to maximize the profit for a 20-year chemicals production system. In addition to the economic objective, the model also incorporates an environmental objective of minimizing life cycle greenhouse gas emissions, analyzing the trade-off between the economic and environmental considerations. The capital cost, operating cost, and revenues for the biorefinery facilities are based on techno-economic analysis, and the proposed approach is illustrated through a case study of Minnesota, with Minneapolis-St. Paul serving as the chemicals distribution hub. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Bio-oil production from palm fronds by fast pyrolysis process in fluidized bed reactor

    NASA Astrophysics Data System (ADS)

    Rinaldi, Nino; Simanungkalit, Sabar P.; Kiky Corneliasari, S.

    2017-01-01

    Fast pyrolysis process of palm fronds has been conducted in the fluidized bed reactor to yield bio-oil product (pyrolysis oil). The process employed sea sand as the heat transfer medium. The objective of this study is to design of the fluidized bed rector, to conduct fast pyrolysis process to product bio-oil from palm fronds, and to characterize the feed and bio-oil product. The fast pyrolysis process was conducted continuously with the feeding rate around 500 g/hr. It was found that the biomass conversion is about 35.5% to yield bio-oil, however this conversion is still minor. It is suggested due to the heating system inside the reactor was not enough to decompose the palm fronds as a feedstock. Moreover, the acids compounds ware mostly observed on the bio-oil product.

  12. Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass

    DOE PAGES

    Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar; ...

    2016-07-12

    The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO 3/TiO 2 and MoO 3/ZrO 2 at 500 °C and H 2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO 3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO 3 mass ratio exposed to the catalytic bed. For biomass to MoO 3 mass ratios <1.5, predominantly olefinic and aromatic hydrocarbons are produced with no detectable oxygen-containing species. For ratios ≥ 1.5, partially deoxygenated species comprised of furans andmore » phenols are observed, with a concomitant decrease of olefinic and aromatic hydrocarbons. For ratios ≥ 5, primary pyrolysis vapours break through the bed, indicating the onset of catalyst deactivation. Product quantification with a tandem micropyrolyzer-GCMS setup shows that fresh supported MoO 3 catalysts convert ca. 27 mol% of the original carbon into hydrocarbons comprised predominantly of aromatics (7 C%), olefins (18 C%) and paraffins (2 C%), comparable to the total hydrocarbon yield obtained with HZSM-5 operated under similar reaction conditions. In conclusion, post-reaction XPS analysis on supported MoO 3/ZrO 2 and MoO 3/TiO 2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo 5+ and Mo 3+), and that catalyst deactivation is likely associated to coking.« less

  13. Electrocatalytic upgrading of biomass pyrolysis oils to chemical and fuel

    NASA Astrophysics Data System (ADS)

    Lam, Chun Ho

    The present project's aim is to liquefy biomass through fast pyrolysis and then upgrade the resulting "bio-oil" to renewable fuels and chemicals by intensifying its energy content using electricity. This choice reflects three points: (a) Liquid hydrocarbons are and will long be the most practical fuels and chemical feedstocks because of their energy density (both mass and volume basis), their stability and relative ease of handling, and the well-established infrastructure for their processing, distribution and use; (b) In the U.S., the total carbon content of annually harvestable, non-food biomass is significantly less than that in a year's petroleum usage, so retention of plant-captured carbon is a priority; and (c) Modern technologies for conversion of sunlight into usable energy forms---specifically, electrical power---are already an order of magnitude more efficient than plants are at storing solar energy in chemical form. Biomass fast pyrolysis (BFP) generates flammable gases, char, and "bio-oil", a viscous, corrosive, and highly oxygenated liquid consisting of large amounts of acetic acid and water together with hundreds of other organic compounds. With essentially the same energy density as biomass and a tendency to polymerize, this material cannot practically be stored or transported long distances. It must be upgraded by dehydration, deoxygenation, and hydrogenation to make it both chemically and energetically compatible with modern vehicles and fuels. Thus, this project seeks to develop low cost, general, scalable, robust electrocatalytic methods for reduction of bio-oil into fuels and chemicals.

  14. Surface-Enhanced Separation of Water from Hydrocarbons: Potential Dewatering Membranes for the Catalytic Fast Pyrolysis of Pine Biomass

    DOE PAGES

    Engtrakul, Dr. Chaiwat; Hu, Michael Z.; Bischoff, Brian L; ...

    2016-01-01

    The impact of surface-selective coatings on water permeation through a membrane when exposed to catalytic fast pyrolysis (CFP) vapor products was studied by tailoring the surface properties of the membrane coating from superhydrophilic to superhydrophobic. Our approach utilized high-performance architectured surface-selective (HiPAS) membranes that were inserted after a CFP reactor. At this insertion point, the inner wall surface of a tubular membrane was exposed to a mixture of water and upgraded product vapors, including light gases and deoxygenated hydrocarbons. Under proper membrane operating conditions, a high selectivity for water over 1-ring upgraded biomass pyrolysis hydrocarbons was observed due to amore » surface-enhanced capillary condensation process. Owing to this surface-enhanced effect, HiPAS membranes have the potential to enable high flux separations suggesting that water can be selectively removed from the CFP product vapors.« less

  15. Surface-Enhanced Separation of Water from Hydrocarbons: Potential Dewatering Membranes for the Catalytic Fast Pyrolysis of Pine Biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Engtrakul, Chaiwat; Hu, Michael Z.; Bischoff, Brian L.

    2016-10-20

    The impact of surface-selective coatings on water permeation through a membrane when exposed to catalytic fast pyrolysis (CFP) vapor products was studied by tailoring the surface properties of the membrane coating from superhydrophilic to superhydrophobic. Our approach used high-performance architectured surface-selective (HiPAS) membranes that were inserted after a CFP reactor. At this insertion point, the inner wall surface of a tubular membrane was exposed to a mixture of water and upgraded product vapors, including light gases and deoxygenated hydrocarbons. Under proper membrane operating conditions, a high selectivity for water over one-ring upgraded biomass pyrolysis hydrocarbons was observed as a resultmore » of a surface-enhanced capillary condensation process. Owing to this surface-enhanced effect, HiPAS membranes have the potential to enable high flux separations, suggesting that water can be selectively removed from the CFP product vapors.« less

  16. [Bio-oil production from biomass pyrolysis in molten salt].

    PubMed

    Ji, Dengxiang; Cai, Tengyue; Ai, Ning; Yu, Fengwen; Jiang, Hongtao; Ji, Jianbing

    2011-03-01

    In order to investigate the effects of pyrolysis conditions on bio-oil production from biomass in molten salt, experiments of biomass pyrolysis were carried out in a self-designed reactor in which the molten salt ZnCl2-KCl (with mole ratio 7/6) was selected as heat carrier, catalyst and dispersion agent. The effects of metal salt added into ZnCl2-KCl and biomass material on biomass pyrolysis were discussed, and the main compositions of bio-oil were determined by GC-MS. Metal salt added into molten salt could affect pyrolysis production yields remarkably. Lanthanon salt could enhance bio-oil yield and decrease water content in bio-oil, when mole fraction of 5.0% LaCl3 was added, bio-oil yield could reach up to 32.0%, and water content of bio-oil could reduce to 61.5%. The bio-oil and char yields were higher when rice straw was pyrolysed, while gas yield was higher when rice husk was used. Metal salts showed great selectivity on compositions of bio-oil. LiCl and FeCl2 promoted biomass to pyrolyse into smaller molecular weight compounds. CrCl3, CaCl2 and LaCl3 could restrain second pyrolysis of bio-oil. The research provided a scientific reference for production of bio-oil from biomass pyrolysis in molten salt.

  17. Role of potassium exchange in catalytic pyrolysis of biomass over ZSM-5: Formation of alkyl phenols and furans

    USDA-ARS?s Scientific Manuscript database

    Catalytic fast pyrolysis of biomass with ZSM-5 type zeolites is a commonly considered in situ upgrading technique for the production of partially deoxygenated bio-oils. The acidity and structure of ZSM-5 catalysts favor the production of aromatic hydrocarbons from oxygenates present in the pyrolysis...

  18. Low oxygen biomass-derived pyrolysis oils and methods for producing the same

    DOEpatents

    Marinangeli, Richard; Brandvold, Timothy A; Kocal, Joseph A

    2013-08-27

    Low oxygen biomass-derived pyrolysis oils and methods for producing them from carbonaceous biomass feedstock are provided. The carbonaceous biomass feedstock is pyrolyzed in the presence of a catalyst comprising base metal-based catalysts, noble metal-based catalysts, treated zeolitic catalysts, or combinations thereof to produce pyrolysis gases. During pyrolysis, the catalyst catalyzes a deoxygenation reaction whereby at least a portion of the oxygenated hydrocarbons in the pyrolysis gases are converted into hydrocarbons. The oxygen is removed as carbon oxides and water. A condensable portion (the vapors) of the pyrolysis gases is condensed to low oxygen biomass-derived pyrolysis oil.

  19. High-resolution mass spectrometric analysis of biomass pyrolysis vapors

    DOE PAGES

    Christensen, Earl; Evans, Robert J.; Carpenter, Daniel

    2017-01-19

    Vapors generated from the pyrolysis of lignocellulosic biomass are made up of a complex mixture of oxygenated compounds. Direct analysis of these vapors provides insight into the mechanisms of depolymerization of cellulose, hemicellulose, and lignin as well as insight into reactions that may occur during condensation of pyrolysis vapors into bio-oil. Studies utilizing pyrolysis molecular beam mass spectrometry have provided valuable information regarding the chemical composition of pyrolysis vapors. Mass spectrometers generally employed with these instruments have low mass resolution of approximately a mass unit. The presence of chemical species with identical unit mass but differing elemental formulas cannot bemore » resolved with these instruments and are therefore detected as a single ion. In this study we analyzed the pyrolysis vapors of several biomass sources using a high-resolution double focusing mass spectrometer. High-resolution analysis of pyrolysis vapors allowed for speciation of several compounds that would be detected as a single ion with unit mass resolution. Lastly, these data not only provide greater detail into the composition of pyrolysis vapors but also highlight differences between vapors generated from multiple biomass feedstocks.« less

  20. Physicochemical properties of bio-oil and biochar produced by fast pyrolysis of stored single-pass corn stover and cobs.

    PubMed

    Shah, Ajay; Darr, Matthew J; Dalluge, Dustin; Medic, Dorde; Webster, Keith; Brown, Robert C

    2012-12-01

    Short harvest window of corn (Zea mays) stover necessitates its storage before utilization; however, there is not enough work towards exploring the fast pyrolysis behavior of stored biomass. This study investigated the yields and the physicochemical properties (proximate and ultimate analyses, higher heating values and acidity) of the fast pyrolysis products obtained from single-pass stover and cobs stored either inside a metal building or anaerobically within plastic wraps. Biomass samples were pyrolyzed in a 183 cm long and 2.1cm inner diameter free-fall fast pyrolysis reactor. Yields of bio-oil, biochar and non-condensable gases from different biomass samples were in the ranges of 45-55, 25-37 and 11-17 wt.%, respectively, with the highest bio-oil yield from the ensiled single-pass stover. Bio-oils generated from ensiled single-pass cobs and ensiled single-pass stover were, respectively, the most and the least acidic with the modified acid numbers of 95.0 and 65.2 mg g(-1), respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

  1. Understanding the stability of pyrolysis tars from biomass in a view point of free radicals.

    PubMed

    He, Wenjing; Liu, Qingya; Shi, Lei; Liu, Zhenyu; Ci, Donghui; Lievens, Caroline; Guo, Xiaofen; Liu, Muxin

    2014-03-01

    Fast pyrolysis of biomass has attracted increasing attention worldwide to produce bio-tars that can be upgraded into liquid fuels and chemicals. However, the bio-tars are usually poor in quality and stability and are difficult to be upgraded. To better understand the nature of the bio-tars, this work reveals radical concentration of tars derived from pyrolysis of two kinds of biomass. The tars were obtained by condensing the pyrolysis volatiles in 3s. It shows that the tars contain large amounts of radicals, at a level of 10(16)spins/g, and are able to generate more radicals at temperatures of 573K or higher, reaching a level of 10(19)spins/g at 673K in less than 30min. The radical generation in the tar samples is attributed to the formation of THF insoluble matters (coke), which also contain radicals. The radical concentrations of the aqueous liquids obtained in pyrolysis are also studied. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Discernment of synergism in pyrolysis of biomass blends using thermogravimetric analysis.

    PubMed

    Mallick, Debarshi; Poddar, Maneesh Kumar; Mahanta, Pinakeswar; Moholkar, Vijayanand S

    2018-08-01

    This study reports pyrolysis kinetics of biomass blends using isoconversional methods, viz. Friedman, FWO and KAS. Blends of three biomasses, viz. saw dust, bamboo dust and rice husk, were used. Extractives and volatiles in biomass and minerals in ash had marked influence on enhancement of reaction kinetics during co-pyrolysis, as indicated by reduction in activation energy and increase in decomposition intensity. Pyrolysis kinetics of saw dust and rice husk accelerated (positive synergy), while that of bamboo dust decelerated after blending (negative synergy). Predominant reaction mechanism of all biomass blends was 3-D diffusion in lower conversion range (α ≤ 0.5), while for α ≥ 0.5 pyrolysis followed random nucleation (or nucleation and growth mechanism). Higher reaction order for pyrolysis of blends of rice husk with saw dust and bamboo dust was attributed to catalytic effect of minerals in ash. Positive ΔH and ΔG was obtained for pyrolysis of all biomass blends. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Extent of pyrolysis impacts on fast pyrolysis biochar properties.

    PubMed

    Brewer, Catherine E; Hu, Yan-Yan; Schmidt-Rohr, Klaus; Loynachan, Thomas E; Laird, David A; Brown, Robert C

    2012-01-01

    A potential concern about the use of fast pyrolysis rather than slow pyrolysis biochars as soil amendments is that they may contain high levels of bioavailable C due to short particle residence times in the reactors, which could reduce the stability of biochar C and cause nutrient immobilization in soils. To investigate this concern, three corn ( L.) stover fast pyrolysis biochars prepared using different reactor conditions were chemically and physically characterized to determine their extent of pyrolysis. These biochars were also incubated in soil to assess their impact on soil CO emissions, nutrient availability, microorganism population growth, and water retention capacity. Elemental analysis and quantitative solid-state C nuclear magnetic resonance spectroscopy showed variation in O functional groups (associated primarily with carbohydrates) and aromatic C, which could be used to define extent of pyrolysis. A 24-wk incubation performed using a sandy soil amended with 0.5 wt% of corn stover biochar showed a small but significant decrease in soil CO emissions and a decrease in the bacteria:fungi ratios with extent of pyrolysis. Relative to the control soil, biochar-amended soils had small increases in CO emissions and extractable nutrients, but similar microorganism populations, extractable NO levels, and water retention capacities. Corn stover amendments, by contrast, significantly increased soil CO emissions and microbial populations, and reduced extractable NO. These results indicate that C in fast pyrolysis biochar is stable in soil environments and will not appreciably contribute to nutrient immobilization. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  4. Processes for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil, and apparatuses for treating biomass-derived pyrolysis oil

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Baird, Lance Awender; Brandvold, Timothy A.

    Processes and apparatuses for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil are provided herein. An exemplary process for washing a spent ion exchange bed employed in purification of biomass-derived pyrolysis oil includes the step of providing a ion-depleted pyrolysis oil stream having an original oxygen content. The ion-depleted pyrolysis oil stream is partially hydrotreated to reduce the oxygen content thereof, thereby producing a partially hydrotreated pyrolysis oil stream having a residual oxygen content that is less than the original oxygen content. At least a portion of the partially hydrotreated pyrolysis oil stream is passed throughmore » the spent ion exchange bed. Water is passed through the spent ion exchange bed after passing at least the portion of the partially hydrotreated pyrolysis oil stream therethrough.« less

  5. Mass spectrometric studies of fast pyrolysis of cellulose

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Degenstein, John; Hurt, Matt; Murria, Priya

    2015-01-01

    A fast pyrolysis probe/linear quadrupole ion trap mass spectrometer combination was used to study the primary fast pyrolysis products (those that first leave the hot pyrolysis surface) of cellulose, cellobiose, cellotriose, cellotetraose, cellopentaose, and cellohexaose, as well as of cellobiosan, cellotriosan, and cellopentosan, at 600°C. Similar products with different branching ratios were found for the oligosaccharides and cellulose, as reported previously. However, identical products (with the exception of two) with similar branching ratios were measured for cellotriosan (and cellopentosan) and cellulose. This result demonstrates that cellotriosan is an excellent small-molecule surrogate for studies of the fast pyrolysis of cellulose andmore » also that most fast pyrolysis products of cellulose do not originate from the reducing end. Based on several observations, the fast pyrolysis of cellulose is suggested to initiate predominantly via two competing processes: the formation of anhydro-oligosaccharides, such as cellobiosan, cellotriosan, and cellopentosan (major route), and the elimination of glycolaldehyde (or isomeric) units from the reducing end of oligosaccharides formed from cellulose during fast pyrolysis.« less

  6. Predicting properties of gas and solid streams by intrinsic kinetics of fast pyrolysis of wood

    DOE PAGES

    Klinger, Jordan; Bar-Ziv, Ezra; Shonnard, David; ...

    2015-12-12

    Pyrolysis has the potential to create a biocrude oil from biomass sources that can be used as fuel or as feedstock for subsequent upgrading to hydrocarbon fuels or other chemicals. The product distribution/composition, however, is linked to the biomass source. This work investigates the products formed from pyrolysis of woody biomass with a previously developed chemical kinetics model. Different woody feedstocks reported in prior literature are placed on a common basis (moisture, ash, fixed carbon free) and normalized by initial elemental composition through ultimate analysis. Observed product distributions over the full devolatilization range are explored, reconstructed by the model, andmore » verified with independent experimental data collected with a microwave-assisted pyrolysis system. These trends include production of permanent gas (CO, CO 2), char, and condensable (oil, water) species. Elementary compositions of these streams are also investigated. As a result, close agreement between literature data, model predictions, and independent experimental data indicate that the proposed model/method is able to predict the ideal distribution from fast pyrolysis given reaction temperature, residence time, and feedstock composition.« less

  7. Characterization of Bio-Oil from Fast Pyrolysis of Palm Frond and Empty Fruit Bunch

    NASA Astrophysics Data System (ADS)

    Solikhah, M. D.; Pratiwi, F. T.; Heryana, Y.; Wimada, A. R.; Karuana, F.; Raksodewanto, AA; Kismanto, A.

    2018-04-01

    As the world’s biggest producer of palm oil, 109 million tons of palm frond and 46 million tons of empty fruit bunch (EFB) were produced annually in Indonesia. These two kinds of palm biomass were still in low-application and could be potentially used as future energy resources such as biofuel. One of the promising methods to convert palm frond and EFB into biofuel, as a dense and easy to transport material, is fast pyrolysis. Before pyrolysis, biomass feedstock was characterized their component and elemental compositions, moisture content and higher heating value (HHV). Fast pyrolysis processes were conducted at a temperature of 350˚C using thermal oil heater as a heat carrier. The gas phase from pyrolysis was condensed and produced a dark color and water soluble liquid called bio-oil. As GC-MS data shows, the bio-oil from both feed stocks was dominated by acetic acid, furans, phenols, aldehydes, and ketones. The HHV was reported 12.19 and 26.49 MJ/kg, while water content was 41.91 and 11.54 wt% for bio-oil from palm frond and EFB, respectively. The high content of lignin in EFB effects to the low content of water, high content of phenolic compound, and high calorific value in the bio-oil from EFB.

  8. Characterization of fast pyrolysis products generated from several western USA woody species

    Treesearch

    Jacqueline M. Jarvis; Deborah S. Page-Dumroese; Nathaniel M. Anderson; Yuri Corilo; Ryan P. Rodgers

    2014-01-01

    Woody biomass has the potential to be utilized at an alternative fuel source through its pyrolytic conversion. Here, fast pyrolysis bio-oils derived from several western USA woody species are characterized by negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to determine molecular-level composition. The...

  9. Methods and apparatuses for deoxygenating biomass-derived pyrolysis oil

    DOEpatents

    Baird, Lance Awender; Brandvold, Timothy A.

    2015-10-20

    Embodiments of methods and apparatuses for deoxygenating a biomass-derived pyrolysis oil are provided. In one example, a method comprises the steps of separating a low-oxygen biomass-derived pyrolysis oil effluent into a low-oxygen-pyoil organic phase stream and an aqueous phase stream. Phenolic compounds are removed from the aqueous phase stream to form a phenolic-rich diluent recycle stream. A biomass-derived pyrolysis oil stream is diluted and heated with the phenolic-rich diluent recycle stream to form a heated diluted pyoil feed stream. The heated diluted pyoil feed stream is contacted with a deoxygenating catalyst in the presence of hydrogen to deoxygenate the heated diluted pyoil feed stream.

  10. Results of the International Energy Agency Round Robin on Fast Pyrolysis Bio-oil Production

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Elliott, Douglas C.; Meier, Dietrich; Oasmaa, Anja

    An international round robin study of the production of fast pyrolysis bio-oil was undertaken. Fifteen institutions in six countries contributed. Three biomass samples were distributed to the laboratories for processing in fast pyrolysis reactors. Samples of the bio-oil produced were transported to a central analytical laboratory for analysis. The round robin was focused on validating the pyrolysis community understanding of production of fast pyrolysis bio-oil by providing a common feedstock for bio-oil preparation. The round robin included: •distribution of 3 feedstock samples from a common source to each participating laboratory; •preparation of fast pyrolysis bio-oil in each laboratory with themore » 3 feedstocks provided; •return of the 3 bio-oil products (minimum 500 ml) with operational description to a central analytical laboratory for bio-oil property determination. The analyses of interest were: density, viscosity, dissolved water, filterable solids, CHN, S, trace element analysis, ash, total acid number, pyrolytic lignin, and accelerated aging of bio-oil. In addition, an effort was made to compare the bio-oil components to the products of analytical pyrolysis through GC/MS analysis. The results showed that clear differences can occur in fast pyrolysis bio-oil properties by applying different reactor technologies or configurations. The comparison to analytical pyrolysis method suggested that Py-GC/MS could serve as a rapid screening method for bio-oil composition when produced in fluid-bed reactors. Furthermore, hot vapor filtration generally resulted in the most favorable bio-oil product, with respect to water, solids, viscosity, and total acid number. These results can be helpful in understanding the variation in bio-oil production methods and their effects on bio-oil product composition.« less

  11. Comparative study on pyrolysis of lignocellulosic and algal biomass using pyrolysis-gas chromatography/mass spectrometry.

    PubMed

    Li, Kai; Zhang, Liqiang; Zhu, Liang; Zhu, Xifeng

    2017-06-01

    The cornstalk and chlorella were selected as the representative of lignocelulosic and algal biomass, and the pyrolysis experiments of them were carried out using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The physicochemical properties of samples and the pyrolytic product distribution were presented. And then the compositional differences between the two kinds of pyrolytic products were studied, the relevant pyrolysis mechanisms were analyzed systematically. Pyrolytic vapor from lignocellulosic biomass contained more phenolic and carbonyl compounds while that from algal biomass contained more long-chain fatty acids, nitrogen-containing compounds and fewer carbonyl compounds. Maillard reaction is conducive to the conversion of carbonyl compounds to nitrogenous heterocyclic compounds with better thermal stability. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Conventional and fast pyrolysis of automobile shredder residues (ASR).

    PubMed

    Zolezzi, Marcello; Nicolella, Cristiano; Ferrara, Sebastiano; Iacobucci, Cesare; Rovatti, Mauro

    2004-01-01

    This work aims at comparing performance and product yields in conventional pyrolysis and fast pyrolysis of automotive shredded residues. In both processes, carbon conversion to gaseous and liquid products was more than 80%. Gas production was maximised in conventional pyrolysis (about 35% by weight of the initial ASR weight), while fast pyrolysis led to an oil yield higher than 55%. Higher heating values (HHV) of both conventional pyrolysis gas and fast pyrolysis oil increased from 8.8 to 25.07 MJ/Nm3 and from 28.8 and 36.27 MJ/kg with increasing pyrolysis temperature. Copyright 2004 Elsevier Ltd.

  13. Development of a supercritical fluid chromatography method with ultraviolet and mass spectrometry detection for the characterization of biomass fast pyrolysis bio oils.

    PubMed

    Crepier, Julien; Le Masle, Agnès; Charon, Nadège; Albrieux, Florian; Heinisch, Sabine

    2017-08-11

    The characterization of complex mixtures is a challenging issue for the development of innovative processes dedicated to biofuels and bio-products production. The huge number of compounds present in biomass fast pyrolysis oils combined with the large diversity of chemical functions represent a bottleneck as regards analytical technique development. For the extensive characterization of complex samples, supercritical fluid chromatography (SFC) can be alternative to usual separation techniques such as gas (GC) or liquid chromatography (LC). In this study, an approach is proposed to define the best conditions for the SFC separation of a fast pyrolysis bio-oil. This approach was based on SFC data obtained directly from the bio-oil itself instead of selecting model compounds as usually done. SFC conditions were optimized by using three specific, easy-to-use and quantitative criteria aiming at maximizing the separation power. Polar stationary phases (ethylpyridine bonded silica) associated to a mix of acetonitrile and water as polarity modifier provided the best results, with more than 120 peaks detected in SFC-UV. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Finding the chemistry in biomass pyrolysis: Millisecond chemical kinetics and visualization

    NASA Astrophysics Data System (ADS)

    Krumm, Christoph

    Biomass pyrolysis is a promising thermochemical method for producing fuels and chemicals from renewable sources. Development of a fundamental understanding of biomass pyrolysis chemistry is difficult due to the multi-scale and multi-phase nature of the process; biomass length scales span 11 orders of magnitude and pyrolysis phenomena include solid, liquid, and gas phase chemistry in addition to heat and mass transfer. These complexities have a significant effect on chemical product distributions and lead to variability between reactor technologies. A major challenge in the study of biomass pyrolysis is the development of kinetic models capable of describing hundreds of millisecond-scale reactions of biomass into lower molecular weight products. In this work, a novel technique for studying biomass pyrolysis provides the first- ever experimental determination of kinetics and rates of formation of the primary products from cellulose pyrolysis, providing insight into the millisecond-scale chemical reaction mechanisms. These findings highlight the importance of heat and mass transport limitations for cellulose pyrolysis chemistry and are used to identify the length scales at which transport limitations become relevant during pyrolysis. Through this technique, a transition is identified, known as the reactive melting point, between low and high temperature depolymerization. The transition between two mechanisms of cellulose decompositions unifies the mechanisms that govern low temperature char formation, intermediate pyrolysis conditions, and high temperature gas formation. The conditions under which biomass undergoes pyrolysis, including modes of heat transfer, have been shown to significantly affect the distribution of biorenewable chemical and fuel products. High-speed photography is used to observe the liftoff of initially crystalline cellulose particles when impinged on a heated surface, known as the Leidenfrost effect for room-temperature liquids. Order

  15. Effect of Catalytic Pyrolysis Conditions Using Pulse Current Heating Method on Pyrolysis Products of Wood Biomass

    PubMed Central

    Honma, Sensho; Hata, Toshimitsu; Watanabe, Takashi

    2014-01-01

    The influence of catalysts on the compositions of char and pyrolysis oil obtained by pyrolysis of wood biomass with pulse current heating was studied. The effects of catalysts on product compositions were analyzed using GC-MS and TEM. The compositions of some aromatic compounds changed noticeably when using a metal oxide species as the catalyst. The coexistence or dissolution of amorphous carbon and iron oxide was observed in char pyrolyzed at 800°C with Fe3O4. Pyrolysis oil compositions changed remarkably when formed in the presence of a catalyst compared to that obtained from the uncatalyzed pyrolysis of wood meal. We observed a tendency toward an increase in the ratio of polyaromatic hydrocarbons in the pyrolysis oil composition after catalytic pyrolysis at 800°C. Pyrolysis of biomass using pulse current heating and an adequate amount of catalyst is expected to yield a higher content of specific polyaromatic compounds. PMID:25614894

  16. Centrifugal partition chromatography a first dimension for biomass fast pyrolysis oil analysis.

    PubMed

    Le Masle, Agnès; Santin, Sandra; Marlot, Léa; Chahen, Ludovic; Charon, Nadège

    2018-10-31

    Biomass fast pyrolysis oils contain molecules having a large variety of chemical functions and a wide range of molecular weights (from several tens to several thousand grams per mole). The good knowledge of their complex composition is essential for optimizing the conversion of bio-oils to biofuels, thereby requiring powerful separation techniques. In this work, we investigate the interest of centrifugal partition chromatography (CPC) as a first dimension for the analysis of a bio-oil. A CPC method is proposed to separate oxygen containing compounds according to their partition coefficients in the solvent system. This approach is a powerful and easy-to-use technique that enables fractionation of a bio-oil at a semi-preparative scale, without any sample loss related to adsorption on the stationary phase. Collected fractions are then injected in liquid chromatography as a second dimension of separation. Contour plot representations of the CPC × LC separation are established to discuss the potential of this approach. These representations can be used as a veritable fingerprint in the comparison of different samples or samples at different steps of a conversion process but also as a powerful tool to identify new compounds and describe the entire composition of the bio-oil. Copyright © 2018 Elsevier B.V. All rights reserved.

  17. Development and application of a continuous fast microwave pyrolysis system for sewage sludge utilization.

    PubMed

    Zhou, Junwen; Liu, Shiyu; Zhou, Nan; Fan, Liangliang; Zhang, Yaning; Peng, Peng; Anderson, Erik; Ding, Kuan; Wang, Yunpu; Liu, Yuhuan; Chen, Paul; Ruan, Roger

    2018-05-01

    A continuous fast microwave-assisted pyrolysis system was designed, fabricated, and tested with sewage sludge. The system is equipped with continuous biomass feeding, mixing of biomass and microwave absorbent, and separated catalyst upgrading. The effect of the sludge pyrolysis temperature (450, 500, 550, and 600 °C) on the products yield, distribution and potentially energy recovery were investigated. The physical, chemical, and energetic properties of the raw sewage sludge and bio-oil, char and gas products obtained were analyzed using elemental analyzer, GC-MS, Micro-GC, SEM and ICP-OES. While the maximum bio-oil yield of 41.39 wt% was obtained at pyrolysis temperature of 550 °C, the optimal pyrolysis temperature for maximum overall energy recovery was 500 °C. The absence of carrier gas in the process may be responsible for the high HHV of gas products. This work could provide technical support for microwave-assisted system scale-up and sewage sludge utilization. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Aspen Plus Model for In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors for the Conversion of Biomass to Hydrocarbon Fuels

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    This is an Aspen Plus process model for in situ and ex situ upgrading of fast pyrolysis vapors for the conversion of biomass to hydrocarbon fuels. It is based on conceptual designs that allow projections of future commercial implementations of the technologies based on a combination of research and existing commercial technologies. The process model was developed from the ground up at NREL. Results from the model are documented in a detailed design report NREL/TP-5100-62455 (available at http://www.nrel.gov/docs/fy15osti/62455.pdf).

  19. Co-pyrolysis characteristic of biomass and bituminous coal.

    PubMed

    Li, Shuaidan; Chen, Xueli; Liu, Aibin; Wang, Li; Yu, Guangsuo

    2015-03-01

    Co-pyrolysis characteristics of biomass and bituminous coal have been studied in this work. The temperature was up to 900°C with the heating rates of 10, 15, 20, 25 and 30°C/min. Rice straw, saw dust, microcrystalline cellulose, lignin and Shenfu bituminous coal were chosen as samples. Six different biomass ratios were used. The individual thermal behavior of each sample was obtained. The experimental weight fractions of the blended samples and the calculated values were compared. The results show that the weight fractions of the blended samples behave differently with calculated ones during the co-pyrolysis process. With the increasing biomass ratio, relative deviations between experimental weight fractions and calculated ones are larger. H/C molar ratio, heat transfer properties of biomass would affect to the interaction between biomass and coal. The maximum degradation rates are slower than the calculated ones. The activation energy distributions also changed by adding some biomass into coal. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. The slow and fast pyrolysis of cherry seed.

    PubMed

    Duman, Gozde; Okutucu, Cagdas; Ucar, Suat; Stahl, Ralph; Yanik, Jale

    2011-01-01

    The slow and fast pyrolysis of cherry seeds (CWS) and cherry seeds shells (CSS) was studied in fixed-bed and fluidized bed reactors at different pyrolysis temperatures. The effects of reactor type and temperature on the yields and composition of products were investigated. In the case of fast pyrolysis, the maximum bio-oil yield was found to be about 44 wt% at pyrolysis temperature of 500 °C for both CWS and CSS, whereas the bio yields were of 21 and 15 wt% obtained at 500 °C from slow pyrolysis of CWS and CSS, respectively. Both temperature and reactor type affected the composition of bio-oils. The results showed that bio-oils obtained from slow pyrolysis of CWS and CSS can be used as a fuel for combustion systems in industry and the bio-oil produced from fast pyrolysis can be evaluated as a chemical feedstock. Copyright © 2010 Elsevier Ltd. All rights reserved.

  1. Cultivation, characterization, and properties of Chlorella vulgaris microalgae with different lipid contents and effect on fast pyrolysis oil composition.

    PubMed

    Adamakis, Ioannis-Dimosthenis; Lazaridis, Polykarpos A; Terzopoulou, Evangelia; Torofias, Stylianos; Valari, Maria; Kalaitzi, Photeini; Rousonikolos, Vasilis; Gkoutzikostas, Dimitris; Zouboulis, Anastasios; Zalidis, Georgios; Triantafyllidis, Konstantinos S

    2018-06-01

    A systematic study of the effect of nitrogen levels in the cultivation medium of Chlorella vulgaris microalgae grown in photobioreactor (PBR) on biomass productivity, biochemical and elemental composition, fatty acid profile, heating value (HHV), and composition of the algae-derived fast pyrolysis (bio-oil) is presented in this work. A relatively high biomass productivity and cell concentration (1.5 g of dry biomass per liter of cultivation medium and 120 × 10 6 cells/ml, respectively) were achieved after 30 h of cultivation under N-rich medium. On the other hand, the highest lipid content (ca. 36 wt.% on dry biomass) was obtained under N-depletion cultivation conditions. The medium and low N levels favored also the increased concentration of the saturated and mono-unsaturated C16:0 and C18:1(n-9) fatty acids (FA) in the lipid/oil fraction, thus providing a raw lipid feedstock that can be more efficiently converted to high-quality biodiesel or green diesel (via hydrotreatment). In terms of overall lipid productivity, taking in consideration both the biomass concentration in the medium and the content of lipids on dry biomass, the most effective system was the N-rich one. The thermal (non-catalytic) pyrolysis of Chlorella vulgaris microalgae produced a highly complex bio-oil composition, including fatty acids, phenolics, ethers, ketones, etc., as well as aromatics, alkanes, and nitrogen compounds (pyrroles and amides), originating from the lipid, protein, and carbohydrate fractions of the microalgae. However, the catalytic fast pyrolysis using a highly acidic ZSM-5 zeolite, afforded a bio-oil enriched in mono-aromatics (BTX), reducing at the same time significantly oxygenated compounds such as phenolics, acids, ethers, and ketones. These effects were even more pronounced in the catalytic fast pyrolysis of Chlorella vulgaris residual biomass (after extraction of lipids), thus showing for the first time the potential of transforming this low value by

  2. An exergy based assessment of the production and conversion of switchgrass, equine waste and forest residue to bio-oil using fast pyrolysis

    USDA-ARS?s Scientific Manuscript database

    The resource efficiency of biofuel production via biomass pyrolysis is evaluated using exergy as an assessment metric. Three feedstocks, important to various sectors of US agriculture, switchgrass, forest residue and equine waste are considered for conversion to bio-oil (pyrolysis oil) via fast pyro...

  3. Understanding the fast pyrolysis of lignin.

    PubMed

    Patwardhan, Pushkaraj R; Brown, Robert C; Shanks, Brent H

    2011-11-18

    In the present study, pyrolysis of corn stover lignin was investigated by using a micro-pyrolyzer coupled with a GC-MS/FID (FID=flame ionization detector). The system has pyrolysis-vapor residence times of 15-20 ms, thus providing a regime of minimal secondary reactions. The primary pyrolysis product distribution obtained from lignin is reported. Over 84 % mass balance and almost complete closure on carbon balance is achieved. In another set of experiments, the pyrolysis vapors emerging from the micro-pyrolyzer are condensed to obtain lignin-derived bio-oil. The chemical composition of the bio-oil is analyzed by using GC-MS and gel permeation chromatography techniques. The comparison between results of two sets of experiments indicates that monomeric compounds are the primary pyrolysis products of lignin, which recombine after primary pyrolysis to produce oligomeric compounds. Further, the effect of minerals (NaCl, KCl, MgCl(2), and CaCl(2)) and temperature on the primary pyrolysis product distribution is investigated. The study provides insights into the fundamental mechanisms of lignin pyrolysis and a basis for developing more descriptive models of biomass pyrolysis. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Product Chemistry and Process Efficiency of Biomass Torrefaction, Pyrolysis and Gasification Studied by High-Throughput Techniques and Multivariate Analysis

    NASA Astrophysics Data System (ADS)

    Xiao, Li

    ), fast growing energy crops (switchgrass), and popular forage crop (alfalfa), as well as biochar derived from those materials and their mixtures. It demonstrated that Py-MBMS coupled with MVA could be used as fast analytical tools for the study of not only biomass composition but also its thermal decomposition behaviors. It found that the impact of biomass composition heavily depends on the thermal decomposition temperature because at different temperature, the composition of biomass decomposed and the impact of minerals on the decomposition reaction varies. At low temperature (200-500°C), organic compounds attribute to the majority of variation in thermal decomposition products. At higher temperature, inorganics dramatically changed the pyrolysis pathway of carbohydrates and possibly lignin. In gasification, gasification tar formation is also observed to be impacted by ash content in vapor and char. In real reactor, biochar structure also has interactions with other fractions to make the final pyrolysis and gasification product. Based on the evaluation of process efficiencies during torrefaction, temperature ranging from 275°C to 300°C with short residence time (<10min) are proposed to be optimal torrefaction conditions. 500°C is preferred to 700°C as primary pyrolysis temperature in two stage gasification because higher primary pyrolysis temperature resulted in more tar and less gasification char. Also, in terms of carbon yield, more carbon is lost in tar while less carbon is retained in gas product using 700°C as primary pyrolysis temperature. In addition, pyrolysis char is found to produce less tar and more gas during steam gasification compared with gasification of pyrolysis vapor. Thus it is suggested that torrefaction might be an efficient pretreatment for biomass gasification because it can largely improve the yield of pyrolysis char during the primary pyrolysis step of gasification thus reduce the total tar of the overall gasification products. Future work

  5. A comparison of fast and reactive pyrolysis with insitu derivatisation of fructose, inulin and Jerusalem artichoke (Helianthus tuberosus).

    PubMed

    Mattonai, Marco; Ribechini, Erika

    2018-08-09

    Reactive pyrolysis is a technique that provides mechanistic information by performing pyrolysis of the substrate in a sealed glass capsule at elevated temperature and pressure for relatively long time. This technique has already shown great potential for the analysis of biomass, favouring the formation of only the most thermostable compounds. In this work, both fast and reactive pyrolysis with on-line gas chromatography-mass spectrometry analysis (Py-GC/MS) are used to study fructose, inulin and Jerusalem artichoke tubers (Heliantus tuberosus). Interesting differences were found between the two systems, and became even more evident as the reaction time was increased. The most striking result was the formation of di-fructose dianhydrides (DFAs), a class of compounds with interesting biological activities. DFAs were obtained in high yields from reactive pyrolysis, but not from fast pyrolysis. Hypotheses on the pyrolysis mechanisms were made based upon the composition of the pyrolysates. This work describes for the first time the behaviour of fructans under reactive pyrolysis. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Mass production of chemicals from biomass-derived oil by directly atmospheric distillation coupled with co-pyrolysis

    NASA Astrophysics Data System (ADS)

    Zhang, Xue-Song; Yang, Guang-Xi; Jiang, Hong; Liu, Wu-Jun; Ding, Hong-Sheng

    2013-01-01

    Production of renewable commodity chemicals from bio-oil derived from fast pyrolysis of biomass has received considerable interests, but hindered by the presence of innumerable components in bio-oil. In present work, we proposed and experimentally demonstrated an innovative approach combining atmospheric distillation of bio-oil with co-pyrolysis for mass production of renewable chemicals from biomass, in which no waste was produced. It was estimated that 51.86 wt.% of distillate just containing dozens of separable organic components could be recovered using this approach. Ten protogenetic and three epigenetic compounds in distillate were qualitatively identified by gas chromatography/mass spectrometry and quantified by gas chromatography. Among them, the recovery efficiencies of acetic acid, propanoic acid, and furfural were all higher than 80 wt.%. Formation pathways of the distillate components in this process were explored. This work opens up a fascinating prospect for mass production of chemical feedstock from waste biomass.

  7. Mass production of chemicals from biomass-derived oil by directly atmospheric distillation coupled with co-pyrolysis

    PubMed Central

    Zhang, Xue-Song; Yang, Guang-Xi; Jiang, Hong; Liu, Wu-Jun; Ding, Hong-Sheng

    2013-01-01

    Production of renewable commodity chemicals from bio-oil derived from fast pyrolysis of biomass has received considerable interests, but hindered by the presence of innumerable components in bio-oil. In present work, we proposed and experimentally demonstrated an innovative approach combining atmospheric distillation of bio-oil with co-pyrolysis for mass production of renewable chemicals from biomass, in which no waste was produced. It was estimated that 51.86 wt.% of distillate just containing dozens of separable organic components could be recovered using this approach. Ten protogenetic and three epigenetic compounds in distillate were qualitatively identified by gas chromatography/mass spectrometry and quantified by gas chromatography. Among them, the recovery efficiencies of acetic acid, propanoic acid, and furfural were all higher than 80 wt.%. Formation pathways of the distillate components in this process were explored. This work opens up a fascinating prospect for mass production of chemical feedstock from waste biomass. PMID:23350028

  8. Diffusion of biomass pyrolysis products in H-ZSM-5 by molecular dynamics simulations

    DOE PAGES

    Bu, Lintao; Nimlos, Mark R.; Robichaud, David J.; ...

    2016-12-13

    Diffusion of biomass pyrolysis vapors and their upgraded products is an essential catalytic property of zeolites during catalytic fast pyrolysis and likely plays a critical role in the selectivity of these catalysts. Characterizing the diffusivities of representative biofuel molecules is critical to understand shape selectivity and interpret product distribution. Yet, experimental measurements on the diffusivities of oxygenated biofuel molecules at pyrolysis temperatures are very limited in the literature. As an alternative approach, we conducted MD simulations to measure the diffusion coefficients of several selected molecules that are representative of biomass pyrolysis vapors, namely water, methanol, glycolaldehyde, and toluene in H-ZSM-5more » zeolite. The results show the diffusion coefficients calculated via MD simulations are consistent with available NMR measurements at room temperature. The effect of molecular weight and molecular critical diameter on the diffusivity among the chosen model compounds is also examined. Furthermore, we have characterized the diffusivities of representative biofuel molecules, namely xylene isomers, in H-ZSM-5. Our calculations determined that the ratio of the diffusion coefficients for xylene isomers is p-xylene: o-xylene: m-xylene ≈ 83:3:1 at 700 K. Furthermore, our results also demonstrate the different diffusivity between p-xylene and toluene is due to the molecular orientations when the molecules diffuse along the channels in H-ZSM-5 and provide deep insight into the effect of molecular orientation on its diffusivity.« less

  9. Deactivation of Multilayered MFI Nanosheet Zeolite during Upgrading of Biomass Pyrolysis Vapors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xu, Mengze; Mukarakate, Calvin; Iisa, Kristiina

    Here, the catalytic fast pyrolysis (CFP) of biomass is a promising technology for producing renewable transportation fuels and chemicals. MFI-type catalysts have shown promise for CFP because they produce gasoline range hydrocarbons from oxygenated pyrolysis compounds; however, rapid catalyst deactivation due to coking is one of the major technical barriers inhibiting the commercialization of this technology. Coke deposited on the surface of the catalysts blocks access to active sites in the micropores leading to rapid catalyst deactivation. Our strategy is to minimize rapid catalyst deactivation by adding mesoporosity through forming MFI nanosheet materials. The synthesized MFI nanosheet catalysts were fullymore » characterized and evaluated for cellulose pyrolysis vapor upgrading to produce olefins and aromatic hydrocarbons. The data obtained from pyrolysis-GCMS (py-GCMS), showed that fresh MFI nanosheets produced similar aromatic hydrocarbon and olefin yields compared to conventional HZSM-5. However, MFI nanosheets demonstrated a longer lifetime than HZSM-5 even though coke contents were also higher than for HZSM-5 because the mesopores enabled better accessibility to active acid sites. This conclusion was supported by results from post-reaction analysis of various spent catalysts collected at different points during the deactivation experiments.« less

  10. Deactivation of Multilayered MFI Nanosheet Zeolite during Upgrading of Biomass Pyrolysis Vapors

    DOE PAGES

    Xu, Mengze; Mukarakate, Calvin; Iisa, Kristiina; ...

    2017-05-02

    Here, the catalytic fast pyrolysis (CFP) of biomass is a promising technology for producing renewable transportation fuels and chemicals. MFI-type catalysts have shown promise for CFP because they produce gasoline range hydrocarbons from oxygenated pyrolysis compounds; however, rapid catalyst deactivation due to coking is one of the major technical barriers inhibiting the commercialization of this technology. Coke deposited on the surface of the catalysts blocks access to active sites in the micropores leading to rapid catalyst deactivation. Our strategy is to minimize rapid catalyst deactivation by adding mesoporosity through forming MFI nanosheet materials. The synthesized MFI nanosheet catalysts were fullymore » characterized and evaluated for cellulose pyrolysis vapor upgrading to produce olefins and aromatic hydrocarbons. The data obtained from pyrolysis-GCMS (py-GCMS), showed that fresh MFI nanosheets produced similar aromatic hydrocarbon and olefin yields compared to conventional HZSM-5. However, MFI nanosheets demonstrated a longer lifetime than HZSM-5 even though coke contents were also higher than for HZSM-5 because the mesopores enabled better accessibility to active acid sites. This conclusion was supported by results from post-reaction analysis of various spent catalysts collected at different points during the deactivation experiments.« less

  11. Petroleomic Analysis of Bio- Oils from the Fast Pyrolysis or Biomass: Laser Desorption Ionization-Linear Ion Trap-Orbitrap mass Spectrometry Approach

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Smith, Erica A.; Lee, Young Jin

    2010-08-23

    Fast pyrolysis of biomass produces bio-oils that can be upgraded into biofuels. Despite similar physical properties to petroleum, the chemical properties of bio-oils are quite different and their chemical compositions, particularly those of non-volatile compounds, are not well-known. Here, we report the first time attempt at analyzing bio-oils using high-resolution mass spectrometry (MS), which employed laser desorption ionization-linear ion trap-Orbitrap MS. Besides a few limitations, we could determine chemical compositions for over 100 molecular compounds in a bio-oil sample produced from the pyrolysis of a loblolly pine tree. These compounds consist of 3-6 oxygens and 9-17 double-bond equivalents (DBEs). Amongmore » those, O{sub 4} compounds with a DBE of 9-13 were most abundant. Unlike petroleum oils, the lack of nearby molecules within a {+-}2 Da mass window for major components enabled clear isolation of precursor ions for subsequent MS/MS structural investigations. Petroleomic analysis and a comparison to low-mass components in hydrolytic lignin suggest that they are dimers and trimers of depolymerized lignin.« less

  12. Biomass fast pyrolysis for bio-oil production in a fluidized bed reactor under hot flue atmosphere.

    PubMed

    Li, Ning; Wang, Xiang; Bai, Xueyuan; Li, Zhihe; Zhang, Ying

    2015-10-01

    Fast pyrolysis experiments of corn stalk were performed to investigate the optimal pyrolysis conditions of temperature and bed material for maximum bio-oil production under flue gas atmosphere. Under the optimized pyrolysis conditions, furfural residue, xylose residue and kelp seaweed were pyrolyzed to examine their yield distributions of products, and the physical characteristics of bio-oil were studied. The best flow rate of the flue gas at selected temperature is obtained, and the pyrolysis temperature at 500 degrees C and dolomite as bed material could give a maximum bio-oil yield. The highest bio-oil yield of 43.3% (W/W) was achieved from corn stalk under the optimal conditions. Two main fractions were recovered from the stratified bio-oils: light oils and heavy oils. The physical properties of heavy oils from all feedstocks varied little. The calorific values of heavy oils were much higher than that of light oils. The pyrolysis gas could be used as a gaseous fuel due to a relatively high calorific value of 6.5-8.5 MJ/m3.

  13. Biomass pyrolysis liquid to citric acid via 2-step bioconversion.

    PubMed

    Yang, Zhiguang; Bai, Zhihui; Sun, Hongyan; Yu, Zhisheng; Li, Xingxing; Guo, Yifei; Zhang, Hongxun

    2014-12-31

    The use of fossil carbon sources for fuels and petrochemicals has serious impacts on our environment and is unable to meet the demand in the future. A promising and sustainable alternative is to substitute fossil carbon sources with microbial cell factories converting lignocellulosic biomass into desirable value added products. However, such bioprocesses require tolerance to inhibitory compounds generated during pretreatment of biomass. In this study, the process of sequential two-step bio-conversion of biomass pyrolysis liquid containing levoglucosan (LG) to citric acid without chemical detoxification has been explored, which can greatly improve the utilization efficiency of lignocellulosic biomass. The sequential two-step bio-conversion of corn stover pyrolysis liquid to citric acid has been established. The first step conversion by Phanerochaete chrysosporium (P. chrysosporium) is desirable to decrease the content of other compounds except levoglucosan as a pretreatment for the second conversion. The remaining levoglucosan in solution was further converted into citric acid by Aspergillus niger (A. niger) CBX-209. Thus the conversion of cellulose to citric acid is completed by both pyrolysis and bio-conversion technology. Under experimental conditions, levoglucosan yield is 12% based on the feedstock and the citric acid yield can reach 82.1% based on the levoglucosan content in the pyrolysis liquid (namely 82.1 g of citric acid per 100 g of levoglucosan). The study shows that P. chrysosporium and A. niger have the potential to be used as production platforms for value-added products from pyrolyzed lignocellulosic biomass. Selected P. chrysosporium is able to decrease the content of other compounds except levoglucosan and levoglucosan can be further converted into citric acid in the residual liquids by A. niger. Thus the conversion of cellulose to citric acid is completed by both pyrolysis and bio-conversion technology.

  14. Influence of crystal allomorph and crystallinity on the products and behavior of cellulose during fast pyrolysis

    DOE PAGES

    Mukarakate, Calvin; Mittal, Ashutosh; Ciesielski, Peter N.; ...

    2016-07-19

    Here, cellulose is the primary biopolymer responsible for maintaining the structural and mechanical integrity of cell walls and, during the fast pyrolysis of biomass, may be restricting cell wall expansion and inhibiting phase transitions that would otherwise facilitate efficient escape of pyrolysis products. Here, we test whether modifications in two physical properties of cellulose, its crystalline allomorph and degree of crystallinity, alter its performance during fast pyrolysis. We show that both crystal allomorph and relative crystallinity of cellulose impact the slate of primary products produced by fast pyrolysis. For both cellulose-I and cellulose-II, changes in crystallinity dramatically impact the fastmore » pyrolysis product portfolio. In both cases, only the most highly crystalline samples produced vapors dominated by levoglucosan. Cellulose-III, on the other hand, produces largely the same slate of products regardless of its relative crystallinity and produced as much or more levoglucosan at all crystallinity levels compared to cellulose-I or II. In addition to changes in products, the different cellulose allomorphs affected the viscoelastic properties of cellulose during rapid heating. Real-time hot-stage pyrolysis was used to visualize the transition of the solid material through a molten phase and particle shrinkage. SEM analysis of the chars revealed additional differences in viscoelastic properties and molten phase behavior impacted by cellulose crystallinity and allomorph. Regardless of relative crystallinity, the cellulose-III samples displayed the most obvious evidence of having transitioned through a molten phase.« less

  15. Feedstock Supply System Design and Economics for Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels Conversion Pathway: Fast Pyrolysis and Hydrotreating Bio-Oil Pathway "The 2017 Design Case"

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kevin L. Kenney; Kara G. Cafferty; Jacob J. Jacobson

    The U.S. Department of Energy promotes the production of liquid fuels from lignocellulosic biomass feedstocks by funding fundamental and applied research that advances the state of technology in biomass sustainable supply, logistics, conversion, and overall system sustainability. As part of its involvement in this program, Idaho National Laboratory (INL) investigates the feedstock logistics economics and sustainability of these fuels. Between 2000 and 2012, INL quantified and the economics and sustainability of moving biomass from the field or stand to the throat of the conversion process using conventional equipment and processes. All previous work to 2012 was designed to improve themore » efficiency and decrease costs under conventional supply systems. The 2012 programmatic target was to demonstrate a biomass logistics cost of $55/dry Ton for woody biomass delivered to fast pyrolysis conversion facility. The goal was achieved by applying field and process demonstration unit-scale data from harvest, collection, storage, preprocessing, handling, and transportation operations into INL’s biomass logistics model.« less

  16. Low-temperature co-pyrolysis behaviours and kinetics of oily sludge: effect of agricultural biomass.

    PubMed

    Zhou, Xiehong; Jia, Hanzhong; Qu, Chengtun; Fan, Daidi; Wang, Chuanyi

    2017-02-01

    Pyrolysis is potentially an effective treatment of oily sludge for oil recovery, and its kinetics and efficiency are expected to be affected by additives. In the present study, the pyrolysis parameters, including heating rate, final pyrolysis temperature, and pyrolysis time of oily sludge in the presence of agricultural biomass, apricot shell, were systematically explored. As a result, maximum oil recovery is achieved when optimizing the pyrolysis conditionas15 K/min, 723 K, and 3 h for heating rate, final pyrolysis temperature, and pyrolysis time, respectively. Thermogravimetric experiments of oily sludge samples in the presence of various biomasses conducted with non-isothermal temperature programmes suggest that the pyrolysis process contains three stages, and the main decomposition reaction occurs in the range of 400-740 K. Taking Flynn-Wall-Ozawa analysis of the derivative thermogravimetry and thermogravimetry results, the activation energy (E a ) values for the pyrolysis of oily sludge in the presence and absence of apricot shell were derived to be 35.21 and 39.40 kJ mol -1 , respectively. The present work supports that the presence of biomass promotes the pyrolysis of oily sludge, implying its great potential as addictive in the industrial pyrolysis of oily sludge.

  17. Liquid–Liquid Equilibrium Measurements for Model Systems Related to Catalytic Fast Pyrolysis of Biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jasperson, Louis V.; McDougal, Rubin J.; Diky, Vladimir

    Here in this paper we report liquid-liquid mutual solubilities for binary aqueous mixtures involving 2-, 3-, and 4-ethylphenol, 2-, 3-, and 4-methoxyphenol, benzofuran, and 1H-indene for the temperature range (300 < T/K < 360). Measurements in the water-rich phase for (2-ethylphenol + water) were extended to T = 440 K to facilitate comparison with literature values. Liquid-liquid equilibrium tie-line determinations were made for four ternary systems involving (water + toluene) mixed with a third component; phenol, 3-ethylphenol, 4-methoxyphenol, or 2,4-dimethylphenol. Literature values at higher temperatures are available for the three (ethylphenol + water) systems, and, in general, good agreement ismore » seen. The ternary system (water + toluene + phenol) has been studied previously with inconsistent results reported in the literature, and one report is shown to be anomalous. All systems are modeled with the predictive methods NIST-Modified-UNIFAC and NIST-COSMO-SAC, with generally good success in the temperature range of interest (300 < T/K < 360). This work is part of a larger project on the testing and development of predictive phase equilibrium models for compound types occurring in catalytic fast pyrolysis of biomass, and background information for the larger project is provided.« less

  18. Liquid–Liquid Equilibrium Measurements for Model Systems Related to Catalytic Fast Pyrolysis of Biomass

    DOE PAGES

    Jasperson, Louis V.; McDougal, Rubin J.; Diky, Vladimir; ...

    2016-11-02

    Here in this paper we report liquid-liquid mutual solubilities for binary aqueous mixtures involving 2-, 3-, and 4-ethylphenol, 2-, 3-, and 4-methoxyphenol, benzofuran, and 1H-indene for the temperature range (300 < T/K < 360). Measurements in the water-rich phase for (2-ethylphenol + water) were extended to T = 440 K to facilitate comparison with literature values. Liquid-liquid equilibrium tie-line determinations were made for four ternary systems involving (water + toluene) mixed with a third component; phenol, 3-ethylphenol, 4-methoxyphenol, or 2,4-dimethylphenol. Literature values at higher temperatures are available for the three (ethylphenol + water) systems, and, in general, good agreement ismore » seen. The ternary system (water + toluene + phenol) has been studied previously with inconsistent results reported in the literature, and one report is shown to be anomalous. All systems are modeled with the predictive methods NIST-Modified-UNIFAC and NIST-COSMO-SAC, with generally good success in the temperature range of interest (300 < T/K < 360). This work is part of a larger project on the testing and development of predictive phase equilibrium models for compound types occurring in catalytic fast pyrolysis of biomass, and background information for the larger project is provided.« less

  19. Kinetic Modelling of the Pyrolysis of Biomass for the Development of Charcoal Briquette

    NASA Astrophysics Data System (ADS)

    Idris, Y. R.; Bayu, H. T.; Wintoko, J.; Murachman, B.; Yuliansyah, A. T.; Purwono, S.

    2017-06-01

    Waste of biomass can be utilized as an energy alternative such as a charcoal briquette. In the waste of biomass, there is carbon element bonded in the cellulose which can be utilized as an energy source of solid fuel. Charcoal briquette from waste of biomass can be developed via pyrolysis process. Terminalia Catappa L. and Myristica fragrans (nutmeg seeds shells) shells were used as raw material for the manufacture of charcoal briquettes. Pyrolysis process took place under isothermal conditions at a temperature of 350°C, 400°C, 450°C, 500°C, and 550°C with variation of times were 30 minutes, 60 minutes and 90 minutes. During the pyrolysis process, there were three main components observed, namely liquid (bio oil), gases and solids (char). Data obtained for measuring the kinetics of liquids and gases were taken in interval of 5 minutes. The results showed that the rise in temperature will increase the rate of pyrolysis process and increase the yield of gases and liquids as well as lowering the yield for solid. The best fitted kinetic model is the representation of biomass pyrolysis process involving secondary decomposition of the liquid. The results of briquette development showed that these two biomasses can be used as raw material of energy alternative.

  20. A Comparative study of microwave-induced pyrolysis of lignocellulosic and algal biomass.

    PubMed

    Wang, Nan; Tahmasebi, Arash; Yu, Jianglong; Xu, Jing; Huang, Feng; Mamaeva, Alisa

    2015-08-01

    Microwave (MW) pyrolysis of algal and lignocellulosic biomass samples were studied using a modified domestic oven. The pyrolysis temperature was recorded continuously by inserting a thermocouple into the samples. Temperatures as high as 1170 and 1015°C were achieved for peanut shell and Chlorella vulgaris. The activation energy for MW pyrolysis was calculated by Coats-Redfern method and the values were 221.96 and 214.27kJ/mol for peanut shell and C. vulgaris, respectively. Bio-oil yields reached to 27.7wt.% and 11.0wt.% during pyrolysis of C. vulgaris and peanut shell, respectively. The bio-oil samples from pyrolysis were analyzed by a gas chromatography-mass spectrometry (GC-MS). Bio-oil from lignocellulosic biomass pyrolysis contained more phenolic compounds while that from microalgae pyrolysis contained more nitrogen-containing species. Fourier transform infrared spectroscopy (FTIR) analysis results showed that concentration of OH, CH, CO, OCH3, and CO functional groups in char samples decreased significantly after pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Lignin depolymerization and upgrading via fast pyrolysis and electrocatalysis for the production of liquid fuels and value-added products

    NASA Astrophysics Data System (ADS)

    Garedew, Mahlet

    The production of liquid hydrocarbon fuels from biomass is needed to replace fossil fuels, which are decreasing in supply at an unsustainable rate. Renewable fuels also address the rising levels of greenhouse gases, an issue for which the Intergovernmental Panel on Climate Change implicated humanity in 2013. In response, the Energy Independence and Security Act (EISA) mandates the production of 21 billion gallons of advanced biofuels by 2022. Biomass fast pyrolysis (BFP) uses heat (400-600 °C) without oxygen to convert biomass to liquids fuel precursors offering an alternative to fossil fuels and a means to meet the EISA mandate. The major product, bio-oil, can be further upgraded to liquid hydrocarbon fuels, while biochar can serve as a solid fuel or soil amendment. The combustible gas co-product is typically burned for process heat. Though the most valuable of the pyrolysis products, the liquid bio-oil is highly oxygenated, corrosive, low in energy content and unstable during storage. As a means of improving bio-oil properties, electrocatalytic hydrogenation (ECH) is employed to reduce and deoxygenate reactive compounds. This work specifically focuses on lignin as a feed material for BFP. As lignin comprises up to 30% of the mass and 40% of the energy stored in biomass, it offers great potential for the production of liquid fuels and value-added products by utilizing fast pyrolysis as a conversion method coupled with electrocatalysis as an upgrading method.

  2. Fuel and fuel blending components from biomass derived pyrolysis oil

    DOEpatents

    McCall, Michael J.; Brandvold, Timothy A.; Elliott, Douglas C.

    2012-12-11

    A process for the conversion of biomass derived pyrolysis oil to liquid fuel components is presented. The process includes the production of diesel, aviation, and naphtha boiling point range fuels or fuel blending components by two-stage deoxygenation of the pyrolysis oil and separation of the products.

  3. Conceptual process design and techno-economic assessment of ex situ catalytic fast pyrolysis of biomass: A fixed bed reactor implementation scenario for future feasibility

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dutta, Abhijit; Schaidle, Joshua A.; Humbird, David

    Ex situ catalytic fast pyrolysis of biomass is a promising route for the production of fungible liquid biofuels. There is significant ongoing research on the design and development of catalysts for this process. However, there are a limited number of studies investigating process configurations and their effects on biorefinery economics. Herein we present a conceptual process design with techno-economic assessment; it includes the production of upgraded bio-oil via fixed bed ex situ catalytic fast pyrolysis followed by final hydroprocessing to hydrocarbon fuel blendstocks. This study builds upon previous work using fluidized bed systems, as detailed in a recent design reportmore » led by the National Renewable Energy Laboratory (NREL/TP-5100-62455); overall yields are assumed to be similar, and are based on enabling future feasibility. Assuming similar yields provides a basis for easy comparison and for studying the impacts of areas of focus in this study, namely, fixed bed reactor configurations and their catalyst development requirements, and the impacts of an inline hot gas filter. A comparison with the fluidized bed system shows that there is potential for higher capital costs and lower catalyst costs in the fixed bed system, leading to comparable overall costs. The key catalyst requirement is to enable the effective transformation of highly oxygenated biomass into hydrocarbons products with properties suitable for blending into current fuels. Potential catalyst materials are discussed, along with their suitability for deoxygenation, hydrogenation and C–C coupling chemistry. This chemistry is necessary during pyrolysis vapor upgrading for improved bio-oil quality, which enables efficient downstream hydroprocessing; C–C coupling helps increase the proportion of diesel/jet fuel range product. One potential benefit of fixed bed upgrading over fluidized bed upgrading is catalyst flexibility, providing greater control over chemistry and product composition

  4. Conceptual process design and techno-economic assessment of ex situ catalytic fast pyrolysis of biomass: A fixed bed reactor implementation scenario for future feasibility

    DOE PAGES

    Dutta, Abhijit; Schaidle, Joshua A.; Humbird, David; ...

    2015-10-06

    Ex situ catalytic fast pyrolysis of biomass is a promising route for the production of fungible liquid biofuels. There is significant ongoing research on the design and development of catalysts for this process. However, there are a limited number of studies investigating process configurations and their effects on biorefinery economics. Herein we present a conceptual process design with techno-economic assessment; it includes the production of upgraded bio-oil via fixed bed ex situ catalytic fast pyrolysis followed by final hydroprocessing to hydrocarbon fuel blendstocks. This study builds upon previous work using fluidized bed systems, as detailed in a recent design reportmore » led by the National Renewable Energy Laboratory (NREL/TP-5100-62455); overall yields are assumed to be similar, and are based on enabling future feasibility. Assuming similar yields provides a basis for easy comparison and for studying the impacts of areas of focus in this study, namely, fixed bed reactor configurations and their catalyst development requirements, and the impacts of an inline hot gas filter. A comparison with the fluidized bed system shows that there is potential for higher capital costs and lower catalyst costs in the fixed bed system, leading to comparable overall costs. The key catalyst requirement is to enable the effective transformation of highly oxygenated biomass into hydrocarbons products with properties suitable for blending into current fuels. Potential catalyst materials are discussed, along with their suitability for deoxygenation, hydrogenation and C–C coupling chemistry. This chemistry is necessary during pyrolysis vapor upgrading for improved bio-oil quality, which enables efficient downstream hydroprocessing; C–C coupling helps increase the proportion of diesel/jet fuel range product. One potential benefit of fixed bed upgrading over fluidized bed upgrading is catalyst flexibility, providing greater control over chemistry and product composition

  5. Biofuels via Fast Pyrolysis of Perennial Grasses: A Life Cycle Evaluation of Energy Consumption and Greenhouse Gas Emissions.

    PubMed

    Zaimes, George G; Soratana, Kullapa; Harden, Cheyenne L; Landis, Amy E; Khanna, Vikas

    2015-08-18

    A well-to-wheel (WTW) life cycle assessment (LCA) model is developed to evaluate the environmental profile of producing liquid transportation fuels via fast pyrolysis of perennial grasses: switchgrass and miscanthus. The framework established in this study consists of (1) an agricultural model used to determine biomass growth rates, agrochemical application rates, and other key parameters in the production of miscanthus and switchgrass biofeedstock; (2) an ASPEN model utilized to simulate thermochemical conversion via fast pyrolysis and catalytic upgrading of bio-oil to renewable transportation fuel. Monte Carlo analysis is performed to determine statistical bounds for key sustainability and performance measures including life cycle greenhouse gas (GHG) emissions and Energy Return on Investment (EROI). The results of this work reveal that the EROI and GHG emissions (gCO2e/MJ-fuel) for fast pyrolysis derived fuels range from 1.52 to 2.56 and 22.5 to 61.0 respectively, over the host of scenarios evaluated. Further analysis reveals that the energetic performance and GHG reduction potential of fast pyrolysis-derived fuels are highly sensitive to the choice of coproduct scenario and LCA allocation scheme, and in select cases can change the life cycle carbon balance from meeting to exceeding the renewable fuel standard emissions reduction threshold for cellulosic biofuels.

  6. Hybrid-renewable processes for biofuels production: concentrated solar pyrolysis of biomass residues

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    George, Anthe; Geier, Manfred; Dedrick, Daniel E.

    2014-10-01

    The viability of thermochemically-derived biofuels can be greatly enhanced by reducing the process parasitic energy loads. Integrating renewable power into biofuels production is one method by which these efficiency drains can be eliminated. There are a variety of such potentially viable "hybrid-renewable" approaches; one is to integrate concentrated solar power (CSP) to power biomass-to-liquid fuels (BTL) processes. Barriers to CSP integration into BTL processes are predominantly the lack of fundamental kinetic and mass transport data to enable appropriate systems analysis and reactor design. A novel design for the reactor has been created that can allow biomass particles to be suspendedmore » in a flow gas, and be irradiated with a simulated solar flux. Pyrolysis conditions were investigated and a comparison between solar and non-solar biomass pyrolysis was conducted in terms of product distributions and pyrolysis oil quality. A novel method was developed to analyse pyrolysis products, and investigate their stability.« less

  7. Fixed bed pyrolysis of biomass solid waste for bio-oil

    NASA Astrophysics Data System (ADS)

    Islam, Mohammad Nurul; Ali, Mohamed Hairol Md; Haziq, Miftah

    2017-08-01

    Biomass solid waste in the form of rice husk particle is pyrolyzed in a fixed bed stainless steel pyrolysis reactor of 50 mm diameter and 50 cm length. The biomass solid feedstock is prepared prior to pyrolysis. The reactor bed is heated by means of a cylindrical heater of biomass source. A temperature of 500°C is maintained with an apperent vapor residence time of 3-5 sec. The products obtained are liquid bio-oil, solid char and gases. The liquid product yield is found to be 30% by weight of solid biomass feedstock while the solid product yield is found to be 35% by weight of solid biomass feedtock, the rest is gas. The bio-oil is a single-phase brownish color liquid of acrid smell. The heating value of the oil is determined to be 25 MJ/kg. The density and pH value are found to be 1.125 kg/m3 and 3.78 respectively.

  8. Bio-oil production via fast pyrolysis of biomass residues from cassava plants in a fluidised-bed reactor.

    PubMed

    Pattiya, Adisak

    2011-01-01

    Biomass residues from cassava plants, namely cassava stalk and cassava rhizome, were pyrolysed in a fluidised-bed reactor for production of bio-oil. The aims of this work were to investigate the yields and properties of pyrolysis products produced from both feedstocks as well as to identify the optimum pyrolysis temperature for obtaining the highest organic bio-oil yields. Results showed that the maximum yields of the liquid bio-oils derived from the stalk and rhizome were 62 wt.% and 65 wt.% on dry basis, respectively. The pyrolysis temperatures that gave highest bio-oil yields for both feedstocks were in the range of 475-510 °C. According to the analysis of the bio-oils properties, the bio-oil derived from cassava rhizome showed better quality than that derived from cassava stalk as the former had lower oxygen content, higher heating value and better storage stability. Copyright © 2010 Elsevier Ltd. All rights reserved.

  9. Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.

    PubMed

    Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Wu, Joan; Chen, Shulin

    2016-11-01

    The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Numerical simulation of vortex pyrolysis reactors for condensable tar production from biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Miller, R.S.; Bellan, J.

    1998-08-01

    A numerical study is performed in order to evaluate the performance and optimal operating conditions of vortex pyrolysis reactors used for condensable tar production from biomass. A detailed mathematical model of porous biomass particle pyrolysis is coupled with a compressible Reynolds stress transport model for the turbulent reactor swirling flow. An initial evaluation of particle dimensionality effects is made through comparisons of single- (1D) and multi-dimensional particle simulations and reveals that the 1D particle model results in conservative estimates for total pyrolysis conversion times and tar collection. The observed deviations are due predominantly to geometry effects while directional effects frommore » thermal conductivity and permeability variations are relatively small. Rapid ablative particle heating rates are attributed to a mechanical fragmentation of the biomass particles that is modeled using a critical porosity for matrix breakup. Optimal thermal conditions for tar production are observed for 900 K. Effects of biomass identity, particle size distribution, and reactor geometry and scale are discussed.« less

  11. Recent progress on biomass co-pyrolysis conversion into high-quality bio-oil.

    PubMed

    Hassan, H; Lim, J K; Hameed, B H

    2016-12-01

    Co-pyrolysis of biomass with abundantly available materials could be an economical method for production of bio-fuels. However, elimination of oxygenated compounds poses a considerable challenge. Catalytic co-pyrolysis is another potential technique for upgrading bio-oils for application as liquid fuels in standard engines. This technique promotes the production of high-quality bio-oil through acid catalyzed reduction of oxygenated compounds and mutagenic polyaromatic hydrocarbons. This work aims to review and summarize research progress on co-pyrolysis and catalytic co-pyrolysis, as well as their benefits on enhancement of bio-oils derived from biomass. This review focuses on the potential of plastic wastes and coal materials as co-feed in co-pyrolysis to produce valuable liquid fuel. This paper also proposes future directions for using this technique to obtain high yields of bio-oils. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. H-ZSM5 Catalyzed co-pyrolysis of biomass and plastics

    USDA-ARS?s Scientific Manuscript database

    This study aims at addressing two important problems vital to agriculture, disposal of agricultural plastics and production of drop-in fuels from biomass via co-pyrolysis of both feedstocks. Mixtures of biomass (switchgrass, cellulose, xylan and lignin) and plastic (polyethylene terephthalate (PET),...

  13. Pyrolysis Treatment of Chromite Ore Processing Residue by Biomass: Cellulose Pyrolysis and Cr(VI) Reduction Behavior.

    PubMed

    Zhang, Da-Lei; Zhang, Mei-Yi; Zhang, Chu-Hui; Sun, Ying-Jie; Sun, Xiao; Yuan, Xian-Zheng

    2016-03-15

    The pyrolysis treatment with biomass is a promising technology for the remediation of chromite-ore-processing residue (COPR). However, the mechanism of this process is still unclear. In this study, the behavior of pyrolysis reduction of Cr(VI) by cellulose, the main component of biomass, was elucidated. The results showed that the volatile fraction (VF) of cellulose, ie. gas and tar, was responsible for Cr(VI) reduction. All organic compounds, as well as CO and H2 in VF, potentially reduced Cr(VI). X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine-structure (EXAFS) spectroscopy confirmed the reduction of Cr(VI) to Cr(III) and the formation of amorphous Cr2O3. The remnant Cr(VI) content in COPR can be reduced below the detection limit (2 mg/kg) by the reduction of COPR particle and extension of reaction time between VF and COPR. This study provided a deep insight on the co-pyrolysis of cellulose with Cr(VI) in COPR and an ideal approach by which to characterize and optimize the pyrolysis treatment for COPR by other organics.

  14. Well-to-wheels analysis of fast pyrolysis pathways with the GREET model.

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Han, J.; Elgowainy, A.; Palou-Rivera, I.

    The pyrolysis of biomass can help produce liquid transportation fuels with properties similar to those of petroleum gasoline and diesel fuel. Argonne National Laboratory conducted a life-cycle (i.e., well-to-wheels [WTW]) analysis of various pyrolysis pathways by expanding and employing the Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (GREET) model. The WTW energy use and greenhouse gas (GHG) emissions from the pyrolysis pathways were compared with those from the baseline petroleum gasoline and diesel pathways. Various pyrolysis pathway scenarios with a wide variety of possible hydrogen sources, liquid fuel yields, and co-product application and treatment methods were considered. Atmore » one extreme, when hydrogen is produced from natural gas and when bio-char is used for process energy needs, the pyrolysis-based liquid fuel yield is high (32% of the dry mass of biomass input). The reductions in WTW fossil energy use and GHG emissions relative to those that occur when baseline petroleum fuels are used, however, is modest, at 50% and 51%, respectively, on a per unit of fuel energy basis. At the other extreme, when hydrogen is produced internally via reforming of pyrolysis oil and when bio-char is sequestered in soil applications, the pyrolysis-based liquid fuel yield is low (15% of the dry mass of biomass input), but the reductions in WTW fossil energy use and GHG emissions are large, at 79% and 96%, respectively, relative to those that occur when baseline petroleum fuels are used. The petroleum energy use in all scenarios was restricted to biomass collection and transportation activities, which resulted in a reduction in WTW petroleum energy use of 92-95% relative to that found when baseline petroleum fuels are used. Internal hydrogen production (i.e., via reforming of pyrolysis oil) significantly reduces fossil fuel use and GHG emissions because the hydrogen from fuel gas or pyrolysis oil (renewable sources) displaces that from fossil

  15. Nitrogen conversion under rapid pyrolysis of two types of aquatic biomass and corresponding blends with coal.

    PubMed

    Yuan, Shuai; Chen, Xue-li; Li, Wei-feng; Liu, Hai-feng; Wang, Fu-chen

    2011-11-01

    Rapid pyrolysis of two types of aquatic biomass (blue-green algae and water hyacinth), and their blends with two coals (bituminous and anthracite) was carried out in a high-frequency furnace. Nitrogen conversions during rapid pyrolysis of the two biomass and the interactions between the biomass and coals on nitrogen conversions were investigated. Results show that little nitrogen retained in char after the biomass pyrolysis, and NH(3) yields were higher than HCN. During co-pyrolysis of biomass and coal, interactions between biomass and coal decreased char-N yields and increased volatile-N yields, but the total yields of NH(3)+HCN in volatile-N were decreased in which HCN formations were decreased consistently, while NH(3) formations were only decreased in the high-temperature range but promoted in the low-temperature range. Interactions between blue-green algae and coals are stronger than those between water hyacinth and coal, and interactions between biomass and bituminous are stronger than those between biomass and anthracite. Copyright © 2011 Elsevier Ltd. All rights reserved.

  16. Dewatering and low-temperature pyrolysis of oily sludge in the presence of various agricultural biomasses.

    PubMed

    Zhao, Song; Zhou, Xiehong; Wang, Chuanyi; Jia, Hanzhong

    2017-08-24

    Pyrolysis is potentially an effective treatment of waste oil residues for recovery of petroleum hydrocarbons, and the addition of biomass is expected to improve its dewatering and pyrolysis behavior. In this study, the dewatering and low-temperature co-pyrolysis of oil-containing sludge in the presence of various agricultural biomasses, such as rice husk, walnut shell, sawdust, and apricot shell, were explored. As a result, the water content gradually decreases with the increase of biomass addition within 0-1.0 wt % in original oily sludge. Comparatively, the dewatering efficiency of sludge in the presence of four types of biomasses follows the order of apricot shell > walnut shell > rice husk > sawdust. On the other hand, rice husk and sawdust are relatively more efficient in the recovery of petroleum hydrocarbons compared with walnut shell and apricot shell. The recovery efficiency generally increased with the increase in the biomass content in the range of 0-0.2 wt %, then exhibited a gradually decreasing trend with the increase in the biomass content from 0.2 to 1.0 wt %. The results suggest that optimum amount of biomass plays an important role in the recovery efficiency. In addition, the addition of biomass (such as rice husk) also promotes the formation of C x H y and CO, increasing the calorific value of pyrolysis residue, and controlled the pollution components of the exhaust gas discharged from residue incineration. The present work implies that biomass as addictive holds great potential in the industrial dewatering and pyrolysis of oil-containing sludge.

  17. Pyrolysis Strategies for Effective Utilization of Lignocellulosic and Algal Biomass

    NASA Astrophysics Data System (ADS)

    Maddi, Balakrishna

    Pyrolysis is a processing technique involving thermal degradation of biomass in the absence of oxygen. The bio-oils obtained following the condensation of the pyrolysis vapors form a convenient starting point for valorizing the major components of lignocellulosic as well as algal biomass feed stocks for the production of fuels and value-added chemicals. Pyrolysis can be implemented on whole biomass or on residues left behind following standard fractionation methods. Microalgae and oil seeds predominantly consist of protein, carbohydrate and triglycerides, whereas lignocellulose is composed of carbohydrates (cellulose and hemicellulose) and lignin. The differences in the major components of these two types of biomass will necessitate different pyrolysis strategies to derive the optimal benefits from the resulting bio-oils. In this thesis, novel pyrolysis strategies were developed that enable efficient utilization of the bio-oils (and/or their vapors) from lignocellulose, algae, as well as oil seed feed stocks. With lignocellulosic feed stocks, pyrolysis of whole biomass as well as the lignin residue left behind following well-established pretreatment and saccharification (i.e., depolymerization of cellulose and hemicellulose to their monomeric-sugars) of the biomass was studied with and without catalysts. Following this, pyrolysis of (lipid-deficient) algae and lignocellulosic feed stocks, under similar reactor conditions, was performed for comparison of product (bio-oil, gas and bio-char) yields and composition. In spite of major differences in component bio-polymers, feedstock properties relevant to thermo-chemical conversions, such as overall C, H and O-content, C/O and H/C molar ratio as well as calorific values, were found to be similar for algae and lignocellulosic material. Bio-oil yields from algae and some lignocellulosic materials were similar; however, algal bio-oils were compositionally different and contained several N-compounds (most likely from

  18. Flash Pyrolysis and Fractional Pyrolysis of Oleaginous Biomass in a Fluidized-bed Reactor

    NASA Astrophysics Data System (ADS)

    Urban, Brook

    Thermochemical conversion methods such as pyrolysis have the potential for converting diverse biomass feedstocks into liquid fuels. In particular, bio-oil yields can be maximized by implementing flash pyrolysis to facilitate rapid heat transfer to the solids along with short vapor residence times to minimize secondary degradation of bio-oils. This study first focused on the design and construction of a fluidized-bed flash pyrolysis reactor with a high-efficiency bio-oil recovery unit. Subsequently, the reactor was used to perform flash pyrolysis of soybean pellets to assess the thermochemical conversion of oleaginous biomass feedstocks. The fluidized bed reactor design included a novel feed input mechanism through suction created by flow of carrier gas through a venturi which prevented plugging problems that occur with a more conventional screw feeders. In addition, the uniquely designed batch pyrolysis unit comprised of two tubes of dissimilar diameters. The bottom section consisted of a 1" tube and was connected to a larger 3" tube placed vertically above. At the carrier gas flow rates used in these studies, the feed particles remained fluidized in the smaller diameter tube, but a reduction in carrier gas velocity in the larger diameter "disengagement chamber" prevented the escape of particles into the condensers. The outlet of the reactor was connected to two Allihn condensers followed by an innovative packed-bed dry ice condenser. Due to the high carrier gas flow rates in fluidized bed reactors, bio-oil vapors form dilute aerosols upon cooling which that are difficult to coalesce and recover by traditional heat exchange condensers. The dry ice condenser provided high surface area for inertial impaction of these aerosols and also allowed easy recovery of bio-oils after natural evaporation of the dry ice at the end of the experiments. Single step pyrolysis was performed between 250-610°C with a vapor residence time between 0.3-0.6s. At 550°C or higher, 70% of

  19. Study on pyrolysis characteristics of lignocellulosic biomass impregnated with ammonia source.

    PubMed

    Li, Kai; Zhu, Changpeng; Zhang, Liqiang; Zhu, Xifeng

    2016-06-01

    The current study presents the pyrolysis characteristics of rice husk impregnated with different kinds of ammonia source (ammonium acetate, urea, ammonium sulfate and ammonium dihydrogen phosphate) in a fixed bed reactor. The introduction of ammonia source in pyrolysis process achieved the conversation from carbonyl compounds to nitrogenous heterocyclic compounds. The liquid product of urea-impregnated biomass has higher content of nitrogenous heterocyclic compounds (8.35%) and phenols (30.4%). For ammonium sulfate and ammonium dihydrogen phosphate-impregnated biomass, the quantity of compounds in liquid products reduces remarkably, and the gas products are rich in CO and H2. All the solid products of pyrolysis have great potential application in biochar-based fertilizer and activated carbon for their high N content. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Investigation of waste biomass co-pyrolysis with petroleum sludge using a response surface methodology.

    PubMed

    Hu, Guangji; Li, Jianbing; Zhang, Xinying; Li, Yubao

    2017-05-01

    The treatment of waste biomass (sawdust) through co-pyrolysis with refinery oily sludge was carried out in a fixed-bed reactor. Response surface method was applied to evaluate the main and interaction effects of three experimental factors (sawdust percentage in feedstock, temperature, and heating rate) on pyrolysis oil and char yields. It was found that the oil and char yields increased with sawdust percentage in feedstock. The interaction between heating rate and sawdust percentage as well as between heating rate and temperature was significant on the pyrolysis oil yield. The higher heating value of oil originated from sawdust during co-pyrolysis at a sawdust/oily sludge ratio of 3:1 increased by 5 MJ/kg as compared to that during sawdust pyrolysis alone, indicating a synergistic effect of co-pyrolysis. As a result, petroleum sludge can be used as an effective additive in the pyrolysis of waste biomass for improving its energy recovery. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Catalytic Fast Pyrolysis of Cellulose by Integrating Dispersed Nickel Catalyst with HZSM-5 Zeolite

    NASA Astrophysics Data System (ADS)

    Lei, Xiaojuan; Bi, Yadong; Zhou, Wei; Chen, Hui; Hu, Jianli

    2018-01-01

    The effect of integrating dispersed nickel catalyst with HZSM-5 zeolite on upgrading of vapors produced from pyrolysis of lignocellulosic biomass was investigated. The active component nickel nitrate was introduced onto the cellulose substrate by impregnation technique. Based on TGA experimental results, we discovered that nickel nitrate first released crystallization water, and then successively decomposed into nickel oxide which was reduced in-situ to metallic nickel through carbothermal reduction reaction. In-situ generated nickel nanoparticles were found highly dispersed over carbon substrate, which were responsible for catalyzing reforming and cracking of tars. In catalytic fast pyrolysis of cellulose, the addition of nickel nitrate caused more char formation at the expense of the yield of the condensable liquid products. In addition, the selectivity of linear oxygenates was increased whereas the yield of laevoglucose was reduced. Oxygen-containing compounds in pyrolysis vapors were deoxygenated into aromatics using HZSM-5. Moreover, the amount of condensable liquid products was decreased with the addition of HZSM-5.

  2. Estimation of terpene content in loblolly pine biomass using a hybrid fast-GC and pyrolysis-molecular beam mass spectrometry method

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Harman-Ware, Anne E.; Davis, Mark F.; Peter, Gary F.

    Terpenes can be used as renewable fuels and chemicals and quantifying their presence in biomass is becoming increasingly important. A novel method was developed to rapidly quantify total diterpenoid resin acids using pyrolysis-molecular beam mass spectrometry (py-MBMS). Pine sapling monoterpenes and diterpenoids were extracted from wood using a 1:1 (v/v) mixture of hexane and acetone and analyses were performed before and after extraction to determine the extraction efficiency of the solvent system. The resulting extract was analyzed for total diterpenoid content using py-MBMS and was combined with total monoterpene content that was determined using a low thermal mass modular acceleratedmore » column heater (LTM MACH) fast-GC/FID to measure the terpene content present in pine saplings. Oleoresin extruded from larger pine trees was used to validate mass balance closure of the terpene content in the extract solvent.« less

  3. Estimation of terpene content in loblolly pine biomass using a hybrid fast-GC and pyrolysis-molecular beam mass spectrometry method

    DOE PAGES

    Harman-Ware, Anne E.; Davis, Mark F.; Peter, Gary F.; ...

    2017-01-16

    Terpenes can be used as renewable fuels and chemicals and quantifying their presence in biomass is becoming increasingly important. A novel method was developed to rapidly quantify total diterpenoid resin acids using pyrolysis-molecular beam mass spectrometry (py-MBMS). Pine sapling monoterpenes and diterpenoids were extracted from wood using a 1:1 (v/v) mixture of hexane and acetone and analyses were performed before and after extraction to determine the extraction efficiency of the solvent system. The resulting extract was analyzed for total diterpenoid content using py-MBMS and was combined with total monoterpene content that was determined using a low thermal mass modular acceleratedmore » column heater (LTM MACH) fast-GC/FID to measure the terpene content present in pine saplings. Oleoresin extruded from larger pine trees was used to validate mass balance closure of the terpene content in the extract solvent.« less

  4. Preparation of brightness stabilization agent for lignin containing pulp from biomass pyrolysis oils

    DOEpatents

    Agblevor, Foster A.; Besler-Guran, Serpil

    2001-01-01

    A process for producing a brightness stabilization mixture of water-soluble organic compounds from biomass pyrolysis oils comprising: a) size-reducing biomass material and pyrolyzing the size-reduced biomass material in a fluidized bed reactor; b) separating a char/ash component while maintaining char-pot temperatures to avoid condensation of pyrolysis vapors; c) condensing pyrolysis gases and vapors, and recovering pyrolysis oils by mixing the oils with acetone to obtain an oil-acetone mixture; d) evaporating acetone and recovering pyrolysis oils; e) extracting the pyrolysis oils with water to obtain a water extract; f) slurrying the water extract with carbon while stirring, and filtering the slurry to obtain a colorless filtrate; g) cooling the solution and stabilizing the solution against thermally-induced gelling and solidification by extraction with ethyl acetate to form an aqueous phase lower layer and an organic phase upper layer; h) discarding the upper organic layer and extracting the aqueous layer with ethyl acetate, and discarding the ethyl acetate fraction to obtain a brown-colored solution not susceptible to gelling or solidification upon heating; i) heating the solution to distill off water and other light components and concentrating a bottoms fraction comprising hydroxyacetaldehyde and other non-volatile components having high boiling points; and j) decolorizing the stabilized brown solution with activated carbon to obtain a colorless solution.

  5. Co-pyrolysis of lignocellulosic biomass and microalgae: Products characteristics and interaction effect.

    PubMed

    Chen, Wei; Chen, Yingquan; Yang, Haiping; Xia, Mingwei; Li, Kaixu; Chen, Xu; Chen, Hanping

    2017-12-01

    Co-pyrolysis of biomass has a potential to change the quality of pyrolytic bio-oil. In this work, co-pyrolysis of bamboo, a typical lignocellulosic biomass, and Nannochloropsis sp. (NS), a microalgae, was carried out in a fixed bed reactor at a range of mixing ratio of NS and bamboo, to find out whether the quality of pyrolytic bio-oil was improved. A significant improvement on bio-oil after co-pyrolysis of bamboo and NS was observed that bio-oil yield increased up to 66.63wt% (at 1:1) and the content of long-chain fatty acids in bio-oil also dramatically increased (the maximum up to 50.92% (13.57wt%) at 1:1) whereas acetic acid, O-containing species, and N-containing compounds decreased greatly. Nitrogen transformation mechanism during co-pyrolysis also was explored. Results showed that nitrogen in microalgae preferred to transform into solid char and gas phase during co-pyrolysis, while more pyrrolic-N and quaternary-N generated with diminishing protein-N and pyridinic-N in char. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Torrefaction of agriculture straws and its application on biomass pyrolysis poly-generation.

    PubMed

    Chen, Yingquan; Yang, Haiping; Yang, Qing; Hao, Hongmeng; Zhu, Bo; Chen, Hanping

    2014-03-01

    This study investigated the properties of corn stalk and cotton stalk after torrefaction, and the effects of torrefaction on product properties obtained under the optimal condition of biomass pyrolysis polygeneration. The color of the torrefied biomass chars darkened, and the grindability was upgraded, with finer particles formed and grinding energy consumption reduced. The moisture and oxygen content significantly decreased whereas the carbon content increased considerably. It was found that torrefaction had different effects on the char, liquid oil and biogas from biomass pyrolysis polygeneration. Compared to raw straws, the output of chars from pyrolysis of torrefied straws increased and the quality of chars as a solid fuel had no significant change, while the output of liquid oil and biogas decreased. The liquid oil contained more concentrated phenols with less water content below 40wt.%, and the biogas contained more concentrated H2 and CH4 with higher LHV up to 15MJ/nm(3). Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Catalytic Fast Pyrolysis of Cellulose Using Nano Zeolite and Zeolite/Matrix Catalysts in a GC/Micro-Pyrolyzer.

    PubMed

    Lee, Kyong-Hwan

    2016-05-01

    Cellulose, as a model compound of biomass, was catalyzed over zeolite (HY,.HZSM-5) and zeolite/matrix (HY/Clay, HM/Clay) in a GC/micro-pyrolyzer at 500 degrees C, to produce the valuable products. The catalysts used were pure zeolite and zeolite/matrix including 20 wt% matrix content, which were prepared into different particle sizes (average size; 0.1 mm, 1.6 mm) to study the effect of the particle size of the catalyst for the distribution of product yields. Catalytic pyrolysis had much more volatile products as light components and less content of sugars than pyrolysis only. This phenomenon was strongly influenced by the particle size of the catalyst in catalytic fast pyrolysis. Also, in zeolite and zeolite/matrix catalysts the zeolite type gave the dominant impact on the distribution of product yields.

  8. Reducing the bioavailability and leaching potential of lead in contaminated water hyacinth biomass by phosphate-assisted pyrolysis.

    PubMed

    Shi, Lingna; Wang, Lijun; Zhang, Tao; Li, Jianfa; Huang, Xiaoyi; Cai, Jing; Lü, Jinhong; Wang, Yue

    2017-10-01

    For the purpose of safe disposal of biomass contaminated by biosorption of heavy metals, phosphate-assisted pyrolysis of water hyacinth biomass contaminated by lead (Pb) was tried to reduce the bioavailability and leaching potential of Pb, using direct pyrolysis without additive as a control method. Direct pyrolysis of the contaminated biomass at low temperatures (300 and 400°C) could reduce the bioavailability of Pb, but the leaching potential of Pb was increased with the rising pyrolysis temperature. While phosphate-assisted pyrolysis significantly enhanced the recovery and stability of Pb in the char. Specifically, the percentages of bioavailable Pb and leachable Pb in the chars obtained by phosphate-assisted pyrolysis at low temperatures were reduced to less than 5% and 7%, respectively. The sequential extraction test indicated the transformation of Pb into more stable fractions after phosphate-assisted pyrolysis, which was related to the formation of Pb phosphate minerals including pyromorphite and lead-substituted hydroxyapatite. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Energy Conversion Loop: A Testbed for Nuclear Hybrid Energy Systems Use in Biomass Pyrolysis

    NASA Astrophysics Data System (ADS)

    Verner, Kelley M.

    Nuclear hybrid energy systems are a possible solution for contemporary energy challenges. Nuclear energy produces electricity without greenhouse gas emissions. However, nuclear power production is not as flexible as electrical grids demand and renewables create highly variable electricity. Nuclear hybrid energy systems are able to address both of these problems. Wasted heat can be used in processes such as desalination, hydrogen production, or biofuel production. This research explores the possible uses of nuclear process heat in bio-oil production via biomass pyrolysis. The energy conversion loop is a testbed designed and built to mimic the heat from a nuclear reactor. Small scale biomass pyrolysis experiments were performed and compared to results from the energy conversion loop tests to determine future pyrolysis experimentation with the energy conversion loop. Further improvements must be made to the energy conversion loop before more complex experiments may be performed. The current conditions produced by the energy conversion loop are not conducive for current biomass pyrolysis experimentation.tion.

  10. Characterization and Catalytic Upgrading of Aqueous Stream Carbon from Catalytic Fast Pyrolysis of Biomass

    DOE PAGES

    Starace, Anne K.; Black, Brenna A.; Lee, David D.; ...

    2017-10-23

    Catalytic fast pyrolysis (CFP) of biomass produces a liquid product consisting of organic and aqueous streams. The organic stream is typically slated for hydrotreating to produce hydrocarbon biofuels, while the aqueous stream is considered a waste stream, resulting in the loss of residual biogenic carbon. Here, we report the detailed characterization and catalytic conversion of a CFP wastewater stream with the ultimate aim to improve overall biomass utilization within a thermochemical biorefinery. An aqueous stream derived from CFP of beech wood was comprehensively characterized, quantifying 53 organic compounds to a total of 17% organics. The most abundant classes of compoundsmore » are acids, aldehydes, and alcohols. The most abundant components identified in the aqueous stream were C1-C2 organics, comprising 6.40% acetic acid, 2.16% methanol, and 1.84% formaldehyde on wet basis. The CFP aqueous stream was catalytically upgraded to olefins and aromatic hydrocarbons using a Ga/HZSM-5 catalyst at 500 degrees C. When the conversion yield of the upgraded products was measured with fresh, active catalyst, 33% of the carbon in the aqueous stream was recovered as aromatic hydrocarbons and 29% as olefins. The majority of the experiments were conducted using a molecular beam mass spectrometer and separate GC-MS/FID experiments were used to confirm the assignments and quantification of products with fresh excess catalyst. The recovered 62% carbon in the form of olefins and aromatics can be used to make coproducts and/or fuels potentially improving biorefinery economics and sustainability. Spent catalysts were collected after exposure to varying amounts of the feed, and were characterized using multipoint-Brunauer-Emmett-Teller (BET) adsorption, ammonia temperature programmed desorption (TPD), and thermogravimetric analysis (TGA) to monitor deactivation of Ga/HZSM-5. These characterization data revealed that deactivation was caused by coke deposits, which blocked access

  11. Characterization and Catalytic Upgrading of Aqueous Stream Carbon from Catalytic Fast Pyrolysis of Biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Starace, Anne K.; Black, Brenna A.; Lee, David D.

    Catalytic fast pyrolysis (CFP) of biomass produces a liquid product consisting of organic and aqueous streams. The organic stream is typically slated for hydrotreating to produce hydrocarbon biofuels, while the aqueous stream is considered a waste stream, resulting in the loss of residual biogenic carbon. Here, we report the detailed characterization and catalytic conversion of a CFP wastewater stream with the ultimate aim to improve overall biomass utilization within a thermochemical biorefinery. An aqueous stream derived from CFP of beech wood was comprehensively characterized, quantifying 53 organic compounds to a total of 17% organics. The most abundant classes of compoundsmore » are acids, aldehydes, and alcohols. The most abundant components identified in the aqueous stream were C1-C2 organics, comprising 6.40% acetic acid, 2.16% methanol, and 1.84% formaldehyde on wet basis. The CFP aqueous stream was catalytically upgraded to olefins and aromatic hydrocarbons using a Ga/HZSM-5 catalyst at 500 degrees C. When the conversion yield of the upgraded products was measured with fresh, active catalyst, 33% of the carbon in the aqueous stream was recovered as aromatic hydrocarbons and 29% as olefins. The majority of the experiments were conducted using a molecular beam mass spectrometer and separate GC-MS/FID experiments were used to confirm the assignments and quantification of products with fresh excess catalyst. The recovered 62% carbon in the form of olefins and aromatics can be used to make coproducts and/or fuels potentially improving biorefinery economics and sustainability. Spent catalysts were collected after exposure to varying amounts of the feed, and were characterized using multipoint-Brunauer-Emmett-Teller (BET) adsorption, ammonia temperature programmed desorption (TPD), and thermogravimetric analysis (TGA) to monitor deactivation of Ga/HZSM-5. These characterization data revealed that deactivation was caused by coke deposits, which blocked access

  12. An Idealized Direct-Contact Biomass Pyrolysis Reactor Model

    NASA Technical Reports Server (NTRS)

    Miller, R. S.; Bellan, J.

    1996-01-01

    A numerical study is performed in order to assess the performance of biomass pyrolysis reactors which utilize direct particle-wall thermal conduction heating. An idealized reactor configuration consisting of a flat-plate turbulent boundary layer flow with particle convection along the heated wall and incorporating particle re-entrainment is considered.

  13. The effect of torrefaction on the chemistry of fast-pyrolysis bio-oil.

    PubMed

    Meng, Jiajia; Park, Junyeong; Tilotta, David; Park, Sunkyu

    2012-05-01

    Fast pyrolysis was performed on torrefied loblolly pine and the collected bio-oils were analyzed to compare the effect of the torrefaction treatment on their quality. The results of the analyses show that bio-oils produced from torrefied wood have improved oxygen-to-carbon ratios compared to those from the original wood with the penalty of a decrease in bio-oil yield. The extent of this improvement depends on the torrefaction severity. Based on the GC/MS analysis of the pyrolysis bio-oils, bio-oils produced from torrefied biomass show different compositions compared to that from the original wood. Specifically, the former becomes more concentrated in pyrolytic lignin with less water content than the latter. It was considered that torrefaction could be a potential upgrading method to improve the quality of bio-oil, which might be a useful feedstock for phenolic-based chemicals. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. High quality fuel gas from biomass pyrolysis with calcium oxide.

    PubMed

    Zhao, Baofeng; Zhang, Xiaodong; Chen, Lei; Sun, Laizhi; Si, Hongyu; Chen, Guanyi

    2014-03-01

    The removal of CO2 and tar in fuel gas produced by biomass thermal conversion has aroused more attention due to their adverse effects on the subsequent fuel gas application. High quality fuel gas production from sawdust pyrolysis with CaO was studied in this paper. The results of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments indicate that the mass ratio of CaO to sawdust (Ca/S) remarkably affects the behavior of sawdust pyrolysis. On the basis of Py-GC/MS results, one system of a moving bed pyrolyzer coupled with a fluid bed combustor has been developed to produce high quality fuel gas. The lower heating value (LHV) of the fuel gas was above 16MJ/Nm(3) and the content of tar was under 50mg/Nm(3), which is suitable for gas turbine application to generate electricity and heat. Therefore, this technology may be a promising route to achieve high quality fuel gas for biomass utilization. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. Investigation on the quality of bio-oil produced through fast pyrolysis of biomass-polymer waste mixture

    NASA Astrophysics Data System (ADS)

    Jourabchi, S. A.; Ng, H. K.; Gan, S.; Yap, Z. Y.

    2016-06-01

    A high-impact poly-styrene (HIPS) was mixed with dried and ground coconut shell (CS) at equal weight percentage. Fast pyrolysis was carried out on the mixture in a fixed bed reactor over a temperature range of 573 K to 1073 K, and a nitrogen (N2) linear velocity range of 7.8x10-5 m/s to 6.7x10-2 m/s to produce bio-oil. Heat transfer and fluid dynamics of the pyrolysis process inside the reactor was visualised by using Computational Fluid Dynamics (CFD). The CFD modelling was validated by experimental results and they both indicated that at temperature of 923 K and N2 linear velocity of 7.8x10-5 m/s, the maximum bio-oil yield of 52.02 wt% is achieved.

  16. Renewable hydrocarbons for jet fuels from biomass and plastics via microwave-induced pyrolysis and hydrogenation processes

    NASA Astrophysics Data System (ADS)

    Zhang, Xuesong

    This dissertation aims to enhance the production of aromatic hydrocarbons in the catalytic microwave-induced pyrolysis, and maximize the production of renewable cycloalkanes for jet fuels in the hydrogenation process. In the process, ZSM-5 catalyst as the highly efficient catalyst was employed for catalyzing the pyrolytic volatiles from thermal decomposition of cellulose (a model compound of lignocellulosic biomass). A central composite experiment design (CCD) was used to optimize the product yields as a function of independent factors (e.g. catalytic temperature and catalyst to feed mass ratio). The low-density polyethylene (a mode compound of waste plastics) was then carried out in the catalytic microwave-induced pyrolysis in the presence of ZSM-5 catalyst. Thereafter, the catalytic microwave-induced co-pyrolysis of cellulose with low-density polyethylene (LDPE) was conducted over ZSM-5 catalyst. The results showed that the production of aromatic hydrocarbons was significantly enhanced and the coke formation was also considerably reduced comparing with the catalytic microwave pyrolysis of cellulose or LDPE alone. Moreover, practical lignocellulosic biomass (Douglas fir sawdust pellets) was converted into aromatics-enriched bio-oil by catalytic microwave pyrolysis. The bio-oil was subsequently hydrogenated by using the Raney Ni catalyst. A liquid-liquid extraction step was implemented to recover the liquid organics and remove the water content. Over 20% carbon yield of liquid product regarding lignocellulosic biomass was obtained. Up to 90% selectivity in the liquid product belongs to jet fuel range cycloalkanes. As the integrated processes was developed, catalytic microwave pyrolysis of cellulose with LDPE was conducted to improve aromatic production. After the liquid-liquid extraction by the optimal solvent (n-heptane), over 40% carbon yield of hydrogenated organics based on cellulose and LDPE were achieved in the hydrogenation process. As such, real

  17. Apparatuses and methods for deoxygenating biomass-derived pyrolysis oil

    DOEpatents

    Kalnes, Tom N.

    2015-12-29

    Apparatuses and methods for deoxygenating a biomass-derived pyrolysis oil are provided herein. In one example, the method comprises of dividing a feedstock stream into first and second feedstock portions. The feedstock stream comprises the biomass-derived pyrolysis oil and has a temperature of about 60.degree. C. or less. The first feedstock portion is combined with a heated organic liquid stream to form a first heated diluted pyoil feed stream. The first heated diluted pyoil feed stream is contacted with a first deoxygenating catalyst in the presence of hydrogen to form an intermediate low-oxygen pyoil effluent. The second feedstock portion is combined with the intermediate low-oxygen pyoil effluent to form a second heated diluted pyoil feed stream. The second heated diluted pyoil feed stream is contacted with a second deoxygenating catalyst in the presence of hydrogen to form additional low-oxygen pyoil effluent.

  18. Structural analysis of pyrolytic lignins isolated from switchgrass fast pyrolysis oil

    USDA-ARS?s Scientific Manuscript database

    Structural characterization of lignin extracted from the bio-oil produced by fast pyrolysis of switchgrass (Panicum virgatum) is reported. This new information is important to understanding the utility of lignin as a chemical feedstock in a pyrolysis based biorefinery. Pyrolysis induces a variety of...

  19. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels. Thermochemical Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dutta, Abhijit; Sahir, Asad; Tan, Eric

    This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s efforts to enable the development of technologies for the production of infrastructurecompatible, cost-competitive liquid hydrocarbon fuels from biomass. Specifically, this report details two conceptual designs based on projected product yields and quality improvements via catalyst development and process integration. It is expected that these research improvements will be made within the 2022 timeframe. The two conversion pathways detailed are (1) in situ and (2) ex situ upgrading of vapors produced from the fast pyrolysis of biomass. While the base case conceptual designs and underlying assumptionsmore » outline performance metrics for feasibility, it should be noted that these are only two of many other possibilities in this area of research. Other promising process design options emerging from the research will be considered for future techno-economic analysis.« less

  20. Development of advanced technologies for biomass pyrolysis

    NASA Astrophysics Data System (ADS)

    Xu, Ran

    The utilization of biomass resources as a renewable energy resource is of great importance in responding to concerns over the protection of the environment and the security of energy supply. This PhD research focuses on the investigation of the conversion of negative value biomass residues into value-added fuels through flash pyrolysis. Pyrolysis Process Study. A pilot plant bubbling fluidized bed pyrolyzer has been set up and extensively used to thermally crack various low or negative value agricultural, food and biofuel processing residues to investigate the yields and quality of the liquid [bio-oil] and solid (bio-char] products. Another novel aspect of this study is the establishment of an energy balance from which the thermal self-sustainability of the pyrolysis process can be assessed. Residues such as grape skins and mixture of grape skins and seeds, dried distiller's grains from bio-ethanol plants, sugarcane field residues (internal bagasse, external and whole plant) have been tested. The pyrolysis of each residue has been carried out at temperatures ranging from 300 to 600°C and at different vapor residence times, to determine its pyrolysis behavior including yields and the overall energy balance. The thermal sustainability of the pyrolysis process has been estimated by considering the energy contribution of the product gases and liquid bio-oll in relation to the pyrolysis heat requirements. The optimum pyrolysis conditions have been identified in terms of maximizing the liquid blo-oil yield, energy density and content of the product blo-oil, after ensuring a self-sustainable process by utilizing the product gases and part of char or bio-oil as heat sources. Adownflow pyrolyzer has also been set up. Preliminary tests have been conducted using much shorter residence times. Bio-oil Recovery. Bio-oil recovery from the pyrolysis unit includes condensation followed by demisting. A blo-oil cyclonic condensing system is designed A nearly tangential entry forces

  1. Co-pyrolysis of biomass and plastic wastes: investigation of apparent kinetic parameters and stability of pyrolysis oils

    NASA Astrophysics Data System (ADS)

    Fekhar, B.; Miskolczi, N.; Bhaskar, T.; Kumar, J.; Dhyani, V.

    2018-05-01

    This work is dedicated to the co-pyrolysis of real waste high density polyethylene (HDPE) and biomass (rice straw) obtained from agriculture. Mixtures of raw materials were pyrolyzed in their 0%/100%, 30%/70%, 50%/50%, 70%/30%, 100%/0% ratios using a thermograph. The atmosphere was nitrogen, and a constant heating rate was used. Based on weight loss and DTG curves, the apparent reaction kinetic parameters (e.g., activation energy) were calculated using first-order kinetic approach and Arrhenius equation. It was found that decomposition of pure plastic has approximately 280 kJ/mol activation energy, while that of was considerably less in case of biomass. Furthermore, HDPE decomposition takes by one stage, while that of biomass was three stages. The larger amount of raw materials (100 g) were also pyrolyzed in the batch rig at 550°C to obtain products for analysis focussing to their long-term application. Pyrolysis oils were investigated by Fourier transformed infrared spectroscopy and standardized methods, such as density, viscosity, boiling range determination. It was concluded, that higher plastic ratio in raw material had the advantageous effect to the pyrolysis oil long-term application. E.g., the concentration of oxygenated compounds, such as aldehydes, ketones, carboxylic acids or even phenol and its derivate could be significantly decreased, which had an advantageous effect to their corrosion property. Lower average molecular weight, viscosity, and density were measured as a function of plastic content.

  2. Conventional and catalytic pyrolysis of pinyon juniper biomass

    NASA Astrophysics Data System (ADS)

    Yathavan, Bhuvanesh Kumar

    Pinyon and juniper are invasive woody species in Western United States that occupy over 47 million acres of land. The US Bureau of Land Management (BLM) has embarked on harvesting these woody species to make room for range grasses for grazing. The major application of harvested pinyon-juniper (PJ) is low value firewood. Thus, there is a need to develop new high value products from this woody biomass to reduce the cost of harvesting. In this research PJ biomass was processed through pyrolysis technology to produce value added products. The first part of the thesis demonstrates the effect of PJ wood, bark and mixture biomass and temperature on the product yield and on the quality of the bio-oil produced. The second part focuses on the optimization of process parameters for maximum yield and the third part focuses on upgrading the bio-oil with an industrial catalyst (HZSM5) and an industrial waste product (red mud). The results obtained from the first part showed that PJ wood produced maximum bio-oil yield, followed by PJ mixture and bark. The bio-oil yield from PJ wood had low viscosity when compared to PJ mixture and PJ bark. The second part focused on studying the effect of process parameters (temperature, feed rate and the gas flow rate) on the total liquid, organic, water, char and gas yield. The results show that each response is affected by different factor level combinations, and maximum yield for each response was obtained at different factors level. The third part focused on catalytic pyrolysis of PJ biomass using both HZSM-5 catalyst and red mud. The mechanisms of catalysis by the two catalysts were quite different. Whereas the HZSM-5 rejected oxygen mostly as carbon monoxide and water and produced lower amounts of carbon dioxide, on the contrary the red mud produced more carbon dioxide and water and less carbon monoxide. The higher heating value of the red mud catalyzed oil (29.46 MJ/kg) was slightly higher than that catalyzed by HZSM-5 (28.55 MJ/kg). Thus

  3. Jobs and Economic Development Impact (JEDI) User Reference Guide: Fast Pyrolysis Biorefinery Model

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, Yimin; Goldberg, Marshall

    2015-02-01

    This guide -- the JEDI Fast Pyrolysis Biorefinery Model User Reference Guide -- was developed to assist users in operating and understanding the JEDI Fast Pyrolysis Biorefinery Model. The guide provides information on the model's underlying methodology, as well as the parameters and data sources used to develop the cost data utilized in the model. This guide also provides basic instruction on model add-in features and a discussion of how the results should be interpreted. Based on project-specific inputs from the user, the JEDI Fast Pyrolysis Biorefinery Model estimates local (e.g., county- or state-level) job creation, earnings, and output frommore » total economic activity for a given fast pyrolysis biorefinery. These estimates include the direct, indirect and induced economic impacts to the local economy associated with the construction and operation phases of biorefinery projects.Local revenue and supply chain impacts as well as induced impacts are estimated using economic multipliers derived from the IMPLAN software program. By determining the local economic impacts and job creation for a proposed biorefinery, the JEDI Fast Pyrolysis Biorefinery Model can be used to field questions about the added value biorefineries might bring to a local community.« less

  4. Impact of the lignocellulosic material on fast pyrolysis yields and product quality.

    PubMed

    Carrier, Marion; Joubert, Jan-Erns; Danje, Stephen; Hugo, Thomas; Görgens, Johann; Knoetze, Johannes Hansie

    2013-12-01

    The paper describes the fast pyrolysis conversion of lignocellulosic materials inside a bubbling fluidized bed. The impact of biopolymers distribution in the biomass feed, namely hemicelluloses, cellulose and lignin, on the yields and properties of pyrolytic bio-oils and chars was investigated. Although it is not possible to deconvoluate chemical phenomena from transfer phenomena using bubbling fluidized bed reactors, the key role of hemicelluloses in biomass feedstocks was illustrated by: (i) its influence on the production of pyrolytic water, (ii) its impact on the production of organics, apparently due to its bonding relationship with the lignin and (iii) its ability to inhibit the development of chars porosity, while the cellulose appeared to be the precursor for the microporous character of the biochars. These results are of interest for the selection of suitable feedstocks aimed at producing bio-oil and char as fuels and soil amendment, respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Pyrolysis of corn stalk biomass briquettes in a scaled-up microwave technology.

    PubMed

    Salema, Arshad Adam; Afzal, Muhammad T; Bennamoun, Lyes

    2017-06-01

    Pyrolysis of corn stalk biomass briquettes was carried out in a developed microwave (MW) reactor supplied with 2.45GHz frequency using 3kW power generator. MW power and biomass loading were the key parameters investigated in this study. Highest bio-oil, biochar, and gas yield of 19.6%, 41.1%, and 54.0% was achieved at different process condition. In terms of quality, biochar exhibited good heating value (32MJ/kg) than bio-oil (2.47MJ/kg). Bio-oil was also characterised chemically using FTIR and GC-MS method. This work may open new dimension towards development of large-scale MW pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Summary of Fast Pyrolysis and Upgrading GHG Analyses

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Snowden-Swan, Lesley J.; Male, Jonathan L.

    2012-12-07

    illustrated by the rich dialogue and convergence around the energy content and GHG reduction of cellulosic ethanol (an example of these discussions can be found in Wang 2011). GHG analyses of fast pyrolysis technology routes are being developed and will require significant work to reach the levels of development and maturity of cellulosic ethanol models. This summary provides some of the first fast pyrolysis analyses and clarifies some of the reasons for differing results in an effort to begin the convergence on assumptions, discussion of quality of models, and harmonization.« less

  7. Value added liquid products from waste biomass pyrolysis using pretreatments.

    PubMed

    Das, Oisik; Sarmah, Ajit K

    2015-12-15

    Douglas fir wood, a forestry waste, was attempted to be converted into value added products by pretreatments followed by pyrolysis. Four different types of pretreatments were employed, namely, hot water treatment, torrefaction, sulphuric acid and ammonium phosphate doping. Subsequently, pyrolysis was done at 500°C and the resulting bio-oils were analysed for their chemical composition using Karl Fischer titration, thermogravimetry, ion exchange, and gas chromatography. Pretreatment with acid resulted in the highest yield of bio-oil (~60%). The acid and salt pretreatments were responsible for drastic reduction in the lignin oligomers and enhancement of water content in the pyrolytic liquid. The quantity of xylose/mannose reduced as a result of pretreatments. Although, the content of fermentable sugars remained similar across all the pretreatments, the yield of levoglucosan increased. Pretreatment of the biomass with acid yielded the highest amount of levoglucosan in the bio-oil (13.21%). The acid and salt pretreatments also elevated the amount of acetic acid in the bio-oils. Addition of acid and salt to the biomass altered the interaction of cellulose-lignin in the pyrolysis regime. Application of pretreatments should be based on the intended end use of the liquid product having a desired chemical composition. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Pyrolysis conditions and ozone oxidation effects on ammonia adsorption in biomass generated chars.

    PubMed

    Kastner, James R; Miller, Joby; Das, K C

    2009-05-30

    Ammonia adsorbents were generated via pyrolysis of biomass (peanut hulls and palm oil shells) over a range of temperatures and compared to a commercially available activated carbon (AC) and solid biomass residuals (wood and poultry litter fly ash). Dynamic ammonia adsorption studies (i.e., breakthrough curves) were performed using these adsorbents at 23 degrees C from 6 to 17 ppmv NH(3). Of the biomass chars, palm oil char generated at 500 degrees C had the highest NH(3) adsorption capacity (0.70 mg/g, 6 ppmv, 10% relative humidity (RH)), was similar to the AC, and contrasted to the other adsorbents (including the AC), the NH(3) adsorption capacity significantly increased if the relative humidity was increased (4 mg/g, 7 ppmv, 73% RH). Room temperature ozone treatment of the chars and activated carbon significantly increased the NH(3) adsorption capacity (10% RH); resultant adsorption capacity, q (mg/g) increased by approximately 2, 6, and 10 times for palm oil char, peanut hull char (pyrolysis only), and activated carbon, respectively. However, water vapor (73% RH at 23 degrees C) significantly reduced NH(3) adsorption capacity in the steam and ozone treated biomass, yet had no effect on the palm shell char generated at 500 degrees C. These results indicate the feasibility of using a low temperature (and thus low energy input) pyrolysis and activation process for the generation of NH(3) adsorbents from biomass residuals.

  9. Thermogravimetric analysis and fast pyrolysis of Milkweed.

    PubMed

    Kim, Seung-Soo; Agblevor, Foster A

    2014-10-01

    Pyrolysis of Milkweed was carried out in a thermogravimetric analyzer and a bubbling fluidized bed reactor. Total liquid yield of Milkweed pyrolysis was between 40.74% and 44.19 wt% between 425 °C and 550 °C. The gas yield increased from 27.90 wt% to 33.33 wt% with increasing reaction temperature. The higher heating values (HHV) of the Milkweed bio-oil were relatively high (30.33-32.87 MJ/kg) and varied with reaction temperature, feeding rate and fluidization velocity. The selectivity for CO2 was highest within non-condensable gases, and the molar ratio of CO2/CO was about 3 at the different reaction conditions. The (13)C NMR analysis, of the bio-oil showed that the relative concentration carboxylic group and its derivatives was higher at 425 °C than 475 °C, which resulted in slightly higher oxygen content in bio-oil. The pH of aqueous phase obtained at 475 °C was 7.37 which is the highest reported for any lignocellulosic biomass pyrolysis oils. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Tailoring ZSM-5 Zeolites for the Fast Pyrolysis of Biomass to Aromatic Hydrocarbons.

    PubMed

    Hoff, Thomas C; Gardner, David W; Thilakaratne, Rajeeva; Wang, Kaige; Hansen, Thomas W; Brown, Robert C; Tessonnier, Jean-Philippe

    2016-06-22

    The production of aromatic hydrocarbons from cellulose by zeolite-catalyzed fast pyrolysis involves a complex reaction network sensitive to the zeolite structure, crystallinity, elemental composition, porosity, and acidity. The interplay of these parameters under the reaction conditions represents a major roadblock that has hampered significant improvement in catalyst design for over a decade. Here, we studied commercial and laboratory-synthesized ZSM-5 zeolites and combined data from 10 complementary characterization techniques in an attempt to identify parameters common to high-performance catalysts. Crystallinity and framework aluminum site accessibility were found to be critical to achieve high aromatic yields. These findings enabled us to synthesize a ZSM-5 catalyst with enhanced activity, which offers the highest aromatic hydrocarbon yield reported to date. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Successful scaling-up of self-sustained pyrolysis of oil palm biomass under pool-type reactor.

    PubMed

    Idris, Juferi; Shirai, Yoshihito; Andou, Yoshito; Mohd Ali, Ahmad Amiruddin; Othman, Mohd Ridzuan; Ibrahim, Izzudin; Yamamoto, Akio; Yasuda, Nobuhiko; Hassan, Mohd Ali

    2016-02-01

    An appropriate technology for waste utilisation, especially for a large amount of abundant pressed-shredded oil palm empty fruit bunch (OFEFB), is important for the oil palm industry. Self-sustained pyrolysis, whereby oil palm biomass was combusted by itself to provide the heat for pyrolysis without an electrical heater, is more preferable owing to its simplicity, ease of operation and low energy requirement. In this study, biochar production under self-sustained pyrolysis of oil palm biomass in the form of oil palm empty fruit bunch was tested in a 3-t large-scale pool-type reactor. During the pyrolysis process, the biomass was loaded layer by layer when the smoke appeared on the top, to minimise the entrance of oxygen. This method had significantly increased the yield of biochar. In our previous report, we have tested on a 30-kg pilot-scale capacity under self-sustained pyrolysis and found that the higher heating value (HHV) obtained was 22.6-24.7 MJ kg(-1) with a 23.5%-25.0% yield. In this scaled-up study, a 3-t large-scale procedure produced HHV of 22.0-24.3 MJ kg(-1) with a 30%-34% yield based on a wet-weight basis. The maximum self-sustained pyrolysis temperature for the large-scale procedure can reach between 600 °C and 700 °C. We concluded that large-scale biochar production under self-sustained pyrolysis was successfully conducted owing to the comparable biochar produced, compared with medium-scale and other studies with an electrical heating element, making it an appropriate technology for waste utilisation, particularly for the oil palm industry. © The Author(s) 2015.

  12. Staged thermal fractionation for segregation of lignin and cellulose pyrolysis products: An experimental study of residence time and temperature effects

    DOE PAGES

    Waters, Christopher L.; Janupala, Rajiv R.; Mallinson, Richard G.; ...

    2017-05-25

    Thermal conversion technologies may be the most efficient means of production of transportation fuels from lignocellulosic biomass. In order to increase the viability and improve the carbon emissions profile of pyrolysis biofuels, improvements must be made to the required catalytic upgrading to increase both hydrogen utilization efficiency and final liquid carbon yields. However, no current single catalytic valorization strategy can be optimized to convert the complex mixture of compounds produced upon fast pyrolysis of biomass. Staged thermal fractionation, which entails a series of sequentially increasing temperature steps to decompose biomass, has been proposed as a simple means to create vapormore » product streams of enhanced purity as compared to fast pyrolysis. In this work, we use analytical pyrolysis to investigate the effects of time and temperature on a thermal step designed to segregate the lignin and cellulose pyrolysis products of a biomass which has been pre-torrefied to remove hemicellulose. At process conditions of 380 °C and 180 s isothermal hold time, a stream containing less than 20% phenolics (carbon basis) was produced, and upon subsequent fast pyrolysis of the residual solid a stream of 81.5% levoglucosan (carbon basis) was produced. The thermal segregation comes at the expense of vapor product carbon yield, but the improvement in catalytic performance may offset these losses.« less

  13. Staged thermal fractionation for segregation of lignin and cellulose pyrolysis products: An experimental study of residence time and temperature effects

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Waters, Christopher L.; Janupala, Rajiv R.; Mallinson, Richard G.

    Thermal conversion technologies may be the most efficient means of production of transportation fuels from lignocellulosic biomass. In order to increase the viability and improve the carbon emissions profile of pyrolysis biofuels, improvements must be made to the required catalytic upgrading to increase both hydrogen utilization efficiency and final liquid carbon yields. However, no current single catalytic valorization strategy can be optimized to convert the complex mixture of compounds produced upon fast pyrolysis of biomass. Staged thermal fractionation, which entails a series of sequentially increasing temperature steps to decompose biomass, has been proposed as a simple means to create vapormore » product streams of enhanced purity as compared to fast pyrolysis. In this work, we use analytical pyrolysis to investigate the effects of time and temperature on a thermal step designed to segregate the lignin and cellulose pyrolysis products of a biomass which has been pre-torrefied to remove hemicellulose. At process conditions of 380 °C and 180 s isothermal hold time, a stream containing less than 20% phenolics (carbon basis) was produced, and upon subsequent fast pyrolysis of the residual solid a stream of 81.5% levoglucosan (carbon basis) was produced. The thermal segregation comes at the expense of vapor product carbon yield, but the improvement in catalytic performance may offset these losses.« less

  14. Intermediate pyrolysis of agro-industrial biomasses in bench-scale pyrolyser: Product yields and its characterization.

    PubMed

    Tinwala, Farha; Mohanty, Pravakar; Parmar, Snehal; Patel, Anant; Pant, Kamal K

    2015-01-01

    Pyrolysis of woody biomass, agro-residues and seed was carried out at 500 ± 10 °C in a fixed bed pyrolyser. Bio-oil yield was found varying from 20.5% to 47.5%, whereas the biochar and pyrolysis gas ranged from 27.5% to 40% and 24.5% to 40.5%, respectively. Pyrolysis gas was measured for flame temperature along with CO, CO2, H2, CH4 and other gases composition. HHV of biochar (29.4 MJ/kg) and pyrolitic gas (8.6 MJ/kg) of woody biomass was higher analogous to sub-bituminous coal and steam gasification based producer gas respectively, whereas HHV of bio-oil obtained from seed (25.6 MJ/kg) was significantly more than husks, shells and straws. TGA-DTG studies showed the husks as potential source for the pyrolysis. Bio-oils as a major by-product of intermediate pyrolysis have several applications like substitute of furnace oil, extraction of fine chemicals, whereas biochar as a soil amendment for enhancing soil fertility and gases for thermal application. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Fast pyrolysis of potassium impregnated poplar wood and characterization of its influence on the formation as well as properties of pyrolytic products.

    PubMed

    Hwang, Hyewon; Oh, Shinyoung; Cho, Tae-Su; Choi, In-Gyu; Choi, Joon Weon

    2013-12-01

    TGA results indicated that the maximum decomposition temperature of the biomass decreased from 373.9 to 359.0°C with increasing potassium concentration. For fast pyrolysis, char yield of potassium impregnated biomass doubled regardless of pyrolysis temperature compared to demineralized one. The presence of potassium also affected bio-oil properties. Water content increased from 14.4 to 19.7 wt% and viscosity decreased from 34 to 16.2 cSt, but the pH value of the bio-oil remained stable. Gas chromatography/mass spectroscopy (GC/MS) analysis revealed that potassium promoted thermochemical reactions, thus causing a decrease of levoglucosan and an increase of small molecules and lignin-derived phenols in bio-oil. Additionally, various forms of aromatic hydrocarbons, probably derived from lignins, were detected in non-condensed pyrolytic gas fractions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Pilot-Scale Biorefinery: Sustainable Transport Fuels from Biomass via Integrated Pyrolysis and Catalytic Hydroconversion - Wastewater Cleanup by Catalytic Hydrothermal Gasification

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Elliott, Douglas C.; Olarte, Mariefel V.; Hart, Todd R.

    2015-06-19

    DOE-EE Bioenergy Technologies Office has set forth several goals to increase the use of bioenergy and bioproducts derived from renewable resources. One of these goals is to facilitate the implementation of the biorefinery. The biorefinery will include the production of liquid fuels, power and, in some cases, products. The integrated biorefinery should stand-alone from an economic perspective with fuels and power driving the economy of scale while the economics/profitability of the facility will be dependent on existing market conditions. UOP LLC proposed to demonstrate a fast pyrolysis based integrated biorefinery. Pacific Northwest National Laboratory (PNNL) has expertise in an importantmore » technology area of interest to UOP for use in their pyrolysis-based biorefinery. This CRADA project provides the supporting technology development and demonstration to allow incorporation of this technology into the biorefinery. PNNL developed catalytic hydrothermal gasification (CHG) for use with aqueous streams within the pyrolysis biorefinery. These aqueous streams included the aqueous phase separated from the fast pyrolysis bio-oil and the aqueous byproduct streams formed in the hydroprocessing of the bio-oil to finished products. The purpose of this project was to demonstrate a technically and economically viable technology for converting renewable biomass feedstocks to sustainable and fungible transportation fuels. To demonstrate the technology, UOP constructed and operated a pilot-scale biorefinery that processed one dry ton per day of biomass using fast pyrolysis. Specific objectives of the project were to: The anticipated outcomes of the project were a validated process technology, a range of validated feedstocks, product property and Life Cycle data, and technical and operating data upon which to base the design of a full-scale biorefinery. The anticipated long-term outcomes from successful commercialization of the technology were: (1) the replacement of a

  17. Biomass pyrolysis for biochar or energy applications? A life cycle assessment.

    PubMed

    Peters, Jens F; Iribarren, Diego; Dufour, Javier

    2015-04-21

    The application of biochar as a soil amendment is a potential strategy for carbon sequestration. In this paper, a slow pyrolysis system for generating heat and biochar from lignocellulosic energy crops is simulated and its life-cycle performance compared with that of direct biomass combustion. The use of the char as biochar is also contrasted with alternative use options: cofiring in coal power plants, use as charcoal, and use as a fuel for heat generation. Additionally, the influence on the results of the long-term stability of the biochar in the soil, as well as of biochar effects on biomass yield, is evaluated. Negative greenhouse gas emissions are obtained for the biochar system, indicating a significant carbon abatement potential. However, this is achieved at the expense of lower energy efficiency and higher impacts in the other assessed categories when compared to direct biomass combustion. When comparing the different use options of the pyrolysis char, the most favorable result is obtained for char cofiring substituting fossil coal, even assuming high long-term stability of the char. Nevertheless, a high sensitivity to biomass yield increase is found for biochar systems. In this sense, biochar application to low-quality soils where high yield increases are expected would show a more favorable performance in terms of global warming.

  18. Selective production of chemicals from biomass pyrolysis over metal chlorides supported on zeolite.

    PubMed

    Leng, Shuai; Wang, Xinde; Cai, Qiuxia; Ma, Fengyun; Liu, Yue'e; Wang, Jianguo

    2013-12-01

    Direct biomass conversion into chemicals remains a great challenge because of the complexity of the compounds; hence, this process has attracted less attention than conversion into fuel. In this study, we propose a simple one-step method for converting bagasse into furfural (FF) and acetic acid (AC). In this method, bagasse pyrolysis over ZnCl2/HZSM-5 achieved a high FF and AC yield (58.10%) and a 1.01 FF/AC ratio, but a very low yield of medium-boiling point components. However, bagasse pyrolysis using HZSM-5 alone or ZnCl2 alone still remained large amounts of medium-boiling point components or high-boiling point components. The synergistic effect of HZSM-5 and ZnCl2, which combines pyrolysis, zeolite cracking, and Lewis acid-selective catalysis results in highly efficient bagasse conversion into FF and AC. Therefore, our study provides a novel, simple method for directly converting biomass into high-yield useful chemical. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. Tar Production from Biomass Pyrolysis in a Fluidized Bed Reactor: A Novel Turbulent Multiphase Flow Formulation

    NASA Technical Reports Server (NTRS)

    Bellan, J.; Lathouwers, D.

    2000-01-01

    A novel multiphase flow model is presented for describing the pyrolysis of biomass in a 'bubbling' fluidized bed reactor. The mixture of biomass and sand in a gaseous flow is conceptualized as a particulate phase composed of two classes interacting with the carrier gaseous flow. The solid biomass is composed of three initial species: cellulose, hemicellulose and lignin. From each of these initial species, two new solid species originate during pyrolysis: an 'active' species and a char, thus totaling seven solid-biomass species. The gas phase is composed of the original carrier gas (steam), tar and gas; the last two species originate from the volumetric pyrolysis reaction. The conservation equations are derived from the Boltzmann equations through ensemble averaging. Stresses in the gaseous phase are the sum of the Newtonian and Reynolds (turbulent) contributions. The particulate phase stresses are the sum of collisional and Reynolds contributions. Heat transfer between phases, and heat transfer between classes in the particulate phase is modeled, the last resulting from collisions between sand and biomass. Closure of the equations must be performed by modeling the Reynolds stresses for both phases. The results of a simplified version (first step) of the model are presented.

  20. Numerical Study of Pyrolysis of Biomass in Fluidized Beds

    NASA Technical Reports Server (NTRS)

    Bellan, Josette; Lathouwers, Danny

    2003-01-01

    A report presents a numerical-simulation study of pyrolysis of biomass in fluidized-bed reactors, performed by use of the mathematical model described in Model of Fluidized Bed Containing Reacting Solids and Gases (NPO-30163), which appears elsewhere in this issue of NASA Tech Briefs. The purpose of the study was to investigate the effect of various operating conditions on the efficiency of production of condensable tar from biomass. The numerical results indicate that for a fixed particle size, the fluidizing-gas temperature is the foremost parameter that affects the tar yield. For the range of fluidizing-gas temperatures investigated, and under the assumption that the pyrolysis rate exceeds the feed rate, the optimum steady-state tar collection was found to occur at 750 K. In cases in which the assumption was not valid, the optimum temperature for tar collection was found to be only slightly higher. Scaling up of the reactor was found to exert a small negative effect on tar collection at the optimal operating temperature. It is also found that slightly better scaling is obtained by use of shallower fluidized beds with greater fluidization velocities.

  1. Fluidized bed catalytic pyrolysis of eucalyptus over hzsm-5: effect of acid density and gallium modification on catalyst deactivation

    USDA-ARS?s Scientific Manuscript database

    Catalytic fast pyrolysis of eucalyptus wood was performed on a continuous laboratory scale fluidized bed fast pyrolysis system. Catalytic activity was monitored from use of fresh catalyst up to a cumulative biomass to catalyst ratio (B/C) of 4/1 over extruded pellets of three different ZSM-5 catalys...

  2. Recycling slaughterhouse waste into fertilizer: how do pyrolysis temperature and biomass additions affect phosphorus availability and chemistry?

    PubMed

    Zwetsloot, Marie J; Lehmann, Johannes; Solomon, Dawit

    2015-01-01

    Pyrolysis of slaughterhouse waste could promote more sustainable phosphorus (P) usage through the development of alternative P fertilizers. This study investigated how pyrolysis temperature (220, 350, 550 and 750 °C), rendering before pyrolysis, and wood or corn biomass additions affect P chemistry in bone char, plant availability, and its potential as P fertilizer. Linear combination fitting of synchrotron-based X-ray absorption near edge structure spectra demonstrated that higher pyrolysis temperatures decreased the fit with organic P references, but increased the fit with a hydroxyapatite (HA) reference, used as an indicator of high calcium phosphate (CaP) crystallinity. The fit to the HA reference increased from 0% to 69% in bone with meat residue and from 20% to 95% in rendered bone. Biomass additions to the bone with meat residue reduced the fit to the HA reference by 83% for wood and 95% for corn, and additions to rendered bone by 37% for wood. No detectable aromatic P forms were generated by pyrolysis. High CaP crystallinity was correlated with low water-extractable P, but high formic acid-extractable P indicative of high plant availability. Bone char supplied available P which was only 24% lower than Triple Superphosphate fertilizer and two- to five-fold higher than rock phosphate. Pyrolysis temperature and biomass additions can be used to design P fertilizer characteristics of bone char through changing CaP crystallinity that optimize P availability to plants. © 2014 Society of Chemical Industry.

  3. Analysis and comparison of biomass pyrolysis/gasification condensates: Final report

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Elliott, D.C.

    1986-06-01

    This report provides results of chemical and physical analysis of condensates from eleven biomass gasification and pyrolysis systems. The samples were representative of the various reactor configurations being researched within the Department of Energy, Biomass Thermochemical Conversion program. The condensates included tar phases and aqueous phases. The analyses included gross compositional analysis (elemental analysis, ash, moisture), physical characterization (pour point, viscosity, density, heat of combustion, distillation), specific chemical analysis (gas chromatography/mass spectrometry, infrared spectrophotometry, proton and carbon-13 nuclear magnetic resonance spectrometry) and biological activity (Ames assay and mouse skin tumorigenicity tests). These results are the first step of a longermore » term program to determine the properties, handling requirements, and utility of the condensates recovered from biomass gasification and pyrolysis. The analytical data demonstrates the wide range of chemical composition of the organics recovered in the condensates and suggests a direct relationship between operating temperature and chemical composition of the condensates. A continuous pathway of thermal degradation of the tar components as a function of temperature is proposed. Variations in the chemical composition of the organic components in the tars are reflected in the physical properties of tars and phase stability in relation to water in the condensate. The biological activity appears to be limited to the tars produced at high temperatures. 56 refs., 25 figs., 21 tabs.« less

  4. Pyrolysis kinetics and thermal behavior of waste sawdust biomass using thermogravimetric analysis.

    PubMed

    Mishra, Ranjeet Kumar; Mohanty, Kaustubha

    2018-03-01

    The present study reports pyrolysis behavior of three waste biomass using thermogravimetric analysis to determine kinetic parameters at five different heating rates. Physiochemical characterization confirmed that these biomass have the potential for fuel and energy production. Pyrolysis experiments were carried out at five different heating rates (5-25 °C min -1 ). Five model-free methods such as Kissinger-Akahira-Sunose (KAS), Ozawa-Flynn-Wall (OFW), Friedman, Coats-Redfern, and distributed activation energy (DAEM) were used to calculate the kinetic parameters. The activation energy was found to be 171.66 kJ mol -1 , 148.44 kJ mol -1 , and 171.24 kJ mol -1 from KAS model; 179.29 kJ mol -1 , 156.58 kJ mol -1 , and 179.47 kJ mol -1 from OFW model; 168.58 kJ mol -1 , 181.53 kJ mol -1 , and 184.61 kJ mol -1 from Friedman model; and 206.62 kJ mol -1 , 171.63 kJ mol -1 , and 160.45 kJ mol -1 from DAEM model for PW, SW, AN biomass respectively. The calculated kinetic parameters are in good agreement with other reported biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Influence of NH3 concentration on biomass nitrogen-enriched pyrolysis.

    PubMed

    Chen, Wei; Li, Kaixu; Xia, Mingwei; Chen, Yingquan; Yang, Haiping; Chen, Zhiqun; Chen, Xu; Chen, Hanping

    2018-05-08

    In this study, nitrogen was used to replace oxygen through biomass N-enriched pyrolysis in a fixed-bed reactor to obtain N-containing chemicals and N-doped biochar. Influence of NH 3 concentration on the formation mechanism of N-species and electrochemical performance of N-doped biochar was investigated in depth. Results showed that increasing NH 3 concentration promoted bio-oil and gas generation, and increased H 2 , CH 4 and CO yield at the diminishing of CO 2 . Simultaneously, bio-oil showed lower oxygen content with non-methoxy phenols and N-heterocyclics as the main components, and the maximums were 57.73% and 16.21% at 80 vol% NH 3 concentration, respectively. With regard to solid N-doped biochar, nitrogen content (4.85 wt%), N-containing groups and specific surface area (369.59 m 2 /g) increased greatly, and excellent electrochemical property (120 F/g) was shown with NH 3 concentration increasing. However, NH 3 conversion efficiency decreased gradually with NH 3 increasing, and 40 vol% may be the optimum NH 3 concentration for biomass N-enriched pyrolysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Novel sorbent materials for environmental remediation via Pyrolysis of biomass

    NASA Astrophysics Data System (ADS)

    Zabaniotou, Anastasia

    2013-04-01

    One of the major challenges facing society at this moment is the transition from a non-sustainable, fossil resources-based economy to a sustainable bio-based economy. By producing multiple products, a biorefinery can take advantage of the differences in biomass components and intermediates and maximize the value derived from the biomass feedstock. The high-value products enhance profitability, the high-volume fuel helps meet national energy needs, and the power production reduces costs and avoids greenhouse-gas emissions From pyrolysis, besides gas and liquid products a solid product - char, is derived as well. This char contains the non converted carbon and can be used for activated carbon production and/or as additive in composite material production. Commercially available activated carbons are still considered expensive due to the use of non-renewable and relatively expensive starting material such as coal. The present study describes pyrolysis as a method to produce high added value carbon materials such as activated carbons (AC) from agricultural residues pyrolysis. Olive kernel has been investigated as the precursor of the above materials. The produced activated carbon was characterized by proximate and ultimate analyses, BET method and porosity estimation. Furthermore, its adsorption of pesticide compound in aqueous solution by was studied. Pyrolysis of olive kernel was conducted at 800 oC for 45min in a fixed reactor. For the production of the activated carbon the pyrolytic char was physically activated under steam in the presence of CO2 at 970oC for 3 h in a bench scale reactor. The active carbons obtained from both scales were characterized by N2 adsorption at 77 K, methyl-blue adsorption (MB adsorption) at room temperature and SEM analysis. Surface area and MB adsorption were found to increase with the degree of burn-off. The surface area of the activated carbons was found to increase up to 1500 m2/g at a burn-off level of 60-65wt.%, while SEM analysis

  7. Kinetic Analysis of the Main Temperature Stage of Fast Pyrolysis

    NASA Astrophysics Data System (ADS)

    Yang, Xiaoxiao; Zhao, Yuying; Xu, Lanshu; Li, Rui

    2017-10-01

    Kinetics of the thermal decomposition of eucalyptus chips was evaluated using a high-rate thermogravimetric analyzer (BL-TGA) designed by our research group. The experiments were carried out under non-isothermal condition in order to determine the fast pyrolysis behavior of the main temperature stage (350-540ºC) at heating rates of 60, 120, 180, and 360ºC min-1. The Coats-Redfern integral method and four different reaction mechanism models were adopted to calculate the kinetic parameters including apparent activation energy and pre-exponential factor, and the Flynn-Wall-Ozawa method was employed to testify apparent activation energy. The results showed that estimation value was consistent with the values obtained by linear fitting equations, and the best-fit model for fast pyrolysis was found.

  8. Pyrolytic sugars from cellulosic biomass

    NASA Astrophysics Data System (ADS)

    Kuzhiyil, Najeeb

    Sugars are the feedstocks for many promising advanced cellulosic biofuels. Traditional sugars derived from starch and sugar crops are limited in their availability. In principle, more plentiful supply of sugars can be obtained from depolymerization of cellulose, the most abundant form of biomass in the world. Breaking the glycosidic bonds between the pyranose rings in the cellulose chain to liberate glucose has usually been pursued by enzymatic hydrolysis although a purely thermal depolymerization route to sugars is also possible. Fast pyrolysis of pure cellulose yields primarily levoglucosan, an anhydrosugar that can be hydrolyzed to glucose. However, naturally occurring alkali and alkaline earth metals (AAEM) in biomass are strongly catalytic toward ring-breaking reactions that favor formation of light oxygenates over anhydrosugars. Removing the AAEM by washing was shown to be effective in increasing the yield of anhydrosugars; but this process involves removal of large amount of water from biomass that renders it energy intensive and thereby impractical. In this work passivation of the AAEM (making them less active or inactive) using mineral acid infusion was explored that will increase the yield of anhydrosugars from fast pyrolysis of biomass. Mineral acid infusion was tried by previous researchers, but the possibility of chemical reactions between infused acid and AAEM in the biomass appears to have been overlooked, possibly because metal cations might be expected to already be substantially complexed to chlorine or other strong anions that are found in biomass. Likewise, it appears that previous researchers assumed that as long as AAEM cations were in the biomass, they would be catalytically active regardless of the nature of their complexion with anions. On the contrary, we hypothesized that AAEM can be converted to inactive or less active salts using mineral acids. Various biomass feedstocks were infused with mineral (hydrochloric, nitric, sulfuric and

  9. Catalytic fast pyrolysis of durian rind using silica-alumina catalyst: Effects of pyrolysis parameters.

    PubMed

    Tan, Y L; Abdullah, A Z; Hameed, B H

    2018-05-18

    Silica-alumina catalyst was prepared and used in the catalytic fast pyrolysis of durian rind in a drop-type two-stage reactor. The effects of catalytic temperature (400 °C-600 °C) and catalyst-to-durian rind ratio (1:30-3:30) were evaluated. Bio-oil yield was increased with increased catalytic temperature due to considerable dehydration process, but it was reduced with high catalyst loading due to the overcracking of organics into light gases. Silica-alumina catalyst possessed good selectivity and the products changed according to the temperature. The major components in bio-oil were hydrocarbons, furan derivatives, and aromatic compounds at 400 °C, 500 °C, and 600 °C, respectively. The hydrogen and carbon contents of bio-oil were reduced with high catalyst loading due to the overcracking of organics, and the deoxygenation process became unfavorable. The silica-alumina catalyst worked well in catalytic fast pyrolysis of durian rind, and the condition may be adjusted based on the desired products. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Life cycle water footprint of hydrogenation-derived renewable diesel production from lignocellulosic biomass.

    PubMed

    Wong, Alain; Zhang, Hao; Kumar, Amit

    2016-10-01

    The conversion of lignocellulosic biomass to biofuel requires water. This study is focused on the production of hydrogenation-derived renewable diesel (HDRD) from lignocellulosic biomass. Although there has been considerable focus on the assessment of greenhouse gas (GHG) emissions, there is limited work on the assessment of the life cycle water footprint of HDRD production. This paper presents a life cycle water consumption study on lignocellulosic biomass to HDRD via pyrolysis and hydrothermal liquefaction (HTL) processes. The results of this study show that whole tree (i.e., tree chips) biomass has water requirements of 497.79 L/MJ HDRD and 376.16 L/MJ HDRD for production through fast pyrolysis and the HTL process, respectively. Forest residues (i.e., chips from branches and tops generated during logging operations) have water requirements of 338.58 L/MJ HDRD and 255.85 L/MJ HDRD for production through fast pyrolysis and the HTL process, respectively. Agricultural residues (i.e., straw from wheat, oats, and barley), which are more water efficient, have water requirements of 83.7 L/MJ HDRD and 59.1 L/MJ HDRD through fast pyrolysis and the HTL process, respectively. Differences in water use between feedstocks and conversion processes indicate that the choices of biomass feedstock and conversion pathway water efficiency are crucial factors affecting water use efficiency of HDRD production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Effects of various reactive gas atmospheres on the properties of bio-oil using microwave pyrolysis

    USDA-ARS?s Scientific Manuscript database

    Fast pyrolysis of lignocellulosic biomass produces organic liquids (bio-oil), bio-char, water, and non-condensable gases. The non-condensable gas component typically contains syngas (H2, CO and CO2) as well as small hydrocarbons (CH4, C2H6, and C3H8). Tail Gas Reactive Pyrolysis (TGRP), a patent p...

  12. Pyrolysis kinetic and product analysis of different microalgal biomass by distributed activation energy model and pyrolysis-gas chromatography-mass spectrometry.

    PubMed

    Yang, Xuewei; Zhang, Rui; Fu, Juan; Geng, Shu; Cheng, Jay Jiayang; Sun, Yuan

    2014-07-01

    To assess the energy potential of different microalgae, Chlorella sorokiniana and Monoraphidium were selected for studying the pyrolytic behavior at different heating rates with the analytical method of thermogravimetric analysis (TG), distributed activation energy model (DAEM) and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). Results presented that Monoraphidium 3s35 showed superiority for pyrolysis at low heating rate. Calculated by DAEM, during the conversion rate range from 0.1 to 0.7, the activation energies of C. sorokiniana 21 were much lower than that of Monoraphidium 3s35. Both C. sorokiniana 21 and Monoraphidium 3s35 can produce certain amount (up to 20.50%) of alkane compounds, with 9-Octadecyne (C18H34) as the primary compound. Short-chain alkanes (C7-C13) with unsaturated carbon can be released in the pyrolysis at 500°C for both microalgal biomass. It was also observed that the pyrolysis of C. sorokiniana 21 released more alcohol compounds, while Monoraphidium 3s35 produced more saccharides. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Pyrolysis of agricultural biomass residues: Comparative study of corn cob, wheat straw, rice straw and rice husk.

    PubMed

    Biswas, Bijoy; Pandey, Nidhi; Bisht, Yashasvi; Singh, Rawel; Kumar, Jitendra; Bhaskar, Thallada

    2017-08-01

    Pyrolysis studies on conventional biomass were carried out in fixed bed reactor at different temperatures 300, 350, 400 and 450°C. Agricultural residues such as corn cob, wheat straw, rice straw and rice husk showed that the optimum temperatures for these residues are 450, 400, 400 and 450°C respectively. The maximum bio-oil yield in case of corn cob, wheat straw, rice straw and rice husk are 47.3, 36.7, 28.4 and 38.1wt% respectively. The effects of pyrolysis temperature and biomass type on the yield and composition of pyrolysis products were investigated. All bio-oils contents were mainly composed of oxygenated hydrocarbons. The higher area percentages of phenolic compounds were observed in the corn cob bio-oil than other bio-oils. From FT-IR and 1 H NMR spectra showed a high percentage of aliphatic functional groups for all bio-oils and distribution of products is different due to differences in the composition of agricultural biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Catalytic co-pyrolysis of switchgrass and polyethylene over HZSM-5: catalyst deactivation and coke formation

    USDA-ARS?s Scientific Manuscript database

    When conducted in the presence of a zeolite catalyst such as HZSM-5, fast pyrolysis of biomass can promote the rejection of oxygen and the formation of aromatic hydrocarbons in the organic liquid products. Unfortunately, this pathway removes hydrogen from the already hydrogen deficient biomass start...

  15. Aqueous extractive upgrading of bio-oils created by tail-gas reactive pyrolysis to produce pure hydrocarbons and phenols

    USDA-ARS?s Scientific Manuscript database

    Tail-gas reactive pyrolysis (TGRP) of biomass produces bio-oil that is lower in oxygen (~15 wt% total) and significantly more hydrocarbon-rich than traditional bio-oils or even catalytic fast pyrolysis. TGRP bio-oils lend themselves toward mild and inexpensive upgrading procedures. We isolated oxyge...

  16. Physical pretreatment of biogenic-rich trommel fines for fast pyrolysis.

    PubMed

    Eke, Joseph; Onwudili, Jude A; Bridgwater, Anthony V

    2017-12-01

    Energy from Waste (EfW) technologies such as fluidized bed fast pyrolysis, are beneficial for both energy generation and waste management. Such technologies, however face significant challenges due to the heterogeneous nature, particularly the high ash contents of some municipal solid waste types e.g. trommel fines. A study of the physical/mechanical and thermal characteristics of these complex wastes is important for two main reasons; (a) to inform the design and operation of pyrolysis systems to handle the characteristics of such waste; (b) to control/modify the characteristics of the waste to fit with existing EFW technologies via appropriate feedstock preparation methods. In this study, the preparation and detailed characterisation of a sample of biogenic-rich trommel fines has been carried out with a view to making the feedstock suitable for fast pyrolysis based on an existing fluidized bed reactor. Results indicate that control of feed particle size was very important to prevent problems of dust entrainment in the fluidizing gas as well as to prevent feeder hardware problems caused by large stones and aggregates. After physical separation and size reduction, nearly 70wt% of the trommel fines was obtained within the size range suitable for energy recovery using the existing fast pyrolysis system. This pyrolyzable fraction could account for about 83% of the energy content of the 'as received' trommel fines sample. Therefore there was no significant differences in the thermochemical properties of the raw and pre-treated feedstocks, indicating that suitably prepared trommel fines samples can be used for energy recovery, with significant reduction in mass and volume of the original waste. Consequently, this can lead to more than 90% reduction in the present costs of disposal of trommel fines in landfills. In addition, the recovered plastics and textile materials could be used as refuse derived fuel. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Catalyst Residence Time Distributions in Riser Reactors for Catalytic Fast Pyrolysis. Part 2: Pilot-Scale Simulations and Operational Parameter Study

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Foust, Thomas D.; Ziegler, Jack L.; Pannala, Sreekanth

    2017-02-21

    Here, wsing the validated simulation model developed in part one of this study for biomass catalytic fast pyrolysis (CFP), we assess the functional utility of using this validated model to assist in the development of CFP processes in fluidized catalytic cracking (FCC) reactors to a commercially viable state. Specifically, we examine the effects of mass flow rates, boundary conditions (BCs), pyrolysis vapor molecular weight variation, and the impact of the chemical cracking kinetics on the catalyst residence times. The factors that had the largest impact on the catalyst residence time included the feed stock molecular weight and the degree ofmore » chemical cracking as controlled by the catalyst activity. Lastly, because FCC reactors have primarily been developed and utilized for petroleum cracking, we perform a comparison analysis of CFP with petroleum and show the operating regimes are fundamentally different.« less

  18. Bio-oil production from fast pyrolysis of waste furniture sawdust in a fluidized bed.

    PubMed

    Heo, Hyeon Su; Park, Hyun Ju; Park, Young-Kwon; Ryu, Changkook; Suh, Dong Jin; Suh, Young-Woong; Yim, Jin-Heong; Kim, Seung-Soo

    2010-01-01

    The amount of waste furniture generated in Korea was over 2.4 million tons in the past 3 years, which can be used for renewable energy or fuel feedstock production. Fast pyrolysis is available for thermo-chemical conversion of the waste wood mostly into bio-oil. In this work, fast pyrolysis of waste furniture sawdust was investigated under various reaction conditions (pyrolysis temperature, particle size, feed rate and flow rate of fluidizing medium) in a fluidized-bed reactor. The optimal pyrolysis temperature for increased yields of bio-oil was 450 degrees C. Excessively smaller or larger feed size negatively affected the production of bio-oil. Higher flow and feeding rates were more effective for the production of bio-oil, but did not greatly affect the bio-oil yields within the tested ranges. The use of product gas as the fluidizing medium had a potential for increased bio-oil yields.

  19. Biomass-based pyrolytic polygeneration system on cotton stalk pyrolysis: influence of temperature.

    PubMed

    Chen, Yingquan; Yang, Haiping; Wang, Xianhua; Zhang, Shihong; Chen, Hanping

    2012-03-01

    To study the process of biomass-based pyrolytic polygeneration and its mechanism in depth, the pyrolysis of cotton stalk was investigated in a packed bed, with focus on the evolution of the chemical and physical structures of the solid, liquid and gaseous products. The evolution of product characteristics could be good explaining the process mechanism of biomass pyrolysis. A relationship between the pore distribution of solid products and the fused aromatic rings system revealed by Raman analysis might be exist and need to quantify in further study. Regarding the optimum conditions for obtaining high-quality pyrolytic products from the polygeneration system, the optimum temperature is 550-750°C, with a higher calorific value of the obtained charcoal (≈ 28 MJ/kg) and a higher surface area (>200 m(2)/g). Meanwhile, the calorific value of the gas reaches 8-9 MJ/m(3) and the liquid oil would be used as a platform product in biorefinery. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

  20. Intrinsic activation: the relationship between biomass inorganic content and porosity formation during pyrolysis.

    PubMed

    Stratford, James P; Hutchings, Tony R; de Leij, Frans A A M

    2014-05-01

    The utility of pyrolytic carbons is closely related to their porosity and surface area, there is a clear benefit to the development of biomass pyrolysis processes which produce highly porous carbons. The results presented in this work demonstrate that by using biomass precursors with high inorganic content along with specified process conditions, carbons can be consistently produced with specific surface areas between 900 and 1600 m(2)/g. Results from 12 different source materials show that the formation of increased porosity in pyrolytic carbons is strongly associated with the presence of inorganic elements in the precursors including: magnesium, potassium and sulfur. It was found that pyrolysis of macro-algae can produce especially high specific surface area carbons (mean: 1500 m(2)/g), without externally applied activating agents. Using cheap readily available agricultural residues such as oilseed rape straw, pyrolytic carbons can be produced with specific surface areas of around 950 m(2)/g. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. Portable in-woods pyrolysis: Using forest biomass to reduce forest fuels, increase soil productivity, and sequester carbon

    Treesearch

    Deborah Page-Dumroese; Mark Coleman; Greg Jones; Tyron Venn; R. Kasten Dumroese; Nathanial Anderson; Woodam Chung; Dan Loeffler; Jim Archuleta; Mark Kimsey; Phil Badger; Terry Shaw; Kristin McElligott

    2009-01-01

    We describe the use of an in-woods portable pyrolysis unit that converts forest biomass to bio-oil and the application of the byproduct bio-char in a field trial. We also discuss how in-woods processing may reduce the need for long haul distances of lowvalue woody biomass and eliminate open, currently wasteful burning of forest biomass. If transportation costs can be...

  2. Molecular Analysis of Primary Vapor and Char Products during Stepwise Pyrolysis of Poplar Biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jones, Roger W.; Reinot, Tonu; McClelland, John F.

    2010-08-03

    Pyrolysis of biomass produces both pyrolysis oil and solid char. In this study, poplar has been pyrolyzed in a stepwise fashion over a series of temperatures from 200 to 500°C, and both the primary products contributing to pyrolysis oil and the changes in the pyrolyzing poplar surface leading toward char have been characterized at each step. The primary products were identified by direct analysis in real time (DART) mass spectrometry, and the changes in the poplar surface were monitored using Fourier transform infrared (FTIR) photoacoustic spectroscopy, with a sampling depth of a few micrometers. The primary products from pyrolyzing cellulose,more » xylan, and lignin under similar conditions were also characterized to identify the sources of the poplar products.« less

  3. Molecular Analysis of Primary Vapor and Char Products during Stepwise Pyrolysis of Poplar Biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jones, Roger W.; Reinot, Tonu; McClelland, John F.

    2010-08-30

    Pyrolysis of biomass produces both pyrolysis oil and solid char. In this study, poplar has been pyrolyzed in a stepwise fashion over a series of temperatures from 200 to 500 C, and both the primary products contributing to pyrolysis oil and the changes in the pyrolyzing poplar surface leading toward char have been characterized at each step. The primary products were identified by direct analysis in real time (DART) mass spectrometry, and the changes in the poplar surface were monitored using Fourier transform infrared (FTIR) photoacoustic spectroscopy, with a sampling depth of a few micrometers. The primary products from pyrolyzingmore » cellulose, xylan, and lignin under similar conditions were also characterized to identify the sources of the poplar products.« less

  4. Biotechnological Perspectives of Pyrolysis Oil for a Bio-Based Economy.

    PubMed

    Arnold, Stefanie; Moss, Karin; Henkel, Marius; Hausmann, Rudolf

    2017-10-01

    Lignocellulosic biomass is an important feedstock for a potential future bio-based economy. Owing to its compact structure, suitable decomposition technologies will be necessary to make it accessible for biotechnological conversion. While chemical and enzymatic hydrolysis are currently established methods, a promising alternative is provided by fast pyrolysis. The main resulting product thereof, referred to as pyrolysis oil, is an energy-rich and easily transportable liquid. Many of the identified constituents of pyrolysis oil, however, have previously been reported to display adverse effects on microbial growth. In this Opinion we discuss relevant biological, biotechnological, and technological challenges that need to be addressed to establish pyrolysis oil as a reliable microbial feedstock for a bio-based economy of the future. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Optimizing anti-coking abilities of zeolites by ethylene diamine tetraacetie acid modification on catalytic fast pyrolysis of corn stalk

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Zhong, Zhaoping; Song, Zuwei; Ding, Kuan; Chen, Paul; Ruan, Roger

    2015-12-01

    In order to minimize coke yield during biomass catalytic fast pyrolysis (CFP) process, ethylene diamine tetraacetie acid (EDTA) chemical modification method is carried out to selectively remove the external framework aluminum of HZSM-5 catalyst. X-ray diffraction (XRD), nitrogen (N2)-adsorption and ammonia-temperature programmed desorption (NH3-TPD) techniques are employed to investigate the porosity and acidity characteristics of original and modified HZSM-5 samples. Py-GC/MS and thermo-gravimetric analyzer (TGA) experiments are further conducted to explore the catalytic effect of modified HZSM-5 samples on biomass CFP and to verify the positive effect on coke reduction. Results show that EDTA treatment does not damage the crystal structure of HZSM-5 zeolites, but leads to a slight increase of pore volume and pore size. Meanwhile, the elimination of the strong acid peak indicates the dealumination of outer surface of HZSM-5 zeolites. Treatment time of 2 h (labeled EDTA-2H) is optimal for acid removal and hydrocarbon formation. Among all modified catalysts, EDTA-2H performs the best for deacidification and can obviously increase the yields of positive chemical compositions in pyrolysis products. Besides, EDTA modification can improve the anti-coking properties of HZSM-5 zeolites, and EDTA-2H gives rise to the lowest coke yield.

  6. Quantitative 13C NMR characterization of fast pyrolysis oils

    DOE PAGES

    Happs, Renee M.; Lisa, Kristina; Ferrell, III, Jack R.

    2016-10-20

    Quantitative 13C NMR analysis of model catalytic fast pyrolysis (CFP) oils following literature procedures showed poor agreement for aromatic hydrocarbons between NMR measured concentrations and actual composition. Furthermore, modifying integration regions based on DEPT analysis for aromatic carbons resulted in better agreement. Solvent effects were also investigated for hydrotreated CFP oil.

  7. Quantitative 13C NMR characterization of fast pyrolysis oils

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Happs, Renee M.; Lisa, Kristina; Ferrell, III, Jack R.

    Quantitative 13C NMR analysis of model catalytic fast pyrolysis (CFP) oils following literature procedures showed poor agreement for aromatic hydrocarbons between NMR measured concentrations and actual composition. Furthermore, modifying integration regions based on DEPT analysis for aromatic carbons resulted in better agreement. Solvent effects were also investigated for hydrotreated CFP oil.

  8. Can portable pyrolysis units make biomass utilization affordable while using bio-char to enhance soil productivity and sequester carbon?

    Treesearch

    Mark Coleman; Deborah Page-Dumroese; Jim Archuleta; Phil Badger; Woodum Chung; Tyron Venn; Dan Loeffler; Greg Jones; Kristin McElligott

    2010-01-01

    We describe a portable pyrolysis system for bioenergy production from forest biomass that minimizes long-distance transport costs and provides for nutrient return and long-term soil carbon storage. The cost for transporting biomass to conversion facilities is a major impediment to utilizing forest biomass. If forest biomass could be converted into bio-oil in the field...

  9. Performance of compact fast pyrolysis reactor with Auger-type modules for the continuous liquid biofuel production

    NASA Astrophysics Data System (ADS)

    Nishimura, Shun; Ebitani, Kohki

    2018-01-01

    Development of a compact fast pyrolysis reactor constructed using Auger-type technology to afford liquid biofuel with high yield has been an interesting concept in support of local production for local consumption. To establish a widely useable module package, details of the performance of the developing compact module reactor were investigated. This study surveyed the properties of as-produced pyrolysis oil as a function of operation time, and clarified the recent performance of the developing compact fast pyrolysis reactor. Results show that after condensation in the scrubber collector, e.g. approx. 10 h for a 25 kg/h feedstock rate, static performance of pyrolysis oil with approximately 20 MJ/kg (4.8 kcal/g) calorific values were constantly obtained after an additional 14 h. The feeding speed of cedar chips strongly influenced the time for oil condensation process: i.e. 1.6 times higher feeding speed decreased the condensation period by half (approx. 5 h in the case of 40 kg/h). Increasing the reactor throughput capacity is an important goal for the next stage in the development of a compact fast pyrolysis reactor with Auger-type modules.

  10. Field-to-Fuel Performance Testing of Lignocellulosic Feedstocks for Fast Pyrolysis and Upgrading: Techno-economic Analysis and Greenhouse Gas Life Cycle Analysis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Meyer, Pimphan A.; Snowden-Swan, Lesley J.; Rappé, Kenneth G.

    This work shows preliminary results from techno-economic analysis and life cycle greenhouse gas analysis of the conversion of seven (7) biomass feedstocks to produce liquid transportation fuels via fast pyrolysis and upgrading via hydrodeoxygenation. The biomass consists of five (5) pure feeds (pine, tulip poplar, hybrid poplar, switchgrass, corn stover) and two blends. Blend 1 consists of equal weights of pine, tulip poplar and switchgrass, and blend 2 is 67% pine and 33% hybrid poplar. Upgraded oil product yield is one of the most significant parameters affecting the process economics, and is a function of both fast pyrolysis oil yieldmore » and hydrotreating oil yield. Pure pine produced the highest overall yield, while switchgrass produced the lowest. Interestingly, herbaceous materials blended with woody biomass performed nearly as well as pure woody feedstock, suggesting a non-trivial relationship between feedstock attributes and production yield. Production costs are also highly dependent upon hydrotreating catalyst-related costs. The catalysts contribute an average of ~15% to the total fuel cost, which can be reduced through research and development focused on achieving performance at increased space velocity (e.g., reduced catalyst loading) and prolonging catalyst lifetime. Green-house-gas reduction does not necessarily align with favorable economics. From the greenhouse gas analysis, processing tulip poplar achieves the largest GHG emission reduction relative to petroleum (~70%) because of its lower hydrogen consumption in the upgrading stage that results in a lower natural gas requirement for hydrogen production. Conversely, processing blend 1 results in the smallest GHG emission reduction from petroleum (~58%) because of high natural gas demand for hydrogen production.« less

  11. Determination of silicon in biomass and products of pyrolysis process via high-resolution continuum source atomic absorption spectrometry.

    PubMed

    Nakadi, Flávio V; Prodanov, Caroline; Boschetti, Wiliam; Vale, Maria Goreti R; Welz, Bernhard; de Andrade, Jailson B

    2018-03-01

    Thermochemical processes can convert the biomass into fuels, such as bio-oil. The biomass submitted to pyrolysis process, such as fibers, are generally rich in silicon, an element that can lead to damages in an engine when there is high concentration in a fuel. High-resolution continuum source atomic absorption spectrometry (HR-CS AAS) is an interesting alternative for Si determination in the products and byproducts of the pyrolysis process because, besides the flame (F) and graphite furnace (GF) atomizers, it has enhanced the application of direct analysis of solid samples (SS) within GF. This study aimed the development of methods to determine Si in biomass samples, their products and byproducts using HR-CS AAS. A high-resolution continuum source atomic absorption spectrometer contrAA 700 equipped with F and GF atomizers was used throughout the study. HR-CS F AAS (λ = 251.611nm, 1 detection pixel, N 2 O/C 2 H 2 flame) was used to evaluate Si content in biomass and ash, after a microwave-assisted acid digestion with HNO 3 and HF. HR-CS GF AAS (T pyr = 1400°C, T atom = 2650°C) has evaluated Si in pyrolysis water and bio-oil at 251.611nm, and in peach pit biomass and ash at 221.174nm using SS, both wavelengths with 1 detection pixel. Rhodium (300μg) was applied as permanent modifier and 10μgPd + 6μg Mg were pipetted onto the standards/samples at each analysis. Three different biomass samples were studied: palm tree fiber, coconut fiber and peach pit, and three certified reference materials (CRM) were used to verify the accuracy of the methods. The figures of merit were LOD 0.09-20mgkg -1 , and LOQ 0.3-20mgkg -1 , considering all the methods. There were no significant differences between the CRM certified values and the determined ones, using a Student t-test with a confidence interval of 95% (n = 5). Si concentration ranged from 0.11-0.92% mm -1 , 1.1-1.7mgkg -1 , 3.3-13mgkg -1 , and 0.41-1.4%mm -1 , in biomass, bio-oil, pyrolysis water and ash, respectively

  12. Pyrolysis for exploitation of biomasses selected for soil phytoremediation: Characterization of gaseous and solid products.

    PubMed

    Giudicianni, Paola; Pindozzi, Stefania; Grottola, Corinna Maria; Stanzione, Fernando; Faugno, Salvatore; Fagnano, Massimo; Fiorentino, Nunzio; Ragucci, Raffaele

    2017-03-01

    Biomasses to be used in the phytoremediation process are generally selected to match agronomic parameters and heavy metals uptake ability. A proper selection can be made greatly effective if knowledge of the properties of the residual char from pyrolysis is available to identify possible valorization routes. In this study a comparative analysis of the yields and characteristics of char obtained from slow pyrolysis of five uncontaminated biomasses (Populus nigra, Salix alba, Fraxinus oxyphylla, Eucalyptus occidentalis and Arundo donax) was carried out under steam atmosphere to better develop char porosity. Moreover, the dependence of the properties of solid residue on the process final temperature was studied for E. occidentalis in the temperature range of 688-967K. The results demonstrate that, among the studied biomasses, chars from P. nigra and E. occidentalis have to be preferred for applications regulated by surface phenomena given their highest surface area (270-300m 2 /g), whereas char from E. occidentalis is the best choice when the goal is to maximize energy recovery. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Kinetic compensation effect in logistic distributed activation energy model for lignocellulosic biomass pyrolysis.

    PubMed

    Xu, Di; Chai, Meiyun; Dong, Zhujun; Rahman, Md Maksudur; Yu, Xi; Cai, Junmeng

    2018-06-04

    The kinetic compensation effect in the logistic distributed activation energy model (DAEM) for lignocellulosic biomass pyrolysis was investigated. The sum of square error (SSE) surface tool was used to analyze two theoretically simulated logistic DAEM processes for cellulose and xylan pyrolysis. The logistic DAEM coupled with the pattern search method for parameter estimation was used to analyze the experimental data of cellulose pyrolysis. The results showed that many parameter sets of the logistic DAEM could fit the data at different heating rates very well for both simulated and experimental processes, and a perfect linear relationship between the logarithm of the frequency factor and the mean value of the activation energy distribution was found. The parameters of the logistic DAEM can be estimated by coupling the optimization method and isoconversional kinetic methods. The results would be helpful for chemical kinetic analysis using DAEM. Copyright © 2018 Elsevier Ltd. All rights reserved.

  14. Methods and apparatuses for preparing upgraded pyrolysis oil

    DOEpatents

    Brandvold, Timothy A; Baird, Lance Awender; Frey, Stanley Joseph

    2013-10-01

    Methods and apparatuses for preparing upgraded pyrolysis oil are provided herein. In an embodiment, a method of preparing upgraded pyrolysis oil includes providing a biomass-derived pyrolysis oil stream having an original oxygen content. The biomass-derived pyrolysis oil stream is hydrodeoxygenated under catalysis in the presence of hydrogen to form a hydrodeoxygenated pyrolysis oil stream comprising a cyclic paraffin component. At least a portion of the hydrodeoxygenated pyrolysis oil stream is dehydrogenated under catalysis to form the upgraded pyrolysis oil.

  15. Microwave pyrolysis using self-generated pyrolysis gas as activating agent: An innovative single-step approach to convert waste palm shell into activated carbon

    NASA Astrophysics Data System (ADS)

    Yek, Peter Nai Yuh; Keey Liew, Rock; Shahril Osman, Mohammad; Chung Wong, Chee; Lam, Su Shiung

    2017-11-01

    Waste palm shell (WPS) is a biomass residue largely available from palm oil industries. An innovative microwave pyrolysis method was developed to produce biochar from WPS while the pyrolysis gas generated as another product is simultaneously used as activating agent to transform the biochar into waste palm shell activated carbon (WPSAC), thus allowing carbonization and activation to be performed simultaneously in a single-step approach. The pyrolysis method was investigated over a range of process temperature and feedstock amount with emphasis on the yield and composition of the WPSAC obtained. The WPSAC was tested as dye adsorbent in removing methylene blue. This pyrolysis approach provided a fast heating rate (37.5°/min) and short process time (20 min) in transforming WPS into WPSAC, recording a product yield of 40 wt%. The WPSAC was detected with high BET surface area (≥ 1200 m2/g), low ash content (< 5 wt%), and high pore volume (≥ 0.54 cm3/g), thus recording high adsorption efficiency of 440 mg of dye/g. The desirable process features (fast heating rate, short process time) and the recovery of WPSAC suggest the exceptional promise of the single-step microwave pyrolysis approach to produce high-grade WPSAC from WPS.

  16. Two-step catalytic hydrodeoxygenation of fast pyrolysis oil to hydrocarbon liquid fuels.

    PubMed

    Xu, Xingmin; Zhang, Changsen; Liu, Yonggang; Zhai, Yunpu; Zhang, Ruiqin

    2013-10-01

    Two-step catalytic hydrodeoxygenation (HDO) of fast pyrolysis oil was investigated for translating pyrolysis oil to transportation grade hydrocarbon liquid fuels. At the first mild HDO step, various organic solvents were employed to promote HDO of bio-oil to overcome coke formation using noble catalyst (Ru/C) under mild conditions (300 °C, 10 MPa). At the second deep HDO step, conventional hydrogenation setup and catalyst (NiMo/Al2O3) were used under severe conditions (400 °C, 13 MPa) for obtaining hydrocarbon fuel. Results show that the phenomenon of coke formation is effectively eliminated, and the properties of products have been significantly improved, such as oxygen content decreases from 48 to 0.5 wt% and high heating value increases from 17 to 46 MJ kg(-1). GC-MS analysis indicates that the final products include C11-C27 aliphatic hydrocarbons and aromatic hydrocarbons. In short, the fast pyrolysis oils were successfully translated to hydrocarbon liquid fuels using a two-step catalytic HDO process. Copyright © 2013 Elsevier Ltd. All rights reserved.

  17. In-situ upgrading of biomass pyrolysis vapors: catalyst screening on a fixed bed reactor.

    PubMed

    Stefanidis, S D; Kalogiannis, K G; Iliopoulou, E F; Lappas, A A; Pilavachi, P A

    2011-09-01

    In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500°C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon-hydrogen-oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields. Copyright © 2011 Elsevier Ltd. All rights reserved.

  18. Biomass Catalytic Pyrolysis on Ni/ZSM-5: Effects of Nickel Pretreatment and Loading

    DOE PAGES

    Yung, Matthew M.; Starace, Anne K.; Mukarakate, Calvin; ...

    2016-04-25

    Here in this work, Ni/ZSM-5 catalysts with varied nickel loadings were evaluated for their ability to produce aromatic hydrocarbons by upgrading of pine pyrolysis vapors. The effect of catalyst pretreatment by hydrogen reduction was also investigated. Results indicate that the addition of nickel increases the yield of aromatic hydrocarbons while simultaneously increasing the conversion of oxygenates, relative to ZSM-5, and these effects are more pronounced with increasing nickel loading. Additionally, while initial activity differences were observed between the oxidized and reduced forms of nickel on ZSM-5 (i.e., NiO/ZSM-5 versus Ni/ZSM-5), the activity of both catalysts converges with increasing time onmore » stream. These reaction results coupled with characterization of pristine and spent catalysts suggest that the catalysts reach similar active states during catalytic pyrolysis, regardless of pretreatment, as NiO undergoes in situ reduction to Ni by biomass pyrolysis vapors. This reduction of NiO to Ni was confirmed by reaction results and characterization by NH 3 temperature-programmed desorption, temperature-programmed reduction, and X-ray diffraction. This finding is significant in that the ability to reduce or eliminate the need for a pre-reaction H 2 reduction of Ni-modified zeolite catalysts could reduce process complexity and operating costs in a biorefinery-based vapor-phase upgrading process to produce biomass-derived fuels and chemicals. The ability to monitor catalyst activity in real time with a molecular beam mass spectrometer used to measure uncondensed, hot pyrolysis vapors allows for an improved understanding of the mechanism for improved activity with Ni addition to ZSM-5, which is attributed to the ability to prevent deactivation by deposition of coke and capping of zeolite micropores.« less

  19. Acetylene from the co-pyrolysis of biomass and waste tires or coal in the H{sub 2}/Ar plasma

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bao, W.; Cao, Q.; Lv, Y.

    Acetylene from carbon-containing materials via plasma pyrolysis is not only simple but also environmentally friendly. In this article, the acetylene produced from co-pyrolyzing biomass with waste tire or coal under the conditions of H{sub 2}/Ar DC arc plasma jet was investigated. The experimental results showed that the co-pyrolysis of mixture with biomass and waste tire or coal can improve largely the acetylene relative volume fraction (RVF) in gaseous products and the corresponding yield of acetylene. The change trends for the acetylene yield of plasma pyrolysis from mixture with raw sample properties were the same as relevant RVF. But the yieldmore » change trend with feeding rate is different from its RVF. The effects of the feeding rate of raw materials and the electric current of plasmatron on acetylene formation are also discussed.« less

  20. Chemical and ecotoxicological properties of three bio-oils from pyrolysis of biomasses.

    PubMed

    Campisi, Tiziana; Samorì, Chiara; Torri, Cristian; Barbera, Giuseppe; Foschini, Anna; Kiwan, Alisar; Galletti, Paola; Tagliavini, Emilio; Pasteris, Andrea

    2016-10-01

    In view of the potential use of pyrolysis-based technologies, it is crucial to understand the environmental hazards of pyrolysis-derived products, in particular bio-oils. Here, three bio-oils were produced from fast pyrolysis of pine wood and intermediate pyrolysis of corn stalk and poultry litter. They were fully characterized by chemical analysis and tested for their biodegradability and their ecotoxicity on the crustacean Daphnia magna and the green alga Raphidocelis subcapitata. These tests were chosen as required by the European REACH regulation. These three bio-oils were biodegradable, with 40-60% of biodegradation after 28 days, and had EC50 values above 100mgL(-1) for the crustacean and above 10mgL(-1) for the alga, showing low toxicity to the aquatic life. The toxic unit approach was applied to verify whether the observed toxicity could be predicted from the data available for the substances detected in the bio-oils. The predicted values largely underestimated the experimental values. Copyright © 2016 Elsevier Inc. All rights reserved.

  1. Pyrolysis kinetics of coking coal mixed with biomass under non-isothermal and isothermal conditions.

    PubMed

    Jeong, Ha Myung; Seo, Myung Won; Jeong, Sang Mun; Na, Byung Ki; Yoon, Sang Jun; Lee, Jae Goo; Lee, Woon Jae

    2014-03-01

    To investigate the kinetic characteristics of coking coal mixed with biomass during pyrolysis, thermogravimetric (TG) and thermo-balance reactor (TBR) analyses were conducted under non-isothermal and isothermal condition. Yellow poplar as a biomass (B) was mixed with weak coking coal (WC) and hard coking coal (HC), respectively. The calculated activation energies of WC/B blends were higher than those of HC/B blends under non-isothermal and isothermal conditions. The coal/biomass blends show increased reactivity and decreased activation energy with increasing biomass blend ratio, regardless of the coking properties of the coal. The different char structures of the WC/B and HC/B blends were analyzed by BET and SEM. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor

    DOE PAGES

    Jarvis, Mark W.; Olstad, Jessica; Parent, Yves; ...

    2018-01-02

    We investigate and quantitate the changes in hydrocarbon product composition while evaluating the performance and operability of the National Renewable Energy Laboratory's Davison Circulating Riser (DCR) reactor system when biomass model compounds are cofed with traditional fluid catalyst cracking (FCC) feeds and catalyst: vacuum gas oil (VGO) and equilibrium zeolite catalyst (E-Cat). Three compounds (acetic acid, guaiacol, and sorbitan monooleate) were selected to represent the major classes of oxygenates present in biomass pyrolysis vapors. These vapors can contain 30-50% oxygen as oxygenates, which create conversion complications (increased reactivity and coking) when integrating biomass vapors and liquids into fuel and chemicalmore » processes long dominated by petroleum feedstocks. We used these model compounds to determine the appropriate conditions for coprocessing with petroleum and ultimately pure pyrolysis vapors only as compared with standard baseline conditions obtained with VGO and E-Cat only in the DCR. Model compound addition decreased the DCR catalyst circulation rate, which controls reactor temperature and measures reaction heat demand, while increasing catalyst coking rates. Liquid product analyses included 2-dimensional gas chromatography time-of-flight mass spectroscopy (2D GCxGC TOFS), simulated distillation (SIM DIST), 13C NMR, and carbonyl content. Aggregated results indicated that the model compounds were converted during reaction, and despite functional group differences, product distributions for each model compound were very similar. In addition, we determined that adding model compounds to the VGO feed did not significantly affect the DCR's operability or performance. Future work will assess catalytic upgrading of biomass pyrolysis vapor to fungible hydrocarbon products using upgrading catalysts currently being developed at NREL and at Johnson Matthey.« less

  3. Catalytic Upgrading of Biomass Pyrolysis Oxygenates with Vacuum Gas Oil Using a Davison Circulating Riser Reactor

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jarvis, Mark W.; Olstad, Jessica; Parent, Yves

    We investigate and quantitate the changes in hydrocarbon product composition while evaluating the performance and operability of the National Renewable Energy Laboratory's Davison Circulating Riser (DCR) reactor system when biomass model compounds are cofed with traditional fluid catalyst cracking (FCC) feeds and catalyst: vacuum gas oil (VGO) and equilibrium zeolite catalyst (E-Cat). Three compounds (acetic acid, guaiacol, and sorbitan monooleate) were selected to represent the major classes of oxygenates present in biomass pyrolysis vapors. These vapors can contain 30-50% oxygen as oxygenates, which create conversion complications (increased reactivity and coking) when integrating biomass vapors and liquids into fuel and chemicalmore » processes long dominated by petroleum feedstocks. We used these model compounds to determine the appropriate conditions for coprocessing with petroleum and ultimately pure pyrolysis vapors only as compared with standard baseline conditions obtained with VGO and E-Cat only in the DCR. Model compound addition decreased the DCR catalyst circulation rate, which controls reactor temperature and measures reaction heat demand, while increasing catalyst coking rates. Liquid product analyses included 2-dimensional gas chromatography time-of-flight mass spectroscopy (2D GCxGC TOFS), simulated distillation (SIM DIST), 13C NMR, and carbonyl content. Aggregated results indicated that the model compounds were converted during reaction, and despite functional group differences, product distributions for each model compound were very similar. In addition, we determined that adding model compounds to the VGO feed did not significantly affect the DCR's operability or performance. Future work will assess catalytic upgrading of biomass pyrolysis vapor to fungible hydrocarbon products using upgrading catalysts currently being developed at NREL and at Johnson Matthey.« less

  4. Preliminary studies of bio-oil from fast pyrolysis of coconut fibers.

    PubMed

    Almeida, Tarciana M; Bispo, Mozart D; Cardoso, Anne R T; Migliorini, Marcelo V; Schena, Tiago; de Campos, Maria Cecilia V; Machado, Maria Elisabete; López, Jorge A; Krause, Laiza C; Caramão, Elina B

    2013-07-17

    This work studied fast pyrolysis as a way to use the residual fiber obtained from the shells of coconut ( Cocos nucifera L. var. Dwarf, from Aracaju, northeastern Brazil). The bio-oil produced by fast pyrolysis and the aqueous phase (formed during the pyrolysis) were characterized by GC/qMS and GC×GC/TOF-MS. Many oxygenated compounds such as phenols, aldehydes, and ketones were identified in the extracts obtained in both phases, with a high predominance of phenolic compounds, mainly alkylphenols. Eighty-one compounds were identified in the bio-oil and 42 in the aqueous phase using GC/qMS, and 95 and 68 in the same samples were identified by GC×GC/TOF-MS. The better performance of GC×GC/TOF-MS was due to the possibility of resolving some coeluted peaks in the one-dimension gas chromatography. Semiquantitative analysis of the samples verified that 59% of the area on the chromatogram of bio-oil is composed by phenols and 12% by aldehydes, mainly furfural. Using the same criterion, 77% of the organic compounds in the aqueous phase are phenols. Therefore, this preliminary assessment indicates that coconut fibers have the potential to be a cost-effective and promising alternative to obtain new products and minimize environmental impact.

  5. Biomass pyrolysis and combustion integral and differential reaction heats with temperatures using thermogravimetric analysis/differential scanning calorimetry.

    PubMed

    Shen, Jiacheng; Igathinathane, C; Yu, Manlu; Pothula, Anand Kumar

    2015-06-01

    Integral reaction heats of switchgrass, big bluestem, and corn stalks were determined using thermogravimetric analysis/differential scanning calorimetry (TGA/DSC). Iso-conversion differential reaction heats using TGA/DSC pyrolysis and combustion of biomass were not available, despite reports available on heats required and released. A concept of iso-conversion differential reaction heats was used to determine the differential reaction heats of each thermal characteristics segment of these materials. Results showed that the integral reaction heats were endothermic from 30 to 700°C for pyrolysis of switchgrass and big bluestem, but they were exothermic for corn stalks prior to 587°C. However, the integral reaction heats for combustion of the materials followed an endothermic to exothermic transition. The differential reaction heats of switchgrass pyrolysis were predominantly endothermic in the fraction of mass loss (0.0536-0.975), and were exothermic for corn stalks (0.0885-0.850) and big bluestem (0.736-0.919). Study results provided better insight into biomass thermal mechanism. Published by Elsevier Ltd.

  6. A case study of pyrolysis of oil palm wastes in Malaysia

    NASA Astrophysics Data System (ADS)

    Abdullah, Nurhayati; Sulaiman, Fauziah; Aliasak, Zalila

    2013-05-01

    Biomass seems to have a great potential as a source of renewable energy compared with other sources. The use of biomass as a source of energy could help to reduce the wastes and also to minimize the dependency on non-renewable energy, hence minimize environmental degradation. Among other types of biomass, oil palm wastes are the major contribution for energy production in Malaysia since Malaysia is one of the primary palm oil producers in the world. Currently, Malaysia's plantation area covers around 5 million hectares. In the oil palm mill, only 10% palm oil is produced and the other 90% is in the form of wastes such as empty fruit bunches (EFB), oil palm shells (OPS), oil palm fibre (OPFb) and palm oil mill effluent (POME). If these wastes are being used as a source of renewable energy, it is believed that it will help to increase the country's economy. Recently, the most potential and efficient thermal energy conversion technology is pyrolysis process. The objective of this paper is to review the current research on pyrolysis of oil palm wastes in Malaysia. The scope of this paper is to discuss on the types of pyrolysis process and its production. At present, most of the research conducted in this country is on EFB and OPS by fast, slow and microwave-assisted pyrolysis processes for fuel applications.

  7. Investigation on thermochemical behaviour of low rank Malaysian coal, oil palm biomass and their blends during pyrolysis via thermogravimetric analysis (TGA).

    PubMed

    Idris, Siti Shawalliah; Abd Rahman, Norazah; Ismail, Khudzir; Alias, Azil Bahari; Abd Rashid, Zulkifli; Aris, Mohd Jindra

    2010-06-01

    This study aims to investigate the behaviour of Malaysian sub-bituminous coal (Mukah Balingian), oil palm biomass (empty fruit bunches (EFB), kernel shell (PKS) and mesocarp fibre (PMF)) and their respective blends during pyrolysis using thermogravimetric analysis (TGA). The coal/palm biomass blends were prepared at six different weight ratios and experiments were carried out under dynamic conditions using nitrogen as inert gas at various heating rates to ramp the temperature from 25 degrees C to 900 degrees C. The derivative thermogravimetric (DTG) results show that thermal decomposition of EFB, PMF and PKS exhibit one, two and three distinct evolution profiles, respectively. Apparently, the thermal profiles of the coal/oil palm biomass blends appear to correlate with the percentage of biomass added in the blends, thus, suggesting lack of interaction between the coal and palm biomass. First-order reaction model were used to determine the kinetics parameters for the pyrolysis of coal, palm biomass and their respective blends. (c) 2010 Elsevier Ltd. All rights reserved.

  8. Evaluation of Brazilian biomasses as potential feedstocks for fuel production via fast pyrolysis

    USDA-ARS?s Scientific Manuscript database

    The utilization of lignocellulosic materials to generate energy is constantly expanding around the world. In addition to the well-known biofuels such as ethanol and biodiesel, advanced biofuels obtained by thermochemical conversion routes have been explored, including pyrolysis oil, biochar and syng...

  9. Catalytic Deoxygenation of Biomass Pyrolysis Vapors to Improve Bio-oil Stability

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dayton, David C.

    2016-12-22

    The President’s Advanced Energy Initiative called for a change in the way Americans fuel their vehicles to promote improved energy security. Increasing biofuels production from domestic lignocellulosic resources requires advanced technology development to achieve the aggressive targets set forth to reduce motor gasoline consumption by 20% in ten years (by 2017). The U.S. Department of Energy (USDOE) Office of the Biomass Program (currently Bioenergy Technologies Office) is actively funding research and development in both biochemical and thermochemical conversion technologies to accelerate the deployment of biofuels technologies in the near future to meet the goals of the Advanced Energy Initiative. Thermochemicalmore » conversion technology options include both gasification and pyrolysis to enable the developing lignocellulosic biorefineries and maximize biomass resource utilization for production of biofuels.« less

  10. Life cycle environmental and economic tradeoffs of using fast pyrolysis products for power generation

    USDA-ARS?s Scientific Manuscript database

    Bio-oils produced from small-scale pyrolysis technology may have economic and environmental benefits for both densifying agricultural biomass and supplying local bio-energy markets (e.g., Renewable Portfolio Standards). This study presents a life cycle assessment (LCA) of a farm-scale bio-oil produ...

  11. Hydrocarbon Liquid Production via Catalytic Hydroprocessing of Phenolic Oils Fractionated from Fast Pyrolysis of Red Oak and Corn Stover

    DOE PAGES

    Elliott, Douglas C.; Wang, Huamin; Rover, Majorie; ...

    2015-04-13

    Phenolic oils were produced from fast pyrolysis of two different biomass feedstocks, red oak and corn stover and evaluated in hydroprocessing tests for production of liquid hydrocarbon products. The phenolic oils were produced with a bio-oil fractionating process in combination with a simple water wash of the heavy ends from the fractionating process. Phenolic oils derived from the pyrolysis of red oak and corn stover were recovered with yields (wet biomass basis) of 28.7 wt% and 14.9 wt%, respectively, and 54.3% and 58.6% on a carbon basis. Both precious metal catalysts and sulfided base metal catalyst were evaluated for hydrotreatingmore » the phenolic oils, as an extrapolation from whole bio-oil hydrotreatment. They were effective in removing heteroatoms with carbon yields as high as 81% (unadjusted for the 90% carbon balance). There was nearly complete heteroatom removal with residual O of only 0.4% to 5%, while N and S were reduced to less than 0.05%. Use of the precious metal catalysts resulted in more saturated products less completely hydrotreated compared to the sulfided base metal catalyst, which was operated at higher temperature. The liquid product was 42-52% gasoline range molecules and about 43% diesel range molecules. Particulate matter in the phenolic oils complicated operation of the reactors, causing plugging in the fixed-beds especially for the corn stover phenolic oil. This difficulty contrasts with the catalyst bed fouling and plugging, which is typically seen with hydrotreatment of whole bio-oil. This problem was substantially alleviated by filtering the phenolic oils before hydrotreating. More thorough washing of the phenolic oils during their preparation from the heavy ends of bio-oil or on-line filtration of pyrolysis vapors to remove particulate matter before condensation of the bio-oil fractions is recommended.« less

  12. Hydrocarbon Liquid Production via Catalytic Hydroprocessing of Phenolic Oils Fractionated from Fast Pyrolysis of Red Oak and Corn Stover

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Elliott, Douglas C.; Wang, Huamin; Rover, Majorie

    Phenolic oils were produced from fast pyrolysis of two different biomass feedstocks, red oak and corn stover and evaluated in hydroprocessing tests for production of liquid hydrocarbon products. The phenolic oils were produced with a bio-oil fractionating process in combination with a simple water wash of the heavy ends from the fractionating process. Phenolic oils derived from the pyrolysis of red oak and corn stover were recovered with yields (wet biomass basis) of 28.7 wt% and 14.9 wt%, respectively, and 54.3% and 58.6% on a carbon basis. Both precious metal catalysts and sulfided base metal catalyst were evaluated for hydrotreatingmore » the phenolic oils, as an extrapolation from whole bio-oil hydrotreatment. They were effective in removing heteroatoms with carbon yields as high as 81% (unadjusted for the 90% carbon balance). There was nearly complete heteroatom removal with residual O of only 0.4% to 5%, while N and S were reduced to less than 0.05%. Use of the precious metal catalysts resulted in more saturated products less completely hydrotreated compared to the sulfided base metal catalyst, which was operated at higher temperature. The liquid product was 42-52% gasoline range molecules and about 43% diesel range molecules. Particulate matter in the phenolic oils complicated operation of the reactors, causing plugging in the fixed-beds especially for the corn stover phenolic oil. This difficulty contrasts with the catalyst bed fouling and plugging, which is typically seen with hydrotreatment of whole bio-oil. This problem was substantially alleviated by filtering the phenolic oils before hydrotreating. More thorough washing of the phenolic oils during their preparation from the heavy ends of bio-oil or on-line filtration of pyrolysis vapors to remove particulate matter before condensation of the bio-oil fractions is recommended.« less

  13. Pyrolysis of coal, biomass and their blends: performance assessment by thermogravimetric analysis.

    PubMed

    Ferrara, Francesca; Orsini, Alessandro; Plaisant, Alberto; Pettinau, Alberto

    2014-11-01

    With the aim to support the experimental tests in a gasification pilot plant, the thermal decomposition of coal, biomass and their mixtures has been carried out through a thermogravimetric analysis (TGA) and a simplified kinetic analysis. The TGA of pure fuels indicates the low reactivity of South African coal and the relatively high reactivity of Sardinian Sulcis coal during pyrolysis. Among the tested fuels, biomass (stone pine wood chips) is the most reactive one. These results fully confirm those obtained during the experimental tests in the gasification pilot plant. As for the fuel blends, the analysis shows that the synergic effects between the considered coals and biomass are negligible when they are co-pyrolyzed. The results of the analysis confirm that TGA could be very useful to generally predict the gasification performance and to optimize the experimental campaigns in pilot-scale gasification plants. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Pyrolysis oil combustion in a horizontal box furnace with an externally mixed nozzle

    USDA-ARS?s Scientific Manuscript database

    Combustion characteristics of neat biomass fast-pyrolysis oil were studied in a horizontal combustion chamber with a rectangular cross-section. An air-assisted externally mixed nozzle known to successfully atomize heavy fuel oils was installed in a modified nominal 100 kW (350,000 BTU/h nominal cap...

  15. Characterization of fast-pyrolysis bio-oil distillation residues and their potential applications

    USDA-ARS?s Scientific Manuscript database

    A typical petroleum refinery makes use of the vacuum gas oil by cracking the large molecular weight compounds into light fuel hydrocarbons. For various types of fast pyrolysis bio-oil, successful analogous methods for processing heavy fractions could expedite integration into a petroleum refinery fo...

  16. Evaluation of the antifungal effects of bio-oil prepared with lignocellulosic biomass using fast pyrolysis technology.

    PubMed

    Kim, Kwang Ho; Jeong, Han Seob; Kim, Jae-Young; Han, Gyu Seong; Choi, In-Gyu; Choi, Joon Weon

    2012-10-01

    This study was performed to investigate the utility of bio-oil, produced via a fast pyrolysis process, as an antifungal agent against wood-rot fungi. Bio-oil solutions (25-100 wt.%) were prepared by diluting the bio-oil with EtOH. Wood block samples (yellow poplar and pitch pine) were treated with diluted bio-oil solutions and then subjected to a leaching process under hot water (70°C) for 72 h. After the wood block samples were thoroughly dried, they were subjected to a soil block test using Tyromyces palustris and Trametes versicolor. The antifungal effect of the 75% and 100% bio-oil solutions was the highest for both wood blocks. Scanning electron microscopy analysis indicated that some chemical components in the bio-oil solution could agglomerate together to form clusters in the inner part of the wood during the drying process, which could act as a wood preservative against fungal growth. According to GC/MS analysis, the components of the agglomerate were mainly phenolic compounds derived from lignin polymers. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Characterization of pyrolytic products obtained from fast pyrolysis of chromated copper arsenate (CCA)- and alkaline copper quaternary compounds (ACQ)-treated wood biomasses.

    PubMed

    Kim, Jae-Young; Kim, Tae-Sung; Eom, In-Yong; Kang, Sung Mo; Cho, Tae-Su; Choi, In Gyu; Choi, Joon Weon

    2012-08-15

    In this study, chromated copper arsenate-treated wood (CCA-W) and alkaline copper quaternary compounds-treated wood (ACQ-W) were subjected to fast pyrolysis at 500°C for ca. 2s to produce bio-oil and char. The physicochemical properties of the pyrolytic products as well as the distribution of heavy metals - arsenic, copper and chrome - during fast pyrolysis were investigated. The water content, viscosity, pH and higher heating value (HHV) of bio-oil from CCA-W were 24.8 wt%, 13.5 cSt, 2.1 and 16 MJ/kg, respectively, whereas those of bio-oil from ACQ-W were 27.9 wt%, 16 cSt, 3.0 and 14.1 MJ/kg, respectively. The yields of bio-oil from CCA-W and ACQ-W were 43.3% and 46.6%, respectively, significantly lower than that of control (61.6%). In the pyrolytic products of CCA-W, the concentrations of arsenic, copper and chromium were determined to be 36.4 wt%, 74.0 wt% and 75.4 wt% in char, respectively, 34.5 wt%, 10.3 wt% and 9.0 wt% in bio-oil, respectively, and 29.0 wt%, 15.7 wt% and 15.5 wt% in gas, respectively. In addition, most of the copper appeared in the char (98.8 wt%) and only a trace amount of copper was detected in the bio-oil (0.2 wt%) produced by ACQ-W. Copyright © 2012 Elsevier B.V. All rights reserved.

  18. Novel technologies to improve the performance of biomass pyrolsis systems

    NASA Astrophysics Data System (ADS)

    Liaw, Shi-Shen

    Biomass pyrolysis is a thermochemical conversion process to convert lignocellosic materials into bio-oil, gas, and char. The bio-oil can be further refined to produce transportation fuels, high-value chemicals and heat. Although fast pyrolysis is a very promising technology for high bio-oil production yield, the reactors used have several technological problems that limit their future techno-economic viability. Current fast pyrolysis reactors use large quantities of carrier gas that reduce their thermal efficiency. The use of sand to accelerate heating rates results in serious attrition problems responsible for sand contamination of the bio-char produced. Most of the fast pyrolysis reactors currently used need to process very small particles which consume large quantities of energy in grinding. The bio-oil produced is also highly acidic and corrosive mainly due to the presence of acetic acid. The lack of a viable technology to use the acetic acid contained in these oils is a major challenge for the development of viable bio-oil refineries. The objective of this dissertation is to evaluate several technologies to improve the techno-economic viability of biomass pyrolysis systems. The main hypotheses of this dissertation are: (1) high yields of bio-oils could also be obtained by using auger pyrolysis reactors using very low volumes of carried gas and no sand as a heat carrier if the system is fed with very small particles (2) The grinding energy can be reduced if the biomass is torrefied. There are torrefaction conditions that will not affect the overall yield of pyrolysis products (3) Acetic acid produced during pyrolysis can be removed with the use of a fractional condensation system (4) The acids produced during the torrefaction and pyrolysis with the use of the fractional condensation system can be anaerobically digested to produce methane. In this dissertation, it was proved through Py-GC/MS studies that yield of most of the pyrolytic products can be explained

  19. Comparative study on the pyrolysis behaviour and kinetics of two macroalgae biomass (Gracilaria changii and Gelidium pusillum) by thermogravimetric analysis

    NASA Astrophysics Data System (ADS)

    Roslee, A. N.; Munajat, N. F.

    2017-10-01

    Macroalgae are often referred as seaweed and could be significant biomass resource for the production of numerous energy carriers including biofuels. In this study, the chemical composition of Gracilaria changii (G. changii) and Gelidium pusillum (G. pusillum) were determined through proximate and ultimate analysis and the thermal degradation behaviour of G. changii and G. pusillum were investigated via thermogravimetric analysis (TGA) in determining the important main composition to be considered as biomass fuels. It has found the pyrolysis of G. changii and G. pusillum consists of three stages and stage II is the main decomposition stage with major mass loss of around 52.16% and 44.42%, respectively. The TGA data were then used for determination of kinetic parameters of the pyrolysis process using three model-free methods: Kissinger, Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The apparent activation energy calculated by using Kissinger method for G. changii was lower than G. Pusillum, i.e.173.12 kJ/mol and 193.22 kJ/mol, respectively. The activation energies calculated from KAS and FWO methods were increased with increasing the pyrolysis conversion with average activation energies of 172.32 kJ/mol and 181.19 kJ/mol for G. changii while for G. pusillum (177.42 kJ/mol and 187.4 kJ/mol). G. pusillum has lower and wider distribution of activation energy and revealed that the pyrolysis process for G. changii was easier than G. pusillum. These data provide information for further application for designing and modelling in thermochemical conversion system of macroalgae biomass.

  20. Novel Fast Pyrolysis/Catalytic Technology for the Production of Stable Upgraded Liquids

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Oyama, Ted; Agblevor, Foster; Battaglia, Francine

    The objective of the proposed research is the demonstration and development of a novel biomass pyrolysis technology for the production of a stable bio-oil. The approach is to carry out catalytic hydrodeoxygenation (HDO) and upgrading together with pyrolysis in a single fluidized bed reactor with a unique two-level design that permits the physical separation of the two processes. The hydrogen required for the HDO will be generated in the catalytic section by the water-gas shift reaction employing recycled CO produced from the pyrolysis reaction itself. Thus, the use of a reactive recycle stream is another innovation in this technology. Themore » catalysts will be designed in collaboration with BASF Catalysts LLC (formerly Engelhard Corporation), a leader in the manufacture of attrition-resistant cracking catalysts. The proposed work will include reactor modeling with state-of-the-art computational fluid dynamics in a supercomputer, and advanced kinetic analysis for optimization of bio-oil production. The stability of the bio-oil will be determined by viscosity, oxygen content, and acidity determinations in real and accelerated measurements. A multi-faceted team has been assembled to handle laboratory demonstration studies and computational analysis for optimization and scaleup.« less

  1. Comparison of ethanol production from corn cobs and switchgrass following a pyrolysis-based biorefinery approach.

    PubMed

    Luque, Luis; Oudenhoven, Stijn; Westerhof, Roel; van Rossum, Guus; Berruti, Franco; Kersten, Sascha; Rehmann, Lars

    2016-01-01

    One of the main obstacles in lignocellulosic ethanol production is the necessity of pretreatment and fractionation of the biomass feedstocks to produce sufficiently pure fermentable carbohydrates. In addition, the by-products (hemicellulose and lignin fraction) are of low value, when compared to dried distillers grains (DDG), the main by-product of corn ethanol. Fast pyrolysis is an alternative thermal conversion technology for processing biomass. It has recently been optimized to produce a stream rich in levoglucosan, a fermentable glucose precursor for biofuel production. Additional product streams might be of value to the petrochemical industry. However, biomass heterogeneity is known to impact the composition of pyrolytic product streams, as a complex mixture of aromatic compounds is recovered with the sugars, interfering with subsequent fermentation. The present study investigates the feasibility of fast pyrolysis to produce fermentable pyrolytic glucose from two abundant lignocellulosic biomass sources in Ontario, switchgrass (potential energy crop) and corn cobs (by-product of corn industry). Demineralization of biomass removes catalytic centers and increases the levoglucosan yield during pyrolysis. The ash content of biomass was significantly decreased by 82-90% in corn cobs when demineralized with acetic or nitric acid, respectively. In switchgrass, a reduction of only 50% for both acids could be achieved. Conversely, levoglucosan production increased 9- and 14-fold in corn cobs when rinsed with acetic and nitric acid, respectively, and increased 11-fold in switchgrass regardless of the acid used. After pyrolysis, different configurations for upgrading the pyrolytic sugars were assessed and the presence of potentially inhibitory compounds was approximated at each step as double integral of the UV spectrum signal of an HPLC assay. The results showed that water extraction followed by acid hydrolysis and solvent extraction was the best upgrading strategy

  2. Biomass Pyrolysis Solids as Reducing Agents: Comparison with Commercial Reducing Agents.

    PubMed

    Adrados, Aitziber; De Marco, Isabel; López-Urionabarrenechea, Alexander; Solar, Jon; Caballero, Blanca M; Gastelu, Naia

    2015-12-23

    Biomass is one of the most suitable options to be used as renewable energy source due to its extensive availability and its contribution to reduce greenhouse gas emissions. Pyrolysis of lignocellulosic biomass under appropriate conditions (slow heating rate and high temperatures) can produce a quality solid product, which could be applicable to several metallurgical processes as reducing agent (biocoke or bioreducer). Two woody biomass samples (olives and eucalyptus) were pyrolyzed to produce biocoke. These biocokes were characterized by means of proximate and ultimate analysis, real density, specific surface area, and porosity and were compared with three commercial reducing agents. Finally, reactivity tests were performed both with the biocokes and with the commercial reducing agents. Bioreducers have lower ash and sulfur contents than commercial reducers, higher surface area and porosity, and consequently, much higher reactivity. Bioreducers are not appropriate to be used as top burden in blast furnaces, but they can be used as fuel and reducing agent either tuyére injected at the lower part of the blast furnace or in non-ferrous metallurgical processes where no mechanical strength is needed as, for example, in rotary kilns.

  3. Biomass Pyrolysis Solids as Reducing Agents: Comparison with Commercial Reducing Agents

    PubMed Central

    Adrados, Aitziber; De Marco, Isabel; López-Urionabarrenechea, Alexander; Solar, Jon; Caballero, Blanca M.; Gastelu, Naia

    2015-01-01

    Biomass is one of the most suitable options to be used as renewable energy source due to its extensive availability and its contribution to reduce greenhouse gas emissions. Pyrolysis of lignocellulosic biomass under appropriate conditions (slow heating rate and high temperatures) can produce a quality solid product, which could be applicable to several metallurgical processes as reducing agent (biocoke or bioreducer). Two woody biomass samples (olives and eucalyptus) were pyrolyzed to produce biocoke. These biocokes were characterized by means of proximate and ultimate analysis, real density, specific surface area, and porosity and were compared with three commercial reducing agents. Finally, reactivity tests were performed both with the biocokes and with the commercial reducing agents. Bioreducers have lower ash and sulfur contents than commercial reducers, higher surface area and porosity, and consequently, much higher reactivity. Bioreducers are not appropriate to be used as top burden in blast furnaces, but they can be used as fuel and reducing agent either tuyére injected at the lower part of the blast furnace or in non-ferrous metallurgical processes where no mechanical strength is needed as, for example, in rotary kilns. PMID:28787805

  4. Prediction of properties and elemental composition of biomass pyrolysis oils by NMR and partial least squares analysis

    USDA-ARS?s Scientific Manuscript database

    Several partial least squares (PLS) models were created correlating various properties and chemical composition measurements with the 1H and 13C NMR spectra of 73 different of pyrolysis bio-oil samples from various biomass sources (crude and intermediate products), finished oils and small molecule s...

  5. Chapter 8: Pyrolysis of Biomass for Aviation Fuel

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Robichaud, David J; Jenkins, Rhodri W.; Sutton, Andrew D.

    2016-07-15

    Pyrolysis, the breaking down of organic material using heat and the absence of oxygen, is a method that has been widely researched for the production of liquid fuels. In this chapter, we review the feedstocks typically used for pyrolysis, the properties and the composition of the liquid fraction (termed 'bio-oil') obtained, the studies in which pyrolysis has been used in an attempt to increase the bio-oil yield, and how the bio-oil has been upgraded to fuel-like molecules. We also discuss the viability of pyrolysis to produce jet fuel hydrocarbons.

  6. Synergistic effect on thermal behavior during co-pyrolysis of lignocellulosic biomass model components blend with bituminous coal.

    PubMed

    Wu, Zhiqiang; Wang, Shuzhong; Zhao, Jun; Chen, Lin; Meng, Haiyu

    2014-10-01

    Co-thermochemical conversion of lignocellulosic biomass and coal has been investigated as an effective way to reduce the carbon footprint. Successful evaluating on thermal behavior of the co-pyrolysis is prerequisite for predicting performance and optimizing efficiency of this process. In this paper, pyrolysis and kinetics characteristics of three kinds of lignocellulosic biomass model components (cellulose, hemicellulose, and lignin) blended with a kind of Chinese bituminous coal were explored by thermogravimetric analyzer and Kissinger-Akahira-Sunose method. The results indicated that the addition of model compounds had different synergistic effects on thermal behavior of the bituminous coal. The cellulose showed positive synergistic effects on the thermal decomposition of the coal bituminous coal with lower char yield than calculated value. For hemicellulose and lignin, whether positive or negative synergistic was related to the mixed ratio and temperature range. The distribution of the average activation energy values for the mixtures showed nonadditivity performance. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Carbon dioxide assisted sustainability enhancement of pyrolysis of waste biomass: A case study with spent coffee ground.

    PubMed

    Cho, Dong-Wan; Cho, Seong-Heon; Song, Hocheol; Kwon, Eilhann E

    2015-01-01

    This work mainly presents the influence of CO2 as a reaction medium in the thermo-chemical process (pyrolysis) of waste biomass. Our experimental work mechanistically validated two key roles of CO2 in pyrolysis of biomass. For example, CO2 expedited the thermal cracking of volatile organic compounds (VOCs) evolved from the thermal degradation of spent coffee ground (SCG) and reacted with VOCs. This enhanced thermal cracking behavior and reaction triggered by CO2 directly led to the enhanced generation of CO (∼ 3000%) in the presence of CO2. As a result, this identified influence of CO2 also directly led to the substantial decrease (∼ 40-60%) of the condensable hydrocarbons (tar). Finally, the morphologic change of biochar was distinctive in the presence of CO2. Therefore, a series of the adsorption experiments with dye were conducted to preliminary explore the physico-chemical properties of biochar induced by CO2. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Comparative study of wet and dry torrefaction of corn stalk and the effect on biomass pyrolysis polygeneration.

    PubMed

    Wang, Xianhua; Wu, Jing; Chen, Yingquan; Pattiya, Adisak; Yang, Haiping; Chen, Hanping

    2018-06-01

    Wet torrefaction (WT) possesses some advantages over dry torrefaction (DT). In this study, a comparative analysis of torrefied corn stalk from WT and DT was conducted along with an investigation of their pyrolysis properties under optimal conditions for biomass pyrolysis polygeneration. Compared with DT, WT removed 98% of the ash and retained twice the amount of hydrogen. The impacts of DT and WT on the biomass macromolecular structure was also found to be different using two-dimensional perturbation correlation infrared spectroscopy (2D-PCIS). WT preserved the active hydroxyl groups and rearranged the macromolecule structure to allow cellulose to be more ordered, while DT removed these active hydroxyl groups and formed inter-crosslinking structures in macromolecules. Correspondingly, the bio-char yield after WT was lower than DT but the bio-char quality was upgraded due to high ash removal. Furthermore, higher bio-oil yield, higher sugar content, and higher H 2 generation, were obtained after WT. Copyright © 2018 Elsevier Ltd. All rights reserved.

  9. Influence of mineral matter on pyrolysis of palm oil wastes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yang, Haiping; Chen, Hanping; Zheng, Chuguang

    2006-09-15

    The influence of mineral matter on pyrolysis of biomass (including pure biomass components, synthesized biomass, and natural biomass) was investigated using a thermogravimetric analyzer (TGA). First, the mineral matter, KCl, K{sub 2}CO{sub 3}, Na{sub 2}CO{sub 3}, CaMg(CO{sub 3}){sub 2}, Fe{sub 2}O{sub 3}, and Al{sub 2}O{sub 3}, was mixed respectively with the three main biomass components (hemicellulose, cellulose, and lignin) at a weight ratio (C/W) of 0.1 and its pyrolysis characteristics were investigated. Most of these mineral additives, except for K{sub 2}CO{sub 3}, demonstrated negligible influence. Adding K{sub 2}CO{sub 3} inhibited the pyrolysis of hemicellulose by lowering its mass loss ratemore » by 0.3 wt%/{sup o}C, while it enhanced the pyrolysis of cellulose by shifting the pyrolysis to a lower temperature. With increased K{sub 2}CO{sub 3} added, the weight loss of cellulose in the lower temperature zone (200-315 {sup o}C) increased greatly, and the activation energies of hemicellulose and cellulose pyrolysis decreased notably from 204 to 42 kJ/mol. Second, studies on the synthetic biomass of hemicellulose, cellulose, lignin, and K{sub 2}CO{sub 3} (as a representative of minerals) indicated that peaks of cellulose and hemicellulose pyrolysis became overlapped with addition of K{sub 2}CO{sub 3} (at C/W=0.05-0.1), due to the catalytic effect of K{sub 2}CO{sub 3} lowering cellulose pyrolysis to a lower temperature. Finally, a local representative biomass--palm oil waste (in the forms of original material and material pretreated through water washing or K{sub 2}CO{sub 3} addition)--was studied. Water washing shifted pyrolysis of palm oil waste to a higher temperature by 20 {sup o}C, while K{sub 2}CO{sub 3} addition lowered the peak temperature of pyrolysis by {approx}50{sup o}C. It was therefore concluded that the obvious catalytic effect of adding K{sub 2}CO{sub 3} might be attributed to certain fundamental changes in terms of chemical structure of

  10. Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

    NASA Astrophysics Data System (ADS)

    Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

    2017-06-01

    Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.

  11. Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

    PubMed Central

    Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

    2017-01-01

    Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes. PMID:28660882

  12. Process for preparing phenolic formaldehyde resole resin products derived from fractionated fast-pyrolysis oils

    DOEpatents

    Chum, Helena L.; Kreibich, Roland E.

    1992-01-01

    A process for preparing phenol-formaldehyde resole resins and adhesive compositions in which portions of the phenol normally contained in said resins are replaced by a phenol/neutral fractions extract obtained from fractionating fast-pyrolysis oils.

  13. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christpher P; Boldingh, Edwin P

    2013-12-17

    A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and show to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hyrdocarbons into hydrocarbons removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  14. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-10-07

    A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub.1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  15. Kinetic and energy production analysis of pyrolysis of lignocellulosic biomass using a three-parallel Gaussian reaction model.

    PubMed

    Chen, Tianju; Zhang, Jinzhi; Wu, Jinhu

    2016-07-01

    The kinetic and energy productions of pyrolysis of a lignocellulosic biomass were investigated using a three-parallel Gaussian distribution method in this work. The pyrolysis experiment of the pine sawdust was performed using a thermogravimetric-mass spectroscopy (TG-MS) analyzer. A three-parallel Gaussian distributed activation energy model (DAEM)-reaction model was used to describe thermal decomposition behaviors of the three components, hemicellulose, cellulose and lignin. The first, second and third pseudocomponents represent the fractions of hemicellulose, cellulose and lignin, respectively. It was found that the model is capable of predicting the pyrolysis behavior of the pine sawdust. The activation energy distribution peaks for the three pseudo-components were centered at 186.8, 197.5 and 203.9kJmol(-1) for the pine sawdust, respectively. The evolution profiles of H2, CH4, CO, and CO2 were well predicted using the three-parallel Gaussian distribution model. In addition, the chemical composition of bio-oil was also obtained by pyrolysis-gas chromatography/mass spectrometry instrument (Py-GC/MS). Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hao, Naijia; Bezerra, Tais Lacerda; Wu, Qiong

    Pyrolysis is a promising method for converting biomass to biofuels. However, some of pyrolysis oil's physiochemical properties still limit its commercial applications. Here, the autohydrolysis pretreatment at 175 ± 3 °C for 40 min was conducted to improve the resulting pine pyrolysis oil’s properties as a fuel. During autohydrolysis, deacetylation and decomposition of hemicellulose was observed by ion-exchange chromatography and Fourier transform infrared spectroscopy (FT-IR). Additionally, the cleavage of lignin ether bonds was clearly determined by 13C cross-polarization/magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR). Phosphitylation followed by 31P NMR analysis of the heavy oils gave detailed structural information ofmore » the hydroxyl groups; the results revealed that autohydrolysis pretreatment led to a reduction of carboxyl acids in the heavy oils generated at all three pyrolysis temperatures (400, 500, and 600 °C). The 31P NMR analysis also revealed that autohydrolysis pretreatment led to a reduction of condensed phenolic hydroxyl groups in the heavy oils produced at 600 °C. 1H- 13C heteronuclear single-quantum correlation (HSQC) NMR analysis showed that at a pyrolysis temperature of 600 °C, the pretreated pine produced lower methoxy group constituents. In both 31P and HSQC NMR results indicated that autohydrolysis pretreatment increased levoglucosan yields in the bio-oils.« less

  17. Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process

    DOE PAGES

    Hao, Naijia; Bezerra, Tais Lacerda; Wu, Qiong; ...

    2017-06-29

    Pyrolysis is a promising method for converting biomass to biofuels. However, some of pyrolysis oil's physiochemical properties still limit its commercial applications. Here, the autohydrolysis pretreatment at 175 ± 3 °C for 40 min was conducted to improve the resulting pine pyrolysis oil’s properties as a fuel. During autohydrolysis, deacetylation and decomposition of hemicellulose was observed by ion-exchange chromatography and Fourier transform infrared spectroscopy (FT-IR). Additionally, the cleavage of lignin ether bonds was clearly determined by 13C cross-polarization/magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR). Phosphitylation followed by 31P NMR analysis of the heavy oils gave detailed structural information ofmore » the hydroxyl groups; the results revealed that autohydrolysis pretreatment led to a reduction of carboxyl acids in the heavy oils generated at all three pyrolysis temperatures (400, 500, and 600 °C). The 31P NMR analysis also revealed that autohydrolysis pretreatment led to a reduction of condensed phenolic hydroxyl groups in the heavy oils produced at 600 °C. 1H- 13C heteronuclear single-quantum correlation (HSQC) NMR analysis showed that at a pyrolysis temperature of 600 °C, the pretreated pine produced lower methoxy group constituents. In both 31P and HSQC NMR results indicated that autohydrolysis pretreatment increased levoglucosan yields in the bio-oils.« less

  18. Hydrothermal carbonization of biomass residuals: A comparative review of the chemistry, processes and applications of wet and dry pyrolysis

    USDA-ARS?s Scientific Manuscript database

    This paper reviews chemistry, processes and application of hydrothermcally carbonized biomass wastes. Potential feedstock for the hydrothermal carbonization (HTC) includes variety of the non-traditional renewable wet agricultural and municipal waste streams. Pyrolysis and HTC show a comparable calor...

  19. Computational Studies of Pyrolysis and Upgrading of Bio-oils: Virtual Special Issue

    DOE PAGES

    Xiong, Qingang; Robichaud, David J.

    2017-03-23

    As research activities continue, our understanding of biomass pyrolysis has been significantly elevated and we sought to arrange this Virtual Special Issue (VSI) in ACS Sustainable Chemistry & Engineering to report recent progress on computational and experimental studies of biomass pyrolysis. Beyond highlighting the five national laboratories' advancements, prestigious researchers in the field of biomass pyrolysis have been invited to report their most recent activities.

  20. Preparation, properties, and bonding utilization of pyrolysis bio-oil

    USDA-ARS?s Scientific Manuscript database

    The rapid increase in energy consumption, limited fossil fuel resource, and environmental concerns have stimulated the research need for biomass-derived fuels and chemicals. Pyrolysis is a thermal degradation process of biomass in the absence of oxygen. The liquid product from pyrolysis is known as ...

  1. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Thermochemical Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dutta, Abhijit; Sahir, A. H.; Tan, Eric

    This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from biomass. Specifically, this report details two conceptual designs based on projected product yields and quality improvements via catalyst development and process integration. It is expected that these research improvements will be made within the 2022 timeframe. The two conversion pathways detailed are (1) in situ and (2) ex situ upgrading of vapors produced from the fast pyrolysis of biomass. While the base case conceptual designs and underlying assumptionsmore » outline performance metrics for feasibility, it should be noted that these are only two of many other possibilities in this area of research. Other promising process design options emerging from the research will be considered for future techno-economic analysis. Both the in situ and ex situ conceptual designs, using the underlying assumptions, project MFSPs of approximately $3.5/gallon gasoline equivalent (GGE). The performance assumptions for the ex situ process were more aggressive with higher distillate (diesel-range) products. This was based on an assumption that more favorable reaction chemistry (such as coupling) can be made possible in a separate reactor where, unlike in an in situ upgrading reactor, one does not have to deal with catalyst mixing with biomass char and ash, which pose challenges to catalyst performance and maintenance. Natural gas was used for hydrogen production, but only when off gases from the process was not sufficient to meet the needs; natural gas consumption is insignificant in both the in situ and ex situ base cases. Heat produced from the burning of char, coke, and off-gases allows for the production of surplus electricity which is sold to the grid allowing a reduction of approximately 5¢/GGE in the MFSP.« less

  2. Bio-oil from fast pyrolysis of lignin: Effects of process and upgrading parameters.

    PubMed

    Fan, Liangliang; Zhang, Yaning; Liu, Shiyu; Zhou, Nan; Chen, Paul; Cheng, Yanling; Addy, Min; Lu, Qian; Omar, Muhammad Mubashar; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Anderson, Erik; Peng, Peng; Lei, Hanwu; Ruan, Roger

    2017-10-01

    Effects of process parameters on the yield and chemical profile of bio-oil from fast pyrolysis of lignin and the processes for lignin-derived bio-oil upgrading were reviewed. Various process parameters including pyrolysis temperature, reactor types, lignin characteristics, residence time, and feeding rate were discussed and the optimal parameter conditions for improved bio-oil yield and quality were concluded. In terms of lignin-derived bio-oil upgrading, three routes including pretreatment of lignin, catalytic upgrading, and co-pyrolysis of hydrogen-rich materials have been investigated. Zeolite cracking and hydrodeoxygenation (HDO) treatment are two main methods for catalytic upgrading of lignin-derived bio-oil. Factors affecting zeolite activity and the main zeolite catalytic mechanisms for lignin conversion were analyzed. Noble metal-based catalysts and metal sulfide catalysts are normally used as the HDO catalysts and the conversion mechanisms associated with a series of reactions have been proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Effect of dry torrefaction on kinetics of catalytic pyrolysis of sugarcane bagasse

    NASA Astrophysics Data System (ADS)

    Daniyanto, Sutijan, Deendarlianto, Budiman, Arief

    2015-12-01

    Decreasing world reserve of fossil resources (i.e. petroleum oil, coal and natural gas) encourage discovery of renewable resources as subtitute for fossil resources. Biomass is one of the main natural renewable resources which is promising resource as alternate resources to meet the world's energy needs and raw material to produce chemical platform. Conversion of biomass, as source of energy, fuel and biochemical, is conducted using thermochemical process such as pyrolysis-gasification process. Pyrolysis step is an important step in the mechanism of pyrolysis - gasification of biomass. The objective of this study is to obtain the kinetic reaction of catalytic pyrolysis of dry torrified sugarcane bagasse which used Ca and Mg as catalysts. The model of kinetic reaction is interpreted using model n-order of single reaction equation of biomass. Rate of catalytic pyrolysis reaction depends on the weight of converted biomass into char and volatile matters. Based on TG/DTA analysis, rate of pyrolysis reaction is influenced by the composition of biomass (i.e. hemicellulose, cellulose and lignin) and inorganic component especially alkali and alkaline earth metallic (AAEM). From this study, it has found two equations rate of reaction of catalytic pyrolysis in sugarcane bagasse using catalysts Ca and Mg. First equation is equation of pyrolysis reaction in rapid zone of decomposition and the second equation is slow zone of decomposition. Value of order reaction for rapid decomposition is n > 1 and for slow decomposition is n<1. Constant and order of reactions for catalytic pyrolysis of dry-torrified sugarcane bagasse with presence of Ca tend to higher than that's of presence of Mg.

  4. Characterization of Products from Fast Micropyrolysis of Municipal Solid Waste Biomass

    DOE PAGES

    Klemetsrud, Bethany; Ukaew, Suchada; Thompson, Vicki S.; ...

    2016-09-05

    Biomass feedstock costs remain one of the largest impediments to biofuel production economics. Municipal solid waste (MSW) represents an attractive feedstock with year-round availability, an established collection infrastructure paid for by waste generators, low cost and the potential to be blended with higher cost feedstocks to reduce overall feedstock costs. Paper waste, yard waste and construction and demolition waste (C&D) were examined for their applicability in the pyrolysis conversion pathway. Paper waste consisted of non-recyclable paper such as mixed low grade paper, food and beverage packaging, kitchen paper wastes and coated paper; yard waste consisted of grass clippings and C&Dmore » wastes consisted of engineered wood products obtained from a construction waste landfill. We tested the waste materials for thermochemical conversion potential using a bench scale fast micro-pyrolysis process. Bio-oil yields were the highest for the C&D materials and lowest for the paper waste. The C&D wastes had the highest level of lignin derived compounds (phenolic and cyclics) while the paper waste had higher levels of carbohydrate derived compounds (aldehydes, organic acids, ketones, alcohols and sugar derived). But, the paper material had higher amounts of lignin derived compounds than expected based upon lignin content that is likely due to the presence of polyphenolic resins used in paper processing. The paper and yard wastes had significantly higher levels of ash content than the C&D wastes (14-15% versus 0.5-1.3%), which further correlated to higher levels of alkali and alkaline earth metals, which are known to reduce pyrolysis bio-oil yields. There appeared to be an inverse correlation of both calcium and potassium content with the amount of chromatographic product peaks, indicative of cracking reactions occurring during product formation. Furthermore the effect of acid washing was evaluated for grass clipping and waste paper and the bio-oil yield was increased

  5. Characterization of Products from Fast Micropyrolysis of Municipal Solid Waste Biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Klemetsrud, Bethany; Ukaew, Suchada; Thompson, Vicki S.

    Biomass feedstock costs remain one of the largest impediments to biofuel production economics. Municipal solid waste (MSW) represents an attractive feedstock with year-round availability, an established collection infrastructure paid for by waste generators, low cost and the potential to be blended with higher cost feedstocks to reduce overall feedstock costs. Paper waste, yard waste and construction and demolition waste (C&D) were examined for their applicability in the pyrolysis conversion pathway. Paper waste consisted of non-recyclable paper such as mixed low grade paper, food and beverage packaging, kitchen paper wastes and coated paper; yard waste consisted of grass clippings and C&Dmore » wastes consisted of engineered wood products obtained from a construction waste landfill. We tested the waste materials for thermochemical conversion potential using a bench scale fast micro-pyrolysis process. Bio-oil yields were the highest for the C&D materials and lowest for the paper waste. The C&D wastes had the highest level of lignin derived compounds (phenolic and cyclics) while the paper waste had higher levels of carbohydrate derived compounds (aldehydes, organic acids, ketones, alcohols and sugar derived). But, the paper material had higher amounts of lignin derived compounds than expected based upon lignin content that is likely due to the presence of polyphenolic resins used in paper processing. The paper and yard wastes had significantly higher levels of ash content than the C&D wastes (14-15% versus 0.5-1.3%), which further correlated to higher levels of alkali and alkaline earth metals, which are known to reduce pyrolysis bio-oil yields. There appeared to be an inverse correlation of both calcium and potassium content with the amount of chromatographic product peaks, indicative of cracking reactions occurring during product formation. Furthermore the effect of acid washing was evaluated for grass clipping and waste paper and the bio-oil yield was increased

  6. Formate-assisted pyrolysis

    DOEpatents

    DeSisto, William Joseph; Wheeler, Marshall Clayton; van Heiningen, Adriaan R. P.

    2015-03-17

    The present invention provides, among other thing, methods for creating significantly deoxygenated bio-oils form biomass including the steps of providing a feedstock, associating the feedstock with an alkali formate to form a treated feedstock, dewatering the treated feedstock, heating the dewatered treated feedstock to form a vapor product, and condensing the vapor product to form a pyrolysis oil, wherein the pyrolysis oil contains less than 30% oxygen by weight.

  7. An approach for upgrading biomass and pyrolysis product quality using a combination of aqueous phase bio-oil washing and torrefaction pretreatment.

    PubMed

    Chen, Dengyu; Cen, Kehui; Jing, Xichun; Gao, Jinghui; Li, Chen; Ma, Zhongqing

    2017-06-01

    Bio-oil undergoes phase separation because of poor stability. Practical application of aqueous phase bio-oil is challenging. In this study, a novel approach that combines aqueous phase bio-oil washing and torrefaction pretreatment was used to upgrade the biomass and pyrolysis product quality. The effects of individual and combined pretreatments on cotton stalk pyrolysis were studied using TG-FTIR and a fixed bed reactor. The results showed that the aqueous phase bio-oil washing pretreatment removed metals and resolved the two pyrolysis peaks in the DTG curve. Importantly, it increased the bio-oil yield and improved the pyrolysis product quality. For example, the water and acid content of bio-oil decreased significantly along with an increase in phenol formation, and the heating value of non-condensable gases improved, and these were more pronounced when combined with torrefaction pretreatment. Therefore, the combined pretreatment is a promising method, which would contribute to the development of polygeneration pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Understanding and Controlling Lignocellulosic Pyrolysis for the Production of Renewable Fuel and Chemical Precursors

    NASA Astrophysics Data System (ADS)

    Pecha, Michael Brennan

    Pyrolysis is a technology for producing fuels, chemicals, and engineered carbons from renewable feedstocks like lignocellulosic biomass. This work aims to address some of the scientific and technical hurdles that need to be overcome to control the products of pyrolysis. The first section aims to address knowledge gaps regarding primary pyrolysis reactions; in this study, pine wood was acid washed and small amounts of acid were impregnated into the biomass prior to pyrolysis. Results showed that the acid mitigated fragmentation reactions caused by residual metals and had further effect on production of sugars and oligomeric lignin products. The next section aims to address knowledge gaps regarding what reactions occur in the liquid intermediate phase in biomass pyrolysis; in these studies, a novel reactor system was built which could perform thin film fast pyrolysis studies at different pressures from 4 mbar to 1 atm with cellulose, milled wood lignin, and hybrid poplar wood. The reactor was carefully characterized to achieve comparable data between the different pressures. The use of vacuum allowed for control of the residence time of cellobiosan (one of cellulose oligomeric products) in the liquid intermediate. In the vacuum cellulose pyrolysis studies, a high resolution FT-ICR-MS was used for the first time to explore reaction chemistry for this system. The Van-Krevelen diagram of the resulting oligomeric products proved to be a powerful tool to study secondary reactions in the liquid intermediate. Our results show that the secondary reactions in the liquid intermediate are dominated by dehydration, fragmentation, and cross-linking reactions. The final section aims to address single particle external heat transfer problems; in this study, 500 microm long particles of pine and aspen poplar with realistic pore and surface morphologies were modeled in COMSOL to determine how microstructure effects the external heat transfer coefficients in the laminar flow regime

  9. Biomass Pyrolysis to Hydrocarbon Fuels in the Petroleum Refining Context: Cooperative Research and Development Final Report, CRADA Number CRD-12-500

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chum, Helena L.

    This work focuses on developing a thermochemical route to produce biofuels from agricultural wastes such as sugar cane bagasse, wood chips or corn stover; more specifically it intends to develop the biomass pyrolysis route, which produces bio-oils. Production of bio-oils by pyrolysis is a commercial technology. However, bio-oils are currently not being used for liquid fuels production. Although bio-oils can be produced by high-pressure liquefaction, pyrolysis is a less expensive technology. Nevertheless, bio-oils cannot be used directly as a transportation fuel without upgrading, since they are generally unstable, viscous, and acidic. Thus NREL and Petrobras intend to use their combinedmore » expertise to develop a two-step route to biofuels production: in the first step, a stable bio-oil is produced by NREL biomass pyrolysis technology, while in the second step it is upgraded by using two distinct catalytic processes under development by Petrobras. The first process converts bio-oil into gasoline, LPG, and fuel oil using the catalytic cracking process, while the second one, converts bio-oil into synthesis gas. Syngas gasification catalysts provided by both NREL and Petrobras will be tested. The work includes experiments at both sites to produce bio-oil and then biofuels, life-cycle analysis of each route, personnel training and development of analytical methods with a duration time of two years.« less

  10. Phenolic compounds containing/neutral fractions extract and products derived therefrom from fractionated fast-pyrolysis oils

    DOEpatents

    Chum, H.L.; Black, S.K.; Diebold, J.P.; Kreibich, R.E.

    1993-06-29

    A process is described for preparing phenol-formaldehyde novolak resins and molding compositions in which portions of the phenol normally contained in said resins are replaced by a phenol/neutral fractions extract obtained from fractionating fast-pyrolysis oils. The fractionation consists of a neutralization stage which can be carried out with aqueous solutions of bases or appropriate bases in the dry state, followed by solvent extraction with an organic solvent having at least a moderate solubility parameter and good hydrogen bonding capacity. Phenolic compounds-containing/neutral fractions extracts obtained by fractionating fast-pyrolysis oils from a lignocellulosic material, is such that the oil is initially in the pH range of 2-4, being neutralized with an aqueous bicarbonate base, and extracted into a solvent having a solubility parameter of approximately 8.4-9.11 [cal/cm[sup 3

  11. Thermogravimetric and calorimetric characteristics during co-pyrolysis of municipal solid waste components.

    PubMed

    Ansah, Emmanuel; Wang, Lijun; Shahbazi, Abolghasem

    2016-10-01

    The thermogravimetric and calorimetric characteristics during pyrolysis of wood, paper, textile and polyethylene terephthalate (PET) plastic in municipal solid wastes (MSW), and co-pyrolysis of biomass-derived and plastic components with and without torrefaction were investigated. The active pyrolysis of the PET plastic occurred at a much higher temperature range between 360°C and 480°C than 220-380°C for the biomass derived components. The plastic pyrolyzed at a heating rate of 10°C/min had the highest maximum weight loss rate of 18.5wt%/min occurred at 420°C, followed by 10.8wt%/min at 340°C for both paper and textile, and 9.9wt%/min at 360°C for wood. At the end of the active pyrolysis stage, the final mass of paper, wood, textile and PET was 28.77%, 26.78%, 21.62% and 18.31%, respectively. During pyrolysis of individual MSW components at 500°C, the wood required the least amount of heat at 665.2J/g, compared to 2483.2J/g for textile, 2059.4J/g for paper and 2256.1J/g for PET plastic. The PET plastic had much higher activation energy of 181.86kJ/mol, compared to 41.47kJ/mol for wood, 50.01kJ/mol for paper and 36.65kJ/mol for textile during pyrolysis at a heating rate of 10°C/min. H2O and H2 peaks were observed on the MS curves for the pyrolysis of three biomass-derived materials but there was no obvious H2O and H2 peaks on the MS curves of PET plastic. There was a significant interaction between biomass and PET plastic during co-pyrolysis if the biomass fraction was dominant. The amount of heat required for the co-pyrolysis of the biomass and plastic mixture increased with the increase of plastic mass fraction in the mixture. Torrefaction at a proper temperature and time could improve the grindability of PET plastic. The increase of torrefaction temperature and time did not affect the temperature where the maximum pyrolytic rates occurred for both biomass and plastic but decreased the maximum pyrolysis rate of biomass and increased the maximum pyrolysis

  12. Bio-oil and biochar production from corn cobs and stover by fast pyrolysis

    USDA-ARS?s Scientific Manuscript database

    Bio-oil and bio-char were produced from corn cobs and corn stover (stalks, leaves and husks) by fast pyrolysis using a pilot scale fluidized bed reactor. Yields of 60% (mass/mass) bio-oil (high heating values are ~20,000 kJ/kg, and densities > 1.0 g/mL) were realized from both corn cobs and from co...

  13. Effects of feedstock characteristics on microwave-assisted pyrolysis - A review.

    PubMed

    Zhang, Yaning; Chen, Paul; Liu, Shiyu; Peng, Peng; Min, Min; Cheng, Yanling; Anderson, Erik; Zhou, Nan; Fan, Liangliang; Liu, Chenghui; Chen, Guo; Liu, Yuhuan; Lei, Hanwu; Li, Bingxi; Ruan, Roger

    2017-04-01

    Microwave-assisted pyrolysis is an important approach to obtain bio-oil from biomass. Similar to conventional electrical heating pyrolysis, microwave-assisted pyrolysis is significantly affected by feedstock characteristics. However, microwave heating has its unique features which strongly depend on the physical and chemical properties of biomass feedstock. In this review, the relationships among heating, bio-oil yield, and feedstock particle size, moisture content, inorganics, and organics in microwave-assisted pyrolysis are discussed and compared with those in conventional electrical heating pyrolysis. The quantitative analysis of data reported in the literature showed a strong contrast between the conventional processes and microwave based processes. Microwave-assisted pyrolysis is a relatively new process with limited research compared with conventional electrical heating pyrolysis. The lack of understanding of some observed results warrant more and in-depth fundamental research. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Enhancing biogas production of corn stover by fast pyrolysis pretreatment.

    PubMed

    Wang, Fang; Zhang, Deli; Wu, Houkai; Yi, Weiming; Fu, Peng; Li, Yongjun; Li, Zhihe

    2016-10-01

    A new thermo-chemical pretreatment by a lower temperature fast pyrolysis (LTFP) was applied to promote anaerobic digestion (AD) efficiency of corn stover (CS). The pretreatment experiment was performed by a fluidized bed pyrolysis reactor at 180, 200 and 220°C with a carrier gas flow rate of 4 and 3m(3)/h. The components characteristics, Scanning Electron Microscope (SEM) images and Crystal Intensity (CrI) of the pretreated CS were tested to explore effectiveness of the pretreatment. The results showed that the cumulative methane production at 180°C for 4 and 3m(3)/h were 199.8 and 200.3mL/g TS, respectively. As compared to the untreated CS, the LTFP pretreatment significantly (a<0.05) increased the methane production by 18.07% and 18.33%, respectively. Methane production was well fitted by the Gompertz models, and the maximum methane potential and AD efficiency was obtained at 180°C for 3m(3)/h. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Organic compounds leached from fast pyrolysis mallee leaf and bark biochars.

    PubMed

    Lievens, Caroline; Mourant, Daniel; Gunawan, Richard; Hu, Xun; Wang, Yi

    2015-11-01

    Characterization of organic compounds leached from biochars is essential in assessing the possible toxicity of the biochar to the soils' biota. In this study the nature of the leached organic compounds from Mallee biochars, produced from pyrolysis of Mallee leaf and bark in a fluidised-bed pyrolyser at 400 and 580°C was investigated. Light bio-oil compounds and aromatic organic compounds were investigated. The 'bio-oil like' light compounds from leaf and bark biochars 'surfaces were obtained after leaching the chars with a solvent, suitable to dissolve the respective bio-oils. GC/MS was implemented to investigate the leachates. Phenolics, which are potentially harmful toxins, were detected and their concentration shown to be dependent on the char's origin and the char production temperature. Further, to simulate biochars amendment to soils, the chars were leached with water. The water-leached aromatic compounds from leaf and bark biochars were characterized using UV-fluorescence spectroscopy. Those results suggested that biochars contain leachable compounds of which the nature and amount is dependent on the biomass feedstock, pyrolysis temperature and leaching time. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Production of bio-oil and biochar from soapstock via microwave-assisted co-catalytic fast pyrolysis.

    PubMed

    Dai, Leilei; Fan, Liangliang; Liu, Yuhuan; Ruan, Roger; Wang, Yunpu; Zhou, Yue; Zhao, Yunfeng; Yu, Zhenting

    2017-02-01

    In this study, production of bio-oil and biochar from soapstock via microwave-assisted co-catalytic fast pyrolysis combining the advantages of in-situ and ex-situ catalysis was performed. The effects of catalyst and pyrolysis temperature on product fractional yields and bio-oil chemical compositions were investigated. From the perspective of bio-oil yield, the optimal pyrolysis temperature was 550°C. The use of catalysts reduced the water content, and the addition of bentonite increased the bio-oil yield. Up to 84.16wt.% selectivity of hydrocarbons in the bio-oil was obtained in the co-catalytic process. In addition, the co-catalytic process can reduce the proportion of oxygenates in the bio-oil to 15.84wt.% and eliminate the N-containing compounds completely. The addition of bentonite enhanced the BET surface area of bio-char. In addition, the bio-char removal efficiency of Cd 2+ from soapstock pyrolysis in presence of bentonite was 27.4wt.% higher than without bentonite. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Fast Pyrolysis Behavior of Banagrass as a Function of Temperature and Volatiles Residence Time in a Fluidized Bed Reactor

    DOE PAGES

    Morgan, Trevor James; Turn, Scott Q.; George, Anthe

    2015-08-26

    A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amountsmore » of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. In conclusion, the reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high

  18. Fast Pyrolysis Behavior of Banagrass as a Function of Temperature and Volatiles Residence Time in a Fluidized Bed Reactor

    PubMed Central

    Morgan, Trevor James; Turn, Scott Q.; George, Anthe

    2015-01-01

    A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amounts of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. The reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali

  19. Fast Pyrolysis Behavior of Banagrass as a Function of Temperature and Volatiles Residence Time in a Fluidized Bed Reactor

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Morgan, Trevor James; Turn, Scott Q.; George, Anthe

    A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amountsmore » of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. In conclusion, the reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high

  20. Formation of nanocarbon spheres by thermal treatment of woody char from fast pyrolysis process

    Treesearch

    Qiangu Yan; Hossein Toghiani; Zhiyong Cai; Jilei Zhang

    2014-01-01

    Influences of thermal treatment conditions of temperature, reaction cycle and time, and purge gas type on nanocarbon formation over bio-chars from fast pyrolysis and effects of thermal reaction cycle and purge gas type on bio-char surface functional groups were investigated by temperature-programmed desorption (TPD) and temperature programmed reduction methods....

  1. Effect of Blended Feedstock on Pyrolysis Oil Composition

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Smith, Kristin M; Gaston, Katherine R

    Current techno-economic analysis results indicate biomass feedstock cost represents 27% of the overall minimum fuel selling price for biofuels produced from fast pyrolysis followed by hydrotreating (hydro-deoxygenation, HDO). As a result, blended feedstocks have been proposed as a way to both reduce cost as well as tailor key chemistry for improved fuel quality. For this study, two feedstocks were provided by Idaho National Laboratory (INL). Both were pyrolyzed and collected under the same conditions in the National Renewable Energy Laboratory's (NREL) Thermochemical Process Development Unit (TCPDU). The resulting oil properties were then analyzed and characterized for statistical differences.

  2. Remediation of Petroleum-Contaminated Soil and Simultaneous Recovery of Oil by Fast Pyrolysis.

    PubMed

    Li, De-Chang; Xu, Wan-Fei; Mu, Yang; Yu, Han-Qing; Jiang, Hong; Crittenden, John C

    2018-05-01

    Petroleum-contaminated soil (PCS) caused by the accidental release of crude oil into the environment, which occurs frequently during oil exploitation worldwide, needs efficient and cost-effective remediation. In this study, a fast pyrolysis technology was implemented to remediate the PCS and concurrently recover the oil. The remediation effect related to pyrolytic parameters, the recovery rate of oil and its possible formation pathway, and the physicochemical properties of the remediated PCS and its suitability for planting were systematically investigated. The results show that 50.9% carbon was recovered in oil, whose quality even exceeds that of crude oil. Both extractable total petroleum hydrocarbon (TPH) and water-soluble organic matter (SOM) in PCS were completely removed at 500 °C within 30 min. The remaining carbon in remediated PCS was determined to be in a stable and innocuous state, which has no adverse effect on wheat growth. On the basis of the systematically characterizations of initial PCS and pyrolytic products, a possible thermochemical mechanism was proposed which involves evaporation, cracking and polymerization. In addition, the energy consumption analysis and remediation effect of various PCSs indicate that fast pyrolysis is a viable and cost-effective method for PCS remediation.

  3. High-yield harvest of nanofibers/mesoporous carbon composite by pyrolysis of waste biomass and its application for high durability electrochemical energy storage.

    PubMed

    Liu, Wu-Jun; Tian, Ke; He, Yan-Rong; Jiang, Hong; Yu, Han-Qing

    2014-12-02

    Disposal and recycling of the large scale biomass waste is of great concern. Themochemically converting the waste biomass to functional carbon nanomaterials and bio-oil is an environmentally friendly apporach by reducing greenhouse gas emissions and air pollution caused by open burning. In this work, we reported a scalable, "green" method for the synthesis of the nanofibers/mesoporous carbon composites through pyrolysis of the Fe(III)-preloaded biomass, which is controllable by adjustment of temperature and additive of catalyst. It is found that the coupled catalytic action of both Fe and Cl species is able to effectively catalyze the growth of the carbon nanofibers on the mesoporous carbon and form magnetic nanofibers/mesoporous carbon composites (M-NMCCs). The mechanism for the growth of the nanofibers is proposed as an in situ vapor deposition process, and confirmed by the XRD and SEM results. M-NMCCs can be directly used as electrode materials for electrochemical energy storage without further separation, and exhibit favorable energy storage performance with high EDLC capacitance, good retention capability, and excellent stability and durability (more than 98% capacitance retention after 10,000 cycles). Considering that biomass is a naturally abundant and renewable resource (over billions tons biomass produced every year globally) and pyrolysis is a proven technique, M-NMCCs can be easily produced at large scale and become a sustainable and reliable resource for clean energy storage.

  4. Oxygen speciation in upgraded fast pyrolysis bio-oils by comprehensive two-dimensional gas chromatography.

    PubMed

    Omais, Badaoui; Crepier, Julien; Charon, Nadège; Courtiade, Marion; Quignard, Alain; Thiébaut, Didier

    2013-04-21

    Biomass fast pyrolysis is considered as a promising route to produce liquid for the transportation field from a renewable resource. However, the derived bio-oils are mainly oxygenated (45-50%w/w O on a wet basis) and contain almost no hydrocarbons. Therefore, upgrading is necessary to obtain a liquid with lower oxygen content and characterization of oxygenated compounds in these products is essential to assist conversion reactions. For this purpose, comprehensive two-dimensional gas chromatography (GC × GC) can be investigated. Oxygen speciation in such matrices is hampered by the large diversity of oxygenated families and the complexity of the hydrocarbon matrix. Moreover, response factors must be taken into account for oxygenate quantification as the Flame Ionisation Detector (FID) response varies when a molecule contains heteroatoms. To conclude, no distillation cuts were accessible and the analysis had to cover a large range of boiling points (30-630 °C). To take up this analytical challenge, a thorough optimization approach was developed. In fact, four GC × GC column sets were investigated to separate oxygenated compounds from the hydrocarbon matrix. Both model mixtures and the upgraded biomass flash pyrolysis oil were injected using GC × GC-FID to reach a suitable chromatographic separation. The advantages and drawbacks of each column combination for oxygen speciation in upgraded bio-oils are highlighted in this study. Among the four sets, an original polar × semi-polar column combination was selected and enabled the identification by GC × GC-ToF/MS of more than 40 compounds belonging to eight chemical families: ketones, furans, alcohols, phenols, carboxylic acids, guaiacols, anisols, and esters. For quantification purpose, the GC × GC-FID chromatogram was divided into more than 60 blobs corresponding to the previously identified analyte and hydrocarbon zones. A database associating each blob to a molecule and its specific response factor (determined

  5. Field-to-Fuel Performance Testing of Lignocellulosic Feedstocks: An Integrated Study of the Fast Pyrolysis/Hydrotreating Pathway

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Howe, Daniel T.; Westover, Tyler; Carpenter, Daniel

    2015-05-21

    Feedstock composition can affect final fuel yields and quality for the fast pyrolysis and hydrotreatment upgrading pathway. However, previous studies have focused on individual unit operations rather than the integrated system. In this study, a suite of six pure lignocellulosic feedstocks (clean pine, whole pine, tulip poplar, hybrid poplar, switchgrass, and corn stover) and two blends (equal weight percentages whole pine/tulip poplar/switchgrass and whole pine/clean pine/hybrid poplar) were prepared and characterized at Idaho National Laboratory. These blends then underwent fast pyrolysis at the National Renewable Energy Laboratory and hydrotreatment at Pacific Northwest National Laboratory. Although some feedstocks showed a highmore » fast pyrolysis bio-oil yield such as tulip poplar at 57%, high yields in the hydrotreater were not always observed. Results showed overall fuel yields of 15% (switchgrass), 18% (corn stover), 23% (tulip poplar, Blend 1, Blend 2), 24% (whole pine, hybrid poplar) and 27% (clean pine). Simulated distillation of the upgraded oils indicated that the gasoline fraction varied from 39% (clean pine) to 51% (corn stover), while the diesel fraction ranged from 40% (corn stover) to 46% (tulip poplar). Little variation was seen in the jet fuel fraction at 11 to 12%. Hydrogen consumption during hydrotreating, a major factor in the economic feasibility of the integrated process, ranged from 0.051 g/g dry feed (tulip poplar) to 0.070 g/g dry feed (clean pine).« less

  6. Role of Brønsted acid in selective production of furfural in biomass pyrolysis.

    PubMed

    Zhang, Haiyan; Liu, Xuejun; Lu, Meizhen; Hu, Xinyue; Lu, Leigang; Tian, Xiaoning; Ji, Jianbing

    2014-10-01

    In this work, the role of Brønsted acid for furfural production in biomass pyrolysis on supported sulfates catalysts was investigated. The introduction of Brønsted acid was shown to improve the degradation of polysaccharides to intermediates for furfural, which did not work well when only Lewis acids were used in the process. Experimental results showed that CuSO4/HZSM-5 catalyst exhibited the best performance for furfural (28% yield), which was much higher than individual HZSM-5 (5%) and CuSO4 (6%). The optimum reaction conditions called for the mass ratio of CuSO4/HZSM-5 to be 0.4 and the catalyst/biomass mass ratio to be 0.5. The recycled catalyst exhibited low productivity (9%). Analysis of the catalysts by Py-IR revealed that the CuSO4/HZSM-5 owned a stronger Brønsted acid intensity than HZSM-5 or the recycled CuSO4/HZSM-5. Therefore, the existence of Brønsted acid is necessary to achieve a more productive degradation of biomass for furfural. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Catalytic fast pyrolysis of white oak wood in-situ using a bubbling fluidized bed reactor

    USDA-ARS?s Scientific Manuscript database

    Catalytic fast pyrolysis was performed on white oak wood using two zeolite-type catalysts as bed material in a bubbling fluidized bed reactor. The two catalysts chosen, based on a previous screening study, were Ca2+ exchanged Y54 (Ca-Y54) and a proprietary ß-zeolite type catalyst (catalyst M) both ...

  8. Numerical Approach to Wood Pyrolysis in Considerating Heat Transfer in Reactor Chamber

    NASA Astrophysics Data System (ADS)

    Idris, M.; Novalia, U.

    2017-03-01

    Pyrolysis is the decomposition process of solid biomass into gas, tar and charcoal through thermochemical methods. The composition of biomass consists of cellulose hemi cellulose and lignin, which each will decompose at different temperatures. Currently pyrolysis has again become an important topic to be discussed. Many researchers make and install the pyrolysis reactor to convert biomass waste into clean energy hardware that can be used to help supply energy that has a crisis. Additionally the clean energy derived from biomass waste is a renewable energy, in addition to abundant source also reduce exhaust emissions of fossil energy that causes global warming. Pyrolysis is a method that has long been known by humans, but until now little is known about the phenomenon of the pyrolysis process that occurs in the reactor. One of the Pyrolysis’s phenomena is the heat transfer process from the temperature of the heat source in the reactor and heat the solid waste of biomass. The solid waste of biomass question in this research is rubber wood obtained from one of the company’s home furnishings. Therefore, this study aimed to describe the process of heat transfer in the reactor during the process. ANSYS software was prepared to make the simulation of heat transfer phenomena at the pyrolysis reactor. That’s the numerical calculation carried out for 1200 seconds. Comparison of temperature performed at T1, T2 and T3 to ensure that thermal conductivity is calculated by numerical accordance with experimental data. The distribution of temperature in the reactor chamber specifies the picture that excellent heat conduction effect of the wood near or attached to wooden components, cellulose, hemicellulose and lignin down into gas.

  9. Fast procedure for the analysis of poly(hydroxyalkanoates) in bacterial cells by off-line pyrolysis/gas-chromatography with flame ionization detector.

    PubMed

    Torri, Cristian; Cordiani, Helena; Samorì, Chiara; Favaro, Lorenzo; Fabbri, Daniele

    2014-09-12

    Poly(hydroxyalkanoates) (PHAs) are polyesters formed by saturated short chain hydroxyacids, among which 3-hydroxybutanoic (HB) and 3-hydroxypentanoic (3-hydroxyvalerate, HV) are the most common monomers of homopolymers (e.g. poly(3-hydroxybutyrate), PHB) and copolymers (e.g. poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), PHB-HC). The most widely used approach for their determination is the polymer methanolysis followed by gas chromatography-mass spectrometry (GC-MS) analysis of the methylated monomers; this procedure generally requires the use of additional reagents (e.g. sulfuric acid) and is performed with harmful chlorinated solvents, such as chloroform. The development of fast routine solventless methods for the quantitative determination of PHAs and their monomeric composition is highly desirable to reduce sample pretreatment, speed up the analysis and decrease overall costs. It has been reported that under thermal treatment (e.g. pyrolysis, Py), PHAs are degraded in high yield (>40%, w/wPHA) into the corresponding 2-alkenoic acid (e.g. crotonic acid from PHB). This work aimed at investigating this reaction for direct analysis of PHAs in bacterial cells. The sample was directly subjected to pyrolysis and trapped pyrolysis products were analyzed by GC-FID. Off-line Py/GC-FID was first optimized on pure polymers with different monomer composition (PHB, PHB-HV, PHB-HC) and then applied to bacterial samples deriving from both mixed microbial cultures or selected strains, containing various types and amounts of PHAs. The Py/GC-FID method provided RSD <15% range, limit of detection of 100μg (1% PHAs in biomass), and results comparable to that of methanolysis (R(2)=0.9855), but with minimal sample pretreatment. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Pyrolysis process for producing fuel gas

    NASA Technical Reports Server (NTRS)

    Serio, Michael A. (Inventor); Kroo, Erik (Inventor); Wojtowicz, Marek A. (Inventor); Suuberg, Eric M. (Inventor)

    2007-01-01

    Solid waste resource recovery in space is effected by pyrolysis processing, to produce light gases as the main products (CH.sub.4, H.sub.2, CO.sub.2, CO, H.sub.2O, NH.sub.3) and a reactive carbon-rich char as the main byproduct. Significant amounts of liquid products are formed under less severe pyrolysis conditions, and are cracked almost completely to gases as the temperature is raised. A primary pyrolysis model for the composite mixture is based on an existing model for whole biomass materials, and an artificial neural network models the changes in gas composition with the severity of pyrolysis conditions.

  11. Understanding the Impacts of AFEX™ Pretreatment and Densification on the Fast Pyrolysis of Corn Stover, Prairie Cord Grass, and Switchgrass.

    PubMed

    Sundaram, Vijay; Muthukumarappan, Kasiviswanathan; Gent, Stephen

    2017-03-01

    Lignocellulosic feedstocks corn stover, prairie cord grass, and switchgrass were subjected to ammonia fiber expansion (AFEX™) pretreatment and densified using extrusion pelleting and ComPAKco densification technique. The effects of AFEX™ pretreatment and densification were studied on the fast pyrolysis product yields. Feedstocks were milled in a hammer mill using three different screen sizes (2, 4, and 8 mm) and were subjected to AFEX™ pretreatment. The untreated and AFEX™-pretreated feedstocks were moisture adjusted at three levels (5, 10, and 15 % wb) and were extruded using a lab-scale single screw extruder. The barrel temperature of the extruder was maintained at 75, 100, and 125 °C. Durability of the extruded pellets made from AFEX™-pretreated corn stover, prairie cord grass, and switchgrass varied from 94.5 to 99.2, 94.3 to 98.7, and 90.1 to 97.5 %, respectively. Results of the thermogravimetric analysis showed the decrease in the decomposition temperature of the all the feedstocks after AFEX™ pretreatment indicating the increase in thermal stability. Loose and densified feedstocks were subjected to fast pyrolysis in a lab-scale reactor, and the yields (bio-oil and bio-char) were measured. Bio-char obtained from the AFEX™-pretreated feedstocks exhibited increased bulk and particle density compared to the untreated feedstocks. The properties of the bio-oil were statistically similar for the untreated, AFEX™-pretreated, and AFEX™-pretreated densified feedstocks. Based on the bio-char and bio-oil yields, the AFEX™-pretreated feedstocks and the densified AFEX™-pretreated feedstocks (pellets and PAKs) exhibited similar behavior. Hence, it can be concluded that densifying the AFEX™-pretreated feedstocks could be a viable option in the biomass-processing depots to reduce the transportation costs and the logistical impediments without affecting the product yields.

  12. A steady state model of agricultural waste pyrolysis: A mini review.

    PubMed

    Trninić, M; Jovović, A; Stojiljković, D

    2016-09-01

    Agricultural waste is one of the main renewable energy resources available, especially in an agricultural country such as Serbia. Pyrolysis has already been considered as an attractive alternative for disposal of agricultural waste, since the technique can convert this special biomass resource into granular charcoal, non-condensable gases and pyrolysis oils, which could furnish profitable energy and chemical products owing to their high calorific value. In this regard, the development of thermochemical processes requires a good understanding of pyrolysis mechanisms. Experimental and some literature data on the pyrolysis characteristics of corn cob and several other agricultural residues under inert atmosphere were structured and analysed in order to obtain conversion behaviour patterns of agricultural residues during pyrolysis within the temperature range from 300 °C to 1000 °C. Based on experimental and literature data analysis, empirical relationships were derived, including relations between the temperature of the process and yields of charcoal, tar and gas (CO2, CO, H2 and CH4). An analytical semi-empirical model was then used as a tool to analyse the general trends of biomass pyrolysis. Although this semi-empirical model needs further refinement before application to all types of biomass, its prediction capability was in good agreement with results obtained by the literature review. The compact representation could be used in other applications, to conveniently extrapolate and interpolate these results to other temperatures and biomass types. © The Author(s) 2016.

  13. Biomass conversion processes for energy and fuels

    NASA Astrophysics Data System (ADS)

    Sofer, S. S.; Zaborsky, O. R.

    The book treats biomass sources, promising processes for the conversion of biomass into energy and fuels, and the technical and economic considerations in biomass conversion. Sources of biomass examined include crop residues and municipal, animal and industrial wastes, agricultural and forestry residues, aquatic biomass, marine biomass and silvicultural energy farms. Processes for biomass energy and fuel conversion by direct combustion (the Andco-Torrax system), thermochemical conversion (flash pyrolysis, carboxylolysis, pyrolysis, Purox process, gasification and syngas recycling) and biochemical conversion (anaerobic digestion, methanogenesis and ethanol fermentation) are discussed, and mass and energy balances are presented for each system.

  14. DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hong, Yongchun; Hensley, Alyssa; McEwen, Jean-Sabin

    Catalytic fast pyrolysis is the most promising approach for biofuel production, due to its simple process and versatility to handle lignocellulosic biomass feedstocks with varying and complex compositions. Compared with in situ catalytic fast pyrolysis, ex situ catalytic pyrolysis has the flexibility of optimizing the pyrolysis step and catalytic process individually to improve the quality of pyrolysis oil (stability, oxygen content, acid number, etc.) and to maximize the carbon efficiency in the conversion of biomass to pyrolysis oil. Hydrodeoxygenation is one of the key catalytic functions in ex situ catalytic fast pyrolysis. Recently, Fe-based catalysts have been reported to exhibitmore » superior catalytic properties in hydrodeoxygenation of model compounds in pyrolysis oil, which potentially makes the ex situ pyrolysis of biomass commercially viable due to the abundance and low cost of Fe. Here, we briefly summarize the recent progress on Fe-based catalysts for hydrodeoxygenation of biomass, and provide perspectives on how to further improve Fe-based catalysts (activity and stability) for their potential applications in the emerging area of biomass conversion.« less

  15. Impact of Macroporosity on Catalytic Upgrading of Fast Pyrolysis Bio-Oil by Esterification over Silica Sulfonic Acids.

    PubMed

    Manayil, Jinesh C; Osatiashtiani, Amin; Mendoza, Alvaro; Parlett, Christopher M A; Isaacs, Mark A; Durndell, Lee J; Michailof, Chrysoula; Heracleous, Eleni; Lappas, Angelos; Lee, Adam F; Wilson, Karen

    2017-09-11

    Fast pyrolysis bio-oils possess unfavorable physicochemical properties and poor stability, in large part, owing to the presence of carboxylic acids, which hinders their use as biofuels. Catalytic esterification offers an atom- and energy-efficient route to upgrade pyrolysis bio-oils. Propyl sulfonic acid (PrSO 3 H) silicas are active for carboxylic acid esterification but suffer mass-transport limitations for bulky substrates. The incorporation of macropores (200 nm) enhances the activity of mesoporous SBA-15 architectures (post-functionalized by hydrothermal saline-promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of the turnover frequency (TOF) enhancement increasing with carboxylic acid chain length from 5 % (C 3 ) to 110 % (C 12 ). Macroporous-mesoporous PrSO 3 H/SBA-15 also provides a two-fold TOF enhancement over its mesoporous analogue for the esterification of a real, thermal fast-pyrolysis bio-oil derived from woodchips. The total acid number was reduced by 57 %, as determined by GC×GC-time-of-flight mass spectrometry (GC×GC-ToFMS), which indicated ester and ether formation accompanying the loss of acid, phenolic, aldehyde, and ketone components. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Slow pyrolysis polygeneration of bamboo (Phyllostachys pubescens): Product yield prediction and biochar formation mechanism.

    PubMed

    Wang, Huihui; Wang, Xin; Cui, Yanshan; Xue, Zhongcai; Ba, Yuxin

    2018-05-11

    Slow pyrolysis of bamboo was conducted at 400-600 °C and pyrolysis products were characterized with FTIR, BET, XRD, SEM, EDS and GC to establish a pyrolysis product yield prediction model and biochar formation mechanism. Pyrolysis biochar yield was predicted based on content of cellulose, hemicellulose and lignin in biomass with their carbonization index of 0.20, 0.35 and 0.45. The formation mechanism of porous structure in pyrolysis biochar was established based on its physicochemical property evolution and emission characteristics of pyrolysis gas. The main components (cellulose, hemicellulose and lignin) had different pyrolysis or chemical reaction pathways to biochar. Lignin had higher aromatic structure, which resulted higher biochar yield. It was the main biochar precursor during biomass pyrolysis. Cellulose was likely to improve porous structure of pyrolysis biochar due to its high mass loss percentage. Higher pyrolysis temperatures (600 °C) promoted inter- and intra-molecular condensation reactions and aromaticity in biochar. Copyright © 2018 Elsevier Ltd. All rights reserved.

  17. Pollutant formation in the pyrolysis and combustion of materials combining biomass and e-waste.

    PubMed

    Soler, Aurora; Conesa, Juan A; Iñiguez, María E; Ortuño, Nuria

    2018-05-01

    Combustion and pyrolysis runs at 850°C were carried out in a laboratory scale horizontal reactor with different materials combining biomass and waste electrical and electronic equipment (WEEE). Analyses are presented of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorinated benzenes (ClBzs), polychlorinated phenols (ClPhs), polybrominated phenols (BrPhs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Results showed that gas emissions were mainly composed of CO and CO 2 ; the high level of CO found in the pyrolytic runs was easily transformed into CO 2 by reaction with oxygen. The total amount of light hydrocarbons emitted was higher in the samples containing WEEE, methane being the most abundant light hydrocarbon in all the runs. However, the presence of WEEE reduced the emission of PAHs which decreased with the increase of the oxygen. The total amount of BrPhs increased in the decomposition of the samples containing WEEE, reaching its maximum in pyrolysis runs. Emission of PCDD/Fs was enhanced in pyrolytic conditions and easily decreased in the presence of oxygen. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-04-29

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  19. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2013-12-17

    A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

  20. One-pot synthesis of carbon supported calcined-Mg/Al layered double hydroxides for antibiotic removal by slow pyrolysis of biomass waste

    PubMed Central

    Tan, Xiaofei; Liu, Shaobo; Liu, Yunguo; Gu, Yanling; Zeng, Guangming; Cai, Xiaoxi; Yan, ZhiLi; Yang, Chunping; Hu, Xinjiang; Chen, Bo

    2016-01-01

    A biochar supported calcined-Mg/Al layered double hydroxides composite (CLDHs/BC) was synthesized by a one-pot slow pyrolysis of LDHs preloaded bagasse biomass. Multiple characterizations of the product illustrated that the calcined-Mg/Al layered double hydroxides (CLDHs) were successfully coated onto the biochar in slow pyrolysis of pre-treated biomass. The as-synthesized CLDHs/BC could efficiently remove antibiotic tetracycline from aqueous solutions. The coating of CLDHs significantly increased the adsorption ability of biochar, and CLDHs/BC exhibited more than 2 times higher adsorption capacity than that of the pristine biochar (BC) in the tested pH range. The maximum adsorption capacity of CLDHs/BC for tetracycline was 1118.12 mg/g at 318 K. The experimental results suggested that the interaction with LDHs on biochar played a dominant role in tetracycline adsorption, accompanied with π–π interaction and hydrogen bond. This study provides a feasible and simple approach for the preparation of high-performance material for antibiotics contaminated wastewater treatment in a cost-effective way. PMID:28000759

  1. One-pot synthesis of carbon supported calcined-Mg/Al layered double hydroxides for antibiotic removal by slow pyrolysis of biomass waste

    NASA Astrophysics Data System (ADS)

    Tan, Xiaofei; Liu, Shaobo; Liu, Yunguo; Gu, Yanling; Zeng, Guangming; Cai, Xiaoxi; Yan, Zhili; Yang, Chunping; Hu, Xinjiang; Chen, Bo

    2016-12-01

    A biochar supported calcined-Mg/Al layered double hydroxides composite (CLDHs/BC) was synthesized by a one-pot slow pyrolysis of LDHs preloaded bagasse biomass. Multiple characterizations of the product illustrated that the calcined-Mg/Al layered double hydroxides (CLDHs) were successfully coated onto the biochar in slow pyrolysis of pre-treated biomass. The as-synthesized CLDHs/BC could efficiently remove antibiotic tetracycline from aqueous solutions. The coating of CLDHs significantly increased the adsorption ability of biochar, and CLDHs/BC exhibited more than 2 times higher adsorption capacity than that of the pristine biochar (BC) in the tested pH range. The maximum adsorption capacity of CLDHs/BC for tetracycline was 1118.12 mg/g at 318 K. The experimental results suggested that the interaction with LDHs on biochar played a dominant role in tetracycline adsorption, accompanied with π-π interaction and hydrogen bond. This study provides a feasible and simple approach for the preparation of high-performance material for antibiotics contaminated wastewater treatment in a cost-effective way.

  2. Linking pyrolysis and anaerobic digestion (Py-AD) for the conversion of lignocellulosic biomass.

    PubMed

    Fabbri, Daniele; Torri, Cristian

    2016-04-01

    Biogas is a mixture of CO2 and CH4 produced by a consortia of Bacteria and Archeae operating in anaerobic digestion (AD) plants. Biogas can be burnt as such in engines to produce electricity and heat or upgraded into biomethane. Biomethane is a drop-in fuel that can be injected in the natural gas grid or utilised as a transport fuel. While a wide array of biomass feedstock can be degraded into biogas, unconverted lignin, hemicellulose and cellulose end up in the co-product digestate leaving a large portion of chemical energy unutilised. Pyrolysis (Py) transforms in a single step and without chemical reagents the lignocellulose matrix into gaseous (syngas), liquid (bio-oil, pyrolysis oil) and solid (biochar) fractions for the development of renewable fuels and materials. The Py route applied downstream to AD is actively investigated in order to valorise the solid digestate presently destined only for soil applications. Coupling Py upstream to AD is an emerging field of research aimed at expanding the feedstock towards biologically recalcitrant substrates (wood, paper, sludge). The biomethanation potential was demonstrated for gaseous (H2/CO) and water soluble pyrolysis products, while the influence of insoluble pyrolytic lignin remains fairly unexplored. Biochar can promote the production of biomethane by acting as a support for microorganism colonisation, conductor for direct interspecies electron transfer, sorbent for hydrophobic inhibitors, and reactant for in situ biogas upgrading. Enhancing the advantages (carbon source) over the side effects (toxicity) of Py fractions represents the main challenge of Py-AD. This can be addressed by increasing the selectivity of the thermochemical process or improving the ecological flexibility of mixed bacterial consortia towards chemically complex environments. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Pyrolysis processing for solid waste resource recovery

    NASA Technical Reports Server (NTRS)

    Wojtowicz, Marek A. (Inventor); Serio, Michael A. (Inventor); Kroo, Erik (Inventor); Suuberg, Eric M. (Inventor)

    2007-01-01

    Solid waste resource recovery in space is effected by pyrolysis processing, to produce light gases as the main products (CH.sub.4, H.sub.2, CO.sub.2, CO, H.sub.2O, NH.sub.3) and a reactive carbon-rich char as the main byproduct. Significant amounts of liquid products are formed under less severe pyrolysis conditions, and are cracked almost completely to gases as the temperature is raised. A primary pyrolysis model for the composite mixture is based on an existing model for whole biomass materials, and an artificial neural network models the changes in gas composition with the severity of pyrolysis conditions.

  4. Charcoal from the pyrolysis of rapeseed plant straw-stalk

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Karaosmanoglu, F.; Tetik, E.

    1999-07-01

    Charcoal is an important product of pyrolysis of biomass sources. Charcoal can be used for domestic, agricultural, metallurgical, and chemical purposes. In this study different characteristics of charcoal, one of the rape seed plant straw-stalk pyrolysis product, was researched and presented as candidates.

  5. A review of catalytic microwave pyrolysis of lignocellulosic biomass for value-added fuel and chemicals.

    PubMed

    Morgan, Hervan Marion; Bu, Quan; Liang, Jianghui; Liu, Yujing; Mao, Hanping; Shi, Aiping; Lei, Hanwu; Ruan, Roger

    2017-04-01

    Lignocellulosic biomass is an abundant renewable resource and can be efficiently converted into bio-energy by a bio-refinery. From the various techniques available for biomass thermo-chemical conversion; microwave assisted pyrolysis (MAP) seems to be the very promising. The principles of microwave technology were reviewed and the parameters for the efficient production of bio-oil using microwave technology were summarized. Microwave technology by itself cannot efficiently produce high quality bio-oil products, catalysts are used to improve the reaction conditions and selectivity for valued products during MAP. The catalysts used to optimize MAP are revised in the development of this article. The origins for bio-oils that are phenol rich or hydrocarbon rich are reviewed and their experimental results were summarized. The kinetics of MAP is discussed briefly in the development of the article. Future prospects and scientific development of MAP are also considered in the development of this article. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Total recovery of nitrogen and phosphorus from three wetland plants by fast pyrolysis technology.

    PubMed

    Liu, Wu-Jun; Zeng, Fan-Xin; Jiang, Hong; Yu, Han-Qing

    2011-02-01

    Fast pyrolysis of three wetland plants (Alligator weed, Oenanthe javanica and Typha angustifolia) in a vertical drop fixed bed reactor was investigated in this study. The experiments were carried out at different pyrolysis temperatures, and the maximum bio-oil yields achieved were 42.3%, 40.2% and 43.6% for Alligator weed, Oenanthe javanica and Typha angustifolia, respectively. The elemental composition of the bio-oil and char were analyzed, and the results show that a low temperature was appropriate for the nitrogen and phosphorus enrichment in char. GC-MS analysis shows that nitrogenous compounds, phenols and oxygenates were the main categories in the bio-oil. A series of leaching tests were carried out to examine the recovery of the nitrogen and phosphorus in the char, and the results indicate that significant fractions of nitrogen and phosphorus could be recovered by leaching process. Copyright © 2010 Elsevier Ltd. All rights reserved.

  7. Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhou, Hui; Energy Research Institute, University of Leeds, Leeds LS2 9JT; Wu, Chunfei, E-mail: c.wu@leeds.ac.uk

    2015-02-15

    Highlights: • PAH from pyrolysis of 9 MSW fractions was investigated. • Pyrolysis of plastics released more PAH than that of biomass. • Naphthalene was the most abundant PAH in the tar. • The mechanism of PAH release from biomass and plastics was proposed. - Abstract: The formation of 2–4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. Themore » results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock.« less

  8. Beneficial synergetic effect on gas production during co-pyrolysis of sewage sludge and biomass in a vacuum reactor.

    PubMed

    Zhang, Weijiang; Yuan, Chengyong; Xu, Jiao; Yang, Xiao

    2015-05-01

    A vacuum fixed bed reactor was used to pyrolyze sewage sludge, biomass (rice husk) and their blend under high temperature (900°C). Pyrolytic products were kept in the vacuum reactor during the whole pyrolysis process, guaranteeing a long contact time (more than 2h) for their interactions. Remarkable synergetic effect on gas production was observed. Gas yield of blend fuel was evidently higher than that of both parent fuels. The syngas (CO and H2) content and gas lower heating value (LHV) were obviously improved as well. It was highly possible that sewage sludge provided more CO2 and H2O during co-pyrolysis, promoting intense CO2-char and H2O-char gasification, which benefited the increase of gas yield and lower heating value. The beneficial synergetic effect, as a result, made this method a feasible one for gas production. Copyright © 2015. Published by Elsevier Ltd.

  9. Influence of a glass wool hot vapour filter on yields and properties of bio-oil derived from rapid pyrolysis of paddy residues.

    PubMed

    Pattiya, Adisak; Suttibak, Suntorn

    2012-07-01

    This article reports experimental results of rapid or fast pyrolysis of rice straw (RS) and rice husk (RH) in a fluidised-bed reactor unit incorporated with a hot vapour filter. The objective of this research was to investigate the effects of pyrolysis temperatures and the use of glass wool hot vapour filtration on pyrolysis products. The results showed that the optimum pyrolysis temperatures for RS and RH were 405 and 452 °C, which gave maximum bio-oil yields of 54.1 and 57.1 wt.% on dry biomass basis, respectively. The use of the hot filter led to a reduction of 4-7 wt.% bio-oil yield. Nevertheless, the glass wool hot filtered bio-oils appeared to have better quality in terms of initial viscosity, solids content and ash content than the non-filtered ones. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Valorization of Rhizoclonium sp. algae via pyrolysis and catalytic pyrolysis.

    PubMed

    Casoni, Andrés I; Zunino, Josefina; Piccolo, María C; Volpe, María A

    2016-09-01

    The valorization of Rhizoclonium sp. algae through pyrolysis for obtaining bio-oils is studied in this work. The reaction is carried out at 400°C, at high contact time. The bio-oil has a practical yield of 35% and is rich in phytol. Besides, it is simpler than the corresponding to lignocellulosic biomass due to the absence of phenolic compounds. This property leads to a bio-oil relatively stable to storage. In addition, heterogeneous catalysts (Al-Fe/MCM-41, SBA-15 and Cu/SBA-15), in contact with algae during pyrolysis, are analyzed. The general trend is that the catalysts decrease the concentration of fatty alcohols and other high molecular weight products, since their mild acidity sites promote degradation reactions. Thus, the amount of light products increases upon the use of the catalysts. Particularly, acetol concentration in the bio-oils obtained from the catalytic pyrolysis with SBA-15 and Cu/SBA-15 is notably high. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Comparison of non-catalytic and catalytic fast pyrolysis of corncob in a fluidized bed reactor.

    PubMed

    Zhang, Huiyan; Xiao, Rui; Huang, He; Xiao, Gang

    2009-02-01

    Fast pyrolysis of corncob with and without catalyst was investigated in a fluidized bed to determine the effects of pyrolysis parameters (temperature, gas flow rate, static bed height and particle size) and a HZSM-5 zeolite catalyst on the product yields and the qualities of the liquid products. The result showed that the optimal conditions for liquid yield (56.8%) were a pyrolysis temperature of 550 degrees C, gas flow rate of 3.4 L/min, static bed height of 10 cm and particle size of 1.0-2.0mm. The presence of the catalyst increased the yields of non-condensable gas, water and coke, while decreased the liquid and char yields. The elemental analysis showed that more than 25% decrease in oxygen content of the collected liquid in the second condenser with HZSM-5 was observed compared with that without catalyst. The H/C, O/C molar ratios and the higher heating value of the oil fraction in the collected liquid with the catalyst were 1.511, 0.149 and 34.6 MJ/kg, respectively. It was indicated that the collected liquid in the second condenser had high qualities and might be used as transport oil.

  12. Survival of Salmonella, Escherichia coli 0157:H7, non-0157 shiga toxin producing E.coli, and potential surrogate bacteria in crop soil as affected by the addition of fast pyrolysis-generated switchgrass biochar

    USDA-ARS?s Scientific Manuscript database

    Fast pyrolysis of switchgrass (and resultant biochar) can be used for bio-fuel production, soil amendments for fertilizing crops, binding heavy metals, and sequestering environmental biocarbon. To determine the influence of fast pyrolysis-generated switchgrass biochar on survival of foodborne path...

  13. Clean fuels from biomass

    NASA Technical Reports Server (NTRS)

    Hsu, Y.-Y.

    1976-01-01

    The paper discusses the U.S. resources to provide fuels from agricultural products, the present status of conversion technology of clean fuels from biomass, and a system study directed to determine the energy budget, and environmental and socioeconomic impacts. Conversion processes are discussed relative to pyrolysis and anaerobic fermentation. Pyrolysis breaks the cellulose molecules to smaller molecules under high temperature in the absence of oxygen, wheras anaerobic fermentation is used to convert biomass to methane by means of bacteria. Cost optimization and energy utilization are also discussed.

  14. Mild Biomass Liquefaction Process for Economic Production of Stabilized Refinery-Ready Bio-oil

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gangwal, Santosh; Meng, Jiajia; McCabe, Kevin

    Southern Research (SR) in cooperation with U.S. Department of Energy (DOE), Bioenergy Technology Office (BETO), investigated a biomass liquefaction process for economic production of stabilized refinery-ready bio-oil. The project was awarded by DOE under a Funding Opportunity Announcement (DE-FOA-0000686) for Bio-oil Stabilization and Commoditization that intended to evaluate the feasibility of using bio-oil as a potential feedstock in an existing petroleum refinery. SR investigated Topic Area 1 of the FOA at Technology Readiness Level 2-3 to develop thermochemical liquefaction technologies for producing a bio-oil feedstock from high-impact biomass that can be utilized within a petroleum refinery. Bio-oil obtained from fastmore » pyrolysis of biomass is a green intermediate that can be further upgraded into a biofuel for blending in a petroleum refinery using a hydro-deoxygenation (HDO) route. Co-processing pyrolysis bio-oil in a petroleum refinery is an attractive approach to leverage the refinery’s existing capital. However, the petroleum industry is reluctant to accept pyrolysis bio-oil because of a lack of a standard definition for an acceptable bio-oil feedstock in existing refinery processes. Also per BETO’s multiyear program plan, fast pyrolysis-based bio-fuel is presently not cost competitive with petroleum-based transportation fuels. SR aims to develop and demonstrate a cost-effective low-severity thermal liquefaction and hydrodeoxygenation (HDO) process to convert woody biomass to stabilized bio-oils that can be directly blended with hydrotreater input streams in a petroleum refinery for production of gasoline and/or diesel range hydrocarbons. The specific project objectives are to demonstrate the processes at laboratory scale, characterize the bio-oil product and develop a plan in partnership with a refinery company to move the technology towards commercialization.« less

  15. Improving the hydrocarbon production via co-pyrolysis of bagasse with bio-plastic and dual-catalysts layout.

    PubMed

    Zhang, Huiyan; Likun, Peter Keliona Wani; Xiao, Rui

    2018-03-15

    Catalytic fast pyrolysis (CFP) of bagasse and bio-plastic (chicken feather keratin) and their mixtures were conducted to produce aromatic hydrocarbons over a HZSM-5, USY, and dual-catalysts layout. The effects of temperature, co-feeding ratios, feed-to-catalyst ratios and dual catalysts on hydrocarbon yields and selectivities were investigated. The results show a general improvement in the aromatic hydrocarbons yields in all cases compared to non-catalytic and pure biomass pyrolysis. The aromatic hydrocarbons increased by 10 fold with the increase of temperature from 400°C to 700°C. The aromatic yields increased 1.5 times at co-feeding, 2.0 greater at feed/HZSM-5 ratio of 1:6, 1.2 times at feed/USY ratio of 1:16, and 2.66 times at USY/HZSM-5 scenario. The selectivities towards benzene increased, at higher co-feeding ratios, while that of toluene shows an opposite trend. Xylenes selectivities were less sensitive to the changes of co-feeding ratios. In contrast, the USY catalyst only produced little amount of toluene and xylenes. The dual catalyst design (USY/HZSM-5) resulted in the highest aromatic yields, than other catalyst design scenarios. The pyrolysis temperature is a significant parameter for hydrocarbon production. Co-feeding bagasse and bio-plastic enhanced biomass conversion to aromatic compounds. For any type of zeolite catalyst, there was an optimum feed-to-catalyst ratio that generated maximum hydrocarbons. Dual catalyst layout shows a new opportunity for efficient conversion of biomass materials into hydrocarbons. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Upgraded bio-oil production via catalytic fast co-pyrolysis of waste cooking oil and tea residual.

    PubMed

    Wang, Jia; Zhong, Zhaoping; Zhang, Bo; Ding, Kuan; Xue, Zeyu; Deng, Aidong; Ruan, Roger

    2017-02-01

    Catalytic fast co-pyrolysis (co-CFP) offers a concise and effective process to achieve an upgraded bio-oil production. In this paper, co-CFP experiments of waste cooking oil (WCO) and tea residual (TR) with HZSM-5 zeolites were carried out. The influences of pyrolysis reaction temperature and H/C ratio on pyrolytic products distribution and selectivities of aromatics were performed. Furthermore, the prevailing synergetic effect of target products during co-CFP process was investigated. Experimental results indicated that H/C ratio played a pivotal role in carbon yields of aromatics and olefins, and with H/C ratio increasing, the synergetic coefficient tended to increase, thus led to a dramatic growth of aromatics and olefins yields. Besides, the pyrolysis temperature made a significant contribution to carbon yields, and the yields of aromatics and olefins increased at first and then decreased at the researched temperature region. Note that 600°C was an optimum temperature as the maximum yields of aromatics and olefins could be achieved. Concerning the transportation fuel dependence and security on fossil fuels, co-CFP of WCO and TR provides a novel way to improve the quality and quantity of pyrolysis bio-oil, and thus contributes bioenergy accepted as a cost-competitive and promising alternative energy. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Comparison of the effect of wet and dry torrefaction on chemical structure and pyrolysis behavior of corncobs.

    PubMed

    Zheng, Anqing; Zhao, Zengli; Chang, Sheng; Huang, Zhen; Zhao, Kun; Wei, Guoqiang; He, Fang; Li, Haibin

    2015-01-01

    Wet and dry torrefaction of corncobs was conducted in high-pressure reactor and tube-type reactor, respectively. Effect of wet and dry torrefaction on chemical structure and pyrolysis behavior of corncobs was compared. The results showed that hemicellulose could be effectively removed from corncobs by torrefaction. However, dry torrefaction caused severe degradation of cellulose and the cross-linking and charring of corncobs. X-ray diffraction analysis revealed that crystallinity degree of corncobs was evidently enhanced during wet torrefaction, but reduced during dry torrefaction as raising treatment temperature. In thermogravimetric analysis, wet torrefied corncobs produced less carbonaceous residues than raw corncobs, while dry torrefied corncobs gave much more residues owing to increased content of acid insoluble lignin. Pyrolysis-gas chromatography/mass spectroscopy analysis indicated that wet torrefaction significantly promoted levoglucosan yield owing to the removal of alkali metals. Therefore, wet torrefaction can be considered as a more effective pretreatment method for fast pyrolysis of biomass. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Effect of torrefaction pretreatment and catalytic pyrolysis on the pyrolysis poly-generation of pine wood.

    PubMed

    Chen, Dengyu; Li, Yanjun; Deng, Minsi; Wang, Jiayang; Chen, Miao; Yan, Bei; Yuan, Qiqiang

    2016-08-01

    Torrefaction of pine wood was performed in a tube furnace at three temperatures (220, 250, and 280°C) for 30min. Then catalytic pyrolysis of raw and torrefied pine wood was performed using HZSM-5 catalyst in a fixed-bed pyrolysis reactor at 550°C for 15min. Torrefaction pretreatment and catalytic pyrolysis have an very important effect on the yield, property, and energy distribution of pyrolysis products. The results showed that the yield of biochar rapidly increased, while that of bio-oil decreased with increasing torrefaction temperature. The oxy-compound content of bio-oil, such as acids and aldehydes, sharply decreased. However, the aromatic hydrocarbon content not only increased but also further promoted by HZSM-5 catalyst. With highest mass yields and energy yields, biochar was also the very important product of pyrolysis. The oxygen content in biomass was mainly removed in the form of CO2 and H2O, leading to increasing CO2 content in non-condensable gas. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Comparison of the pyrolysis behavior of lignins from different tree species.

    PubMed

    Wang, Shurong; Wang, Kaige; Liu, Qian; Gu, Yueling; Luo, Zhongyang; Cen, Kefa; Fransson, Torsten

    2009-01-01

    Despite the increasing importance of biomass pyrolysis, little is known about the pyrolysis behavior of lignin--one of the main components of biomass--due to its structural complexity and the difficulty in its isolation. In the present study, we extracted lignins from Manchurian ash (Fraxinus mandschurica) and Mongolian Scots pine (Pinus sylvestris var. mongolica) using the Bjorkman procedure, which has little effect on the structure of lignin. Fourier transform infrared (FTIR) spectrometry was used to characterize the microstructure of the Bjorkman lignins, i.e., milled wood lignins (MWLs), from the different tree species. The pyrolysis characteristics of MWLs were investigated using a thermogravimetric analyzer, and the release of the main volatile and gaseous products of pyrolysis were detected by FTIR spectroscopy. During the pyrolysis process, MWLs underwent thermo-degradation over a wide temperature range. Manchurian ash MWL showed a much higher thermal degradation rate than Mongolian Scots pine MWL in the temperature range from 290-430 degrees C. High residue yields were achieved at 37 wt.% for Mongolian Scots pine MWL and 26 wt.% for Manchurian ash MWL. In order to further investigate the mechanisms of lignin pyrolysis, we also analyzed the FTIR profiles for the main pyrolysis products (CO(2), CO, methane, methanol, phenols and formaldehyde) and investigated the variation in pyrolysis products between the different MWLs.

  20. Method for Hot Real-Time Sampling of Pyrolysis Vapors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pomeroy, Marc D

    Biomass Pyrolysis has been an increasing topic of research, in particular as a replacement for crude oil. This process utilizes moderate temperatures to thermally deconstruct the biomass which is then condensed into a mixture of liquid oxygenates to be used as fuel precursors. Pyrolysis oils contain more than 400 compounds, up to 60 percent of which do not re-volatilize for subsequent chemical analysis. Vapor chemical composition is also complicated as additional condensation reactions occur during the condensation and collection of the product. Due to the complexity of the pyrolysis oil, and a desire to catalytically upgrade the vapor composition beforemore » condensation, online real-time analytical techniques such as Molecular Beam Mass Spectrometry (MBMS) are of great use. However, in order to properly sample hot pyrolysis vapors, many challenges must be overcome. Sampling must occur within a narrow range of temperatures to reduce product composition changes from overheating or partial condensation or plugging of lines from condensed products. Residence times must be kept at a minimum to reduce further reaction chemistries. Pyrolysis vapors also form aerosols that are carried far downstream and can pass through filters resulting in build-up in downstream locations. The co-produced bio-char and ash from the pyrolysis process can lead to plugging of the sample lines, and must be filtered out at temperature, even with the use of cyclonic separators. A practical approach for considerations and sampling system design, as well as lessons learned are integrated into the hot analytical sampling system of the National Renewable Energy Laboratory's (NREL) Thermochemical Process Development Unit (TCPDU) to provide industrially relevant demonstrations of thermochemical transformations of biomass feedstocks at the pilot scale.« less

  1. Recent developments in fast pyrolysis of ligno-cellulosic materials.

    PubMed

    Kersten, Sascha; Garcia-Perez, Manuel

    2013-06-01

    Pyrolysis is a thermochemical process to convert ligno-cellulosic materials into bio-char and pyrolysis oil. This oil can be further upgraded or refined for electricity, transportation fuels and chemicals production. At the time of writing, several demonstration factories are considered worldwide aiming at maturing the technology. Research is focusing on understanding the underlying processes at all relevant scales, ranging from the chemistry of cell wall deconstruction to optimization of pyrolysis factories, in order to produce better quality oils for targeted uses. Among the several bio-oil applications that are currently investigated the production and fermentation of pyrolytic sugars explores the promising interface between thermochemistry and biotechnology. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Experimental investigation into fast pyrolysis of biomass using an entrained-flow reactor

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bohn, M.; Benham, C.

    1981-02-01

    Pyrolysis experiments were performed using 30 and 90cm entrained-flow reactors, with steam as a carrier gas and two different feedstocks - wheat straw and powdered material drived from municipal solid waste (ECO-II TM). Reactor wall temperature was varied from 700/sup 0/ to 1400/sup 0/C. Gas composition data from the ECO-II tests were comparable to previously reported data but ethylene yield appeared to vary with reactor wall temperature and residence time. The important conclusion from the wheat straw tests is that olefin yields are about one half that obtained from ECO-II. Evidence was found that high olefin yields from ECO-II aremore » due to the presence of plastics in the feedstock. Batch experiments were run on wheat straw using a Pyroprobe/sup TM/. The samples were heated at a high rate (20,000/sup 0/ C/sec) to 1000/sup 0/ and held at 1000/sup 0/C for a variable period of time from 0.05 to 4.95s. For times up to 0.15s volume fractions of ethylene, propylene, and methane increase while that of carbon dioxide decreases. Subsequently, only carbon monoxide and hydrogen are produced. The change may be related to poor thermal contact and suggests caution in using the Pyroprobe.« less

  3. Preparation and characterization of nanostructured metal oxides for application to biomass upgrading Polar (111) metal oxide surfaces for pyrolysis oil upgrading and lignin depolymerization

    NASA Astrophysics Data System (ADS)

    Finch, Kenneth

    2013-01-01

    Pyrolysis oil, or bio-oil, is one of the most promising methods to upgrade a variety of biomass to transportation fuels. Moving toward a more "green" catalytic process requires heterogeneous catalysis over homogeneous catalysis to avoid extraction solvent waste. Nanoscale catalysts are showing great promise due to their high surface area and unusual surfaces. Base catalyzed condensation reactions occur much quicker than acid catalyzed condensation reactions. However, MgO is slightly soluble in water and is susceptible to degradation by acidic environments, similar to those found in fast-pyrolysis oil. Magnesium oxide (111) has a highly active Lewis base surface, which can catalyze Claisen-Schmidt condensation reactions in the organic phase. It has been shown previously that carbon coating a catalyst, such as a metal oxide, provides integrity while leaving the catalytic activity intact. Here, carbon-coated MgO(111) will be discussed with regards to synthesis, characterization and application to bio-oil upgrading through model compounds. Raman spectroscopy and HR-TEM are used to characterize the thickness and carbon-bonding environment of the carbon coating. Propanal self-condensation reactions have been conducted in the aqueous phase with varying amounts of acetic acid present. Quantitative analysis by gas chromatography was completed to determine the catalytic activity of CC-MgO(111). ICP-OES analysis has been conducted to measure the magnesium concentration in the product solution and give insight into the leaching of the catalyst into the reaction solution.

  4. Temperature influence on the fast pyrolysis of manure samples: char, bio-oil and gases production

    NASA Astrophysics Data System (ADS)

    Fernandez-Lopez, Maria; Anastasakis, Kostas; De Jong, Wiebren; Valverde, Jose Luis; Sanchez-Silva, Luz

    2017-11-01

    Fast pyrolysis characterization of three dry manure samples was studied using a pyrolyzer. A heating rate of 600°C/s and a holding time of 10 s were selected to reproduce industrial conditions. The effect of the peak pyrolysis temperature (600, 800 and 1000°C) on the pyrolysis product yield and composition was evaluated. Char and bio-oil were gravimetrically quantified. Scanning electron microscopy (SEM) was used to analyse the char structure. H2, CH4, CO and CO2 were measured by means of gas chromatography (GC). A decrease in the char yield and an increase of the gas yield were observed when temperature increased. From 800°C on, it was observed that the char yield of samples Dig R and SW were constant, which indicated that the primary devolatilization reactions stopped. This fact was also corroborated by GC analysis. The bio-oil yield slightly increased with temperature, showing a maximum of 20.7 and 27.8 wt.% for samples Pre and SW, respectively, whereas sample Dig R showed a maximum yield of 16.5 wt.% at 800°C. CO2 and CO were the main released gases whereas H2 and CH4 production increased with temperature. Finally, an increase of char porosity was observed with temperature.

  5. Effluent Gas Flux Characterization During Pyrolysis of Chicken Manure

    NASA Astrophysics Data System (ADS)

    Clark, S. C.; Ryals, R.; Miller, D. J.; Mullen, C. A.; Pan, D.; Zondlo, M. A.; Boateng, A. A.; Hastings, M. G.

    2017-12-01

    Pyrolysis is a viable option for the production of agricultural resources from diverted organic waste streams and renewable bioenergy. This high temperature thermochemical process yields material with beneficial reuses, including bio-oil and biochar. Gaseous forms of carbon (C) and nitrogen (N) are also emitted during pyrolysis. The effluent mass emission rates from pyrolysis are not well characterized, thus limiting proper evaluation of the environmental benefits or costs of pyrolysis products. We present the first comprehensive suite of C and N mass emission rate measurements of a biomass pyrolysis process using chicken manure as feedstock to produce biochar and bio-oil. Two chicken manure fast pyrolysis experiments were conducted at controlled temperature ranges of 450 - 485 °C and 550 - 585 °C. Mass emission rates of N2O, NO, CO, CO2, CH4 and NH3 were measured using trace gas analyzers. Based on the system mass balance, 23-25% of the total mass of the manure feedstock was emitted as gas, while 52-55% and 23% were converted to bio-oil and biochar, respectively. CO2 and NH3 were the dominant gaseous species by mass, accounting for 58 - 65% of total C mass emitted and 99% of total reactive N mass emitted, respectively. Our gas flux measurements suggest that 1.4 to 2.7 g NH3 -N would be produced from the pyrolysis of one kg of manure. Conservatively scaling up these NH3 pyrolysis emissions in the Chesapeake Bay Watershed, where an estimated 8.64 billion kg of poultry manure is applied to agricultural soils every year, as much as 1.2 x 107 kg of NH3 could be emitted into the atmosphere annually, increasing the potential impact of atmospheric N deposition without a mechanism to capture the gas exhaust during pyrolysis. However, this is considerably less than the potential emissions from NH3 volatilization of raw chicken manure applications, which can be 20-60% of total N applied, and amount to 3.4 x 107 - 1.0 x 108 kg NH3-N yr-1. Pyrolysis has the potential to

  6. Pyrolytic sugars from cellulosic biomass.

    PubMed

    Kuzhiyil, Najeeb; Dalluge, Dustin; Bai, Xianglan; Kim, Kwang Ho; Brown, Robert C

    2012-11-01

    Depolymerization of cellulose offers the prospect of inexpensive sugars from biomass. Breaking the glycosidic bonds of cellulose to liberate glucose has usually been pursued by acid or enzymatic hydrolysis although a purely thermal depolymerization route to sugars is also possible. Fast pyrolysis of pure cellulose yields primarily the anhydrosugar levoglucosan (LG) whereas the presence of naturally occurring alkali and alkaline earth metals (AAEMs) in biomass strongly catalyzes ring-breaking reactions that favor formation of light oxygenates. Here, we show a method of significantly increasing the yield of sugars from biomass by purely thermal means through infusion of certain mineral acids (phosphoric and sulfuric acid) into the biomass to convert the AAEMs into thermally stable salts (particularly potassium sulfates and phosphates). These salts not only passivate AAEMs that normally catalyze fragmentation of pyranose rings, but also buffer the system at pH levels that favor glycosidic bond breakage. It appears that AAEM passivation contributes to 80 % of the enhancement in LG yield while the buffering effect of the acid salts contributes to the balance of the enhancement. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Review of the pyrolysis platform for coproducing bio-oil and biochar

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Laird, David A.; Brown, Robert C.; Amonette, James E.

    2009-09-01

    Pyrolysis is a relatively simple, inexpensive, and robust thermochemical technology for transforming biomass into bio-oil, biochar, and syngas. The robust nature of the pyrolysis technology, which allows considerable flexibility in both the type and quality of the biomass feedstock, combined with a distributed network of small pyrolysis plants, would be compatible with existing agriculture and forestry infrastructure. Bio-oil can be used as a fuel in existing industrial boilers. Biochar can be used with existing infrastructure as a replacement for pulverized coal; however, use of biochar as a soil amendment results in significant environmental and agronomic benefits. Soil application of biocharmore » is a means of sequestering large amounts of C and may have other greenhouse gas benefits. Preliminary reports of the impact of soil biochar applications on crop yields indicate that biochar quality is very important. Biochar is an effective adsorbent for both nutrients and organic contaminants, hence the presence of biochar in soils has been shown to improve water quality in column leaching and field lysimeter studies and it is anticipated to do the same for agricultural watersheds. The pyrolysis platform for producing bio-oil and biochar from biomass appears to be a practical, effective, and environmentally sustainable means of producing large quantities of renewable bioenergy while simultaneously reducing emissions of greenhouse gases. At the present time, the pyrolysis platform is economically marginal because markets for bio-oil and biochar are highly competitive. However, if the USA adopts a program for controlling greenhouse gases, the pyrolysis platform would be highly competitive.« less

  8. Genetic and Quantitative Trait Locus Analysis for Bio-Oil Compounds after Fast Pyrolysis in Maize Cobs.

    PubMed

    Jeffrey, Brandon; Kuzhiyil, Najeeb; de Leon, Natalia; Lübberstedt, Thomas

    2016-01-01

    Fast pyrolysis has been identified as one of the biorenewable conversion platforms that could be a part of an alternative energy future, but it has not yet received the same attention as cellulosic ethanol in the analysis of genetic inheritance within potential feedstocks such as maize. Ten bio-oil compounds were measured via pyrolysis/gas chromatography-mass spectrometry (Py/GC-MS) in maize cobs. 184 recombinant inbred lines (RILs) of the intermated B73 x Mo17 (IBM) Syn4 population were analyzed in two environments, using 1339 markers, for quantitative trait locus (QTL) mapping. QTL mapping was performed using composite interval mapping with significance thresholds established by 1000 permutations at α = 0.05. 50 QTL were found in total across those ten traits with R2 values ranging from 1.7 to 5.8%, indicating a complex quantitative inheritance of these traits.

  9. Quantification of Lignin and Its Structural Features in Plant Biomass Using 13C Lignin as Internal Standard for Pyrolysis-GC-SIM-MS.

    PubMed

    van Erven, Gijs; de Visser, Ries; Merkx, Donny W H; Strolenberg, Willem; de Gijsel, Peter; Gruppen, Harry; Kabel, Mirjam A

    2017-10-17

    Understanding the mechanisms underlying plant biomass recalcitrance at the molecular level can only be achieved by accurate analyses of both the content and structural features of the molecules involved. Current quantification of lignin is, however, majorly based on unspecific gravimetric analysis after sulfuric acid hydrolysis. Hence, our research aimed at specific lignin quantification with concurrent characterization of its structural features. Hereto, for the first time, a polymeric 13 C lignin was used as internal standard (IS) for lignin quantification via analytical pyrolysis coupled to gas chromatography with mass-spectrometric detection in selected ion monitoring mode (py-GC-SIM-MS). In addition, relative response factors (RRFs) for the various pyrolysis products obtained were determined and applied. First, 12 C and 13 C lignin were isolated from nonlabeled and uniformly 13 C labeled wheat straw, respectively, and characterized by heteronuclear single quantum coherence (HSQC), nuclear magnetic resonance (NMR), and py-GC/MS. The two lignin isolates were found to have identical structures. Second, 13 C-IS based lignin quantification by py-GC-SIM-MS was validated in reconstituted biomass model systems with known contents of the 12 C lignin analogue and was shown to be extremely accurate (>99.9%, R 2 > 0.999) and precise (RSD < 1.5%). Third, 13 C-IS based lignin quantification was applied to four common poaceous biomass sources (wheat straw, barley straw, corn stover, and sugar cane bagasse), and lignin contents were in good agreement with the total gravimetrically determined lignin contents. Our robust method proves to be a promising alternative for the high-throughput quantification of lignin in milled biomass samples directly and simultaneously provides a direct insight into the structural features of lignin.

  10. Requirements for transportation of fast pyrolysis bio-oil in Finland

    NASA Astrophysics Data System (ADS)

    Karhunen, Antti; Laihanen, Mika; Ranta, Tapio

    2016-11-01

    The purpose of this paper is to discuss the requirements and challenges of pyrolysis oil's transportation in Finland. Pyrolysis oil is a new type of renewable liquid fuel that can be utilised in applications such as heat and electricity production. It has never been transported on a large scale in Finland. Possible options are transport by road, rail and waterway. The most significant requirements in its transportation are created by acidity and high density of pyrolysis oil, which impose requirements for the materials and transport equipment. The study described here shows that constant domestic transportation of pyrolysis oil is most reasonably operated with tank trucks. Rail-based transport may have potential for domestic fixed routes, and transport by water could be utilised in exporting. All transportation methods have limitations and advantages relative to each other. Ultimately, the production site and end-user's locations will determine the most suitable transport method.

  11. Pyrolysis bio-oil upgrading to renewable fuels.

    DOT National Transportation Integrated Search

    2014-01-01

    This study aims to upgrade woody biomass pyrolysis bio-oil into transportation fuels by catalytic hydrodeoxygenation : (HDO) using nanospring (NS) supported catalyst via the following research objectives: (1) develop nanospring-based : catalysts (nan...

  12. Fast pyrolysis kinetics of alkali lignin: Evaluation of apparent rate parameters and product time evolution.

    PubMed

    Ojha, Deepak Kumar; Viju, Daniel; Vinu, R

    2017-10-01

    In this study, the apparent kinetics of fast pyrolysis of alkali lignin was evaluated by obtaining isothermal mass loss data in the timescale of 2-30s at 400-700°C in an analytical pyrolyzer. The data were analyzed using different reaction models to determine the rate constants and apparent rate parameters. First order and one dimensional diffusion models resulted in good fits with experimental data with apparent activation energy of 23kJmol -1 . Kinetic compensation effect was established using a large number of kinetic parameters reported in the literature for pyrolysis of different lignins. The time evolution of the major functional groups in the pyrolysate was analyzed using in situ Fourier transform infrared spectroscopy. Maximum production of the volatiles occurred around 10-12s. A clear transformation of guaiacols to phenol, catechol and their derivatives, and aromatic hydrocarbons was observed with increasing temperature. The plausible reaction steps involved in various transformations are discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. A detailed kinetic mechanism including methanol and nitrogen pollutants relevant to the gas-phase combustion and pyrolysis of biomass-derived fuels

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Coda Zabetta, Edgardo; Hupa, Mikko

    2008-01-15

    A detailed chemical kinetic mechanism for the simulation of the gas-phase combustion and pyrolysis of biomass-derived fuels was compiled by assembling selected reaction subsets from existing mechanisms (parents). The mechanism, here referred to as ''AaA,'' includes reaction subsets for the oxidation of hydrogen (H{sub 2}), carbon monoxide (CO), light hydrocarbons (C{sub 1} and C{sub 2}), and methanol (CH{sub 3}OH). The mechanism also takes into account reaction subsets of nitrogen pollutants, including the reactions relevant to staged combustion, reburning, and selective noncatalytic reduction (SNCR). The AaA mechanism was validated against suitable experimental data from the literature. Overall, the AaA mechanism gavemore » more accurate predictions than three other mechanisms of reference, although the reference mechanisms performed better occasionally. The predictions from AaA were also found to be consistent with the predictions of its parent mechanisms within most of their range of validity, thus transferring the validity of the parents to the inheriting mechanism (AaA). In parametric studies the AaA mechanism predicted that the effect of methanol on combustion and pollutants is often similar to that of light hydrocarbons, but it also showed that there are important exceptions, thus suggesting that methanol should be taken into account when simulating biomass combustion. To our knowledge, the AaA mechanism is currently the only mechanism that accounts for the chemistry of methanol and nitrogen relevant to the gas-phase combustion and pyrolysis of biomass-derived fuels. (author)« less

  14. Catalytic co-pyrolysis of cellulose and polypropylene over all-silica mesoporous catalyst MCM-41 and Al-MCM-41.

    PubMed

    Chi, Yongchao; Xue, Junjie; Zhuo, Jiankun; Zhang, Dahu; Liu, Mi; Yao, Qiang

    2018-08-15

    Fast pyrolysis is one of the most economical and efficient technologies to convert biomass to bio-oil and valuable chemical products. Co-pyrolysis with hydrogen rich materials such as plastics over zeolite catalysts is one of the significant solutions to various problems of bio-oil such as high oxygen content, low heat value and high acid content. This paper studied pyrolysis of cellulose and polypropylene (PP) separately and co-pyrolysis of cellulose and PP over MCM-41 and Al-MCM-41. The pyrolysis over different heating rates (10K/min, 20K/min, 30K/min) was studied by Thermogravimetry Analysis (TGA) and kinetic parameters were obtained by Coats-Redfern method and isoconversion method. TG and DTG data shows that the two catalysts advance the pyrolysis reaction of PP significantly and reduce its peak temperature of DTG curve from 458°C to 341°C. The activation energy of pyrolysis of PP also has a remarkable reduction over the two catalysts. Py-GC/MS method was used to obtain the product distribution of pyrolysis of cellulose and PP separately and co-pyrolysis of cellulose and PP over MCM-41 and Al-MCM-41 at constant temperature of 650°C. Experiment results proved that co-pyrolysis with PP bring significant changes to the product distribution of cellulose. Oxygenated compounds such as furans are decreased, while yields of olefins and aromatics increase greatly. The yield of furans increases with the catalysis of MCM-41 as for the pyrolysis of cellulose and co-pyrolysis, while the yield of olefins and aromatics both experience significant growth over Al-MCM-41, which can be explained by the abundant acid centers in Al-MCM-41. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Effects of hot water extraction pretreatment on pyrolysis of shrub willow

    USDA-ARS?s Scientific Manuscript database

    Treatment of biomass via hot water extraction (HWE) reduces the amount of hemicellulose and ash in the biomass resulting in a concentration of cellulose and lignin content. In this study, we tested the effect of HWE as a biomass pretreatment on the pyrolysis of shrub willow via both conventional he...

  16. Thermogravimetric kinetic study of agricultural residue biomass pyrolysis based on combined kinetics.

    PubMed

    Wang, Xun; Hu, Mian; Hu, Wanyong; Chen, Zhihua; Liu, Shiming; Hu, Zhiquan; Xiao, Bo

    2016-11-01

    Pyrolytic kinetic of an agricultural residue (AR) feedstock, a mixture of plants (cotton, wheat, rich, corn) stems, was investigated based on combined kinetics. The most suitable mechanism for AR one-step pyrolysis was f(α)=(1-α)(1.1816)α(-1.8428) with kinetic parameters of: apparent activation energy 221.7kJ/mol, pre-exponential factor 4.17E16s(-1). Pyrolysis of AR feedstock could not be described by one-step reaction attributes to heterogeneous features of pyrolysis processes. Combined kinetics three-parallel-reaction (CK-TPR) model fitted the pyrolysis experimental data very well. Reaction mechanisms for pseudo hemicelluloses, cellulose, lignin in CK-TPR model was f(α)=(1-α)(1.6244)α(-0.3371)[-ln(1-α)](-0.0515), f(α)=(1-α)(1.0597)α(-0.6909)[-ln(1-α)](0.9026) and f(α)=(1-α)(2.9577)α(-4.7719), respectively. Apparent activation energy of three pseudo components followed the order of Elignin(197.3kJ/mol)>Ecellulose(176.3kJ/mol)>Ehemicelluloses (151.1kJ/mol). Mechanism of hemicelluloses pyrolysis could be further expressed as f(α)=(1-α)(1.4). The pyrolytic mechanism of cellulose met the Nucleation well. However, mechanism of lignin pyrolysis was complex, which possibly was the combined effects of Nucleation, Diffusion, Geometrical contraction, and Power law. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Review of NMR characterization of pyrolysis oils

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun

    Here, pyrolysis of renewable biomass has been developed as a method to produce green fuels and chemicals in response to energy security concerns as well as to alleviate environmental issues incurred with fossil fuel usage. However, pyrolysis oils still have limited commercial application, mainly because unprocessed oils cannot be readily blended with current petroleum-based transportation fuels. To better understand these challenges, researchers have applied diverse characterization techniques in the development of bio-oil studies. In particular, nuclear magnetic resonance (NMR) is a key spectroscopic characterization method through analysis of bio-oil components. This review highlights the NMR strategies for pyrolysis oil characterizationmore » and critically discusses the applications of 1H, 13C, 31P, 19F, and two-dimensional (2-D NMR) analyses such as heteronuclear single quantum correlation (HSQC) in representative pyrolysis oil studies.« less

  18. Review of NMR characterization of pyrolysis oils

    DOE PAGES

    Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun; ...

    2016-08-24

    Here, pyrolysis of renewable biomass has been developed as a method to produce green fuels and chemicals in response to energy security concerns as well as to alleviate environmental issues incurred with fossil fuel usage. However, pyrolysis oils still have limited commercial application, mainly because unprocessed oils cannot be readily blended with current petroleum-based transportation fuels. To better understand these challenges, researchers have applied diverse characterization techniques in the development of bio-oil studies. In particular, nuclear magnetic resonance (NMR) is a key spectroscopic characterization method through analysis of bio-oil components. This review highlights the NMR strategies for pyrolysis oil characterizationmore » and critically discusses the applications of 1H, 13C, 31P, 19F, and two-dimensional (2-D NMR) analyses such as heteronuclear single quantum correlation (HSQC) in representative pyrolysis oil studies.« less

  19. Economic assessment of flash co-pyrolysis of short rotation coppice and biopolymer waste streams.

    PubMed

    Kuppens, T; Cornelissen, T; Carleer, R; Yperman, J; Schreurs, S; Jans, M; Thewys, T

    2010-12-01

    The disposal problem associated with phytoextraction of farmland polluted with heavy metals by means of willow requires a biomass conversion technique which meets both ecological and economical needs. Combustion and gasification of willow require special and costly flue gas treatment to avoid re-emission of the metals in the atmosphere, whereas flash pyrolysis mainly results in the production of (almost) metal free bio-oil with a relatively high water content. Flash co-pyrolysis of biomass and waste of biopolymers synergistically improves the characteristics of the pyrolysis process: e.g. reduction of the water content of the bio-oil, more bio-oil and less char production and an increase of the HHV of the oil. This research paper investigates the economic consequences of the synergistic effects of flash co-pyrolysis of 1:1 w/w ratio blends of willow and different biopolymer waste streams via cost-benefit analysis and Monte Carlo simulations taking into account uncertainties. In all cases economic opportunities of flash co-pyrolysis of biomass with biopolymer waste are improved compared to flash pyrolysis of pure willow. Of all the biopolymers under investigation, polyhydroxybutyrate (PHB) is the most promising, followed by Eastar, Biopearls, potato starch, polylactic acid (PLA), corn starch and Solanyl in order of decreasing profits. Taking into account uncertainties, flash co-pyrolysis is expected to be cheaper than composting biopolymer waste streams, except for corn starch. If uncertainty increases, composting also becomes more interesting than flash co-pyrolysis for waste of Solanyl. If the investment expenditure is 15% higher in practice than estimated, the preference for flash co-pyrolysis compared to composting biopolymer waste becomes less clear. Only when the system of green current certificates is dismissed, composting clearly is a much cheaper processing technique for disposing of biopolymer waste. Copyright © 2010 Elsevier Ltd. All rights reserved.

  20. The transport phase of pyrolytic oil exiting a fast fluidized bed reactor

    NASA Astrophysics Data System (ADS)

    Daugaard, Daren Einar

    An unresolved and debated aspect in the fast pyrolysis of biomass is whether the bio-oil exits as a vapor or as an aerosol from the pyrolytic reactor. The determination of the bio-oil transport phase will have direct and significant impact on the design of fast pyrolysis systems. Optimization of both the removal of particulate matter and collection of bio-oil will require this information. In addition, the success of catalytic reforming of bio-oil to high-value chemicals will depend upon this transport phase. A variety of experimental techniques were used to identify the transport phase. Some tests were as simple as examining the catch of an inline filter while others attempted to deduce whether vapor or aerosol predominated by examining the pressure drop across a flow restriction. In supplementary testing, the effect of char on aerosol formation and the potential impact of cracking during direct contact filtering are evaluated. The study indicates that for pyrolysis of red oak approximately 90 wt-% of the collected bio-oil existed as a liquid aerosol. Conversely, the pyrolysis of corn starch produced bio-oil predominately in the vapor phase at the exit of the reactor. Furthermore, it was determined that the addition of char promotes the production of aerosols during pyrolysis of corn starch. Direct contact filtering of the product stream did not collect any liquids and the bio-oil yield was not significantly reduced indicating measurable cracking or coking did not occur.

  1. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOEpatents

    Diebold, James P.; Scahill, John W.; Chum, Helena L.; Evans, Robert J.; Rejai, Bahman; Bain, Richard L.; Overend, Ralph P.

    1996-01-01

    A process for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols.

  2. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOEpatents

    Diebold, J.P.; Scahill, J.W.; Chum, H.L.; Evans, R.J.; Rejai, B.; Bain, R.L.; Overend, R.P.

    1996-04-02

    A process is described for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols. 35 figs.

  3. Quantification of Lignin and Its Structural Features in Plant Biomass Using 13C Lignin as Internal Standard for Pyrolysis-GC-SIM-MS

    PubMed Central

    2017-01-01

    Understanding the mechanisms underlying plant biomass recalcitrance at the molecular level can only be achieved by accurate analyses of both the content and structural features of the molecules involved. Current quantification of lignin is, however, majorly based on unspecific gravimetric analysis after sulfuric acid hydrolysis. Hence, our research aimed at specific lignin quantification with concurrent characterization of its structural features. Hereto, for the first time, a polymeric 13C lignin was used as internal standard (IS) for lignin quantification via analytical pyrolysis coupled to gas chromatography with mass-spectrometric detection in selected ion monitoring mode (py-GC-SIM-MS). In addition, relative response factors (RRFs) for the various pyrolysis products obtained were determined and applied. First, 12C and 13C lignin were isolated from nonlabeled and uniformly 13C labeled wheat straw, respectively, and characterized by heteronuclear single quantum coherence (HSQC), nuclear magnetic resonance (NMR), and py-GC/MS. The two lignin isolates were found to have identical structures. Second, 13C-IS based lignin quantification by py-GC-SIM-MS was validated in reconstituted biomass model systems with known contents of the 12C lignin analogue and was shown to be extremely accurate (>99.9%, R2 > 0.999) and precise (RSD < 1.5%). Third, 13C-IS based lignin quantification was applied to four common poaceous biomass sources (wheat straw, barley straw, corn stover, and sugar cane bagasse), and lignin contents were in good agreement with the total gravimetrically determined lignin contents. Our robust method proves to be a promising alternative for the high-throughput quantification of lignin in milled biomass samples directly and simultaneously provides a direct insight into the structural features of lignin. PMID:28926698

  4. Co-production of furfural and acetic acid from corncob using ZnCl2 through fast pyrolysis in a fluidized bed reactor.

    PubMed

    Oh, Seung-Jin; Jung, Su-Hwa; Kim, Joo-Sik

    2013-09-01

    Corncob was pyrolyzed using ZnCl2 in a pyrolysis plant equipped with a fluidized bed reactor to co-produce furfural and acetic acid. The effects of reaction conditions, the ZnCl2 content and contacting method of ZnCl2 with corncob on the yields of furfural and acetic acid were investigated. The pyrolysis was performed within the temperature range between 310 and 410°C, and the bio-oil yield were 30-60 wt% of the product. The furfural yield increased up to 8.2 wt%. The acetic acid yield was maximized with a value of 13.1 wt%. A lower feed rate in the presence of ZnCl2 was advantageous for the production of acetic acid. The fast pyrolysis of a smaller corncob sample mechanically mixed with 20 wt% of ZnCl2 gave rise to a distinct increase in furfural. A high selectivity for furfural and acetic acid in bio-oil would make the pyrolysis of corncob with ZnCl2 very economically attractive. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Effect of filter media size, mass flow rate and filtration stage number in a moving-bed granular filter on the yield and properties of bio-oil from fast pyrolysis of biomass.

    PubMed

    Paenpong, Chaturong; Inthidech, Sudsakorn; Pattiya, Adisak

    2013-07-01

    Fast pyrolysis of cassava rhizome was performed in a bench-scale fluidised-bed reactor unit incorporated with a cross-flow moving-bed granular filter. The objective of this research was to examine several process parameters including the granular size (425-1160 μm) and mass flow rate (0-12 g/min) as well as the number of the filtration stages (1-2 stages) on yields and properties of bio-oil. The results showed that the bio-oil yield decreased from 57.7 wt.% to 42.0-49.2 wt.% when increasing the filter media size, the mass flow rate and the filtration stage number. The effect of the process parameters on various properties of bio-oil is thoroughly discussed. In general, the bio-oil quality in terms of the solids content, ash content, initial viscosity, viscosity change and ageing rate could be enhanced by the hot vapour granular filtration. Therefore, bio-oil of high stability could be produced by the pyrolysis reactor configuration designed in this work. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis.

    PubMed

    Bu, Quan; Lei, Hanwu; Zacher, Alan H; Wang, Lu; Ren, Shoujie; Liang, Jing; Wei, Yi; Liu, Yupeng; Tang, Juming; Zhang, Qin; Ruan, Roger

    2012-11-01

    Catalytic hydrodeoxygenation (HDO) of lignin-derived phenols which are the lowest reactive chemical compounds in biomass pyrolysis oils has been reviewed. The hydrodeoxygenation (HDO) catalysts have been discussed including traditional HDO catalysts such as CoMo/Al(2)O(3) and NiMo/Al(2)O(3) catalysts and transition metal catalysts (noble metals). The mechanism of HDO of lignin-derived phenols was analyzed on the basis of different model compounds. The kinetics of HDO of different lignin-derived model compounds has been investigated. The diversity of bio-oils leads to the complexities of HDO kinetics. The techno-economic analysis indicates that a series of major technical and economical efforts still have to be investigated in details before scaling up the HDO of lignin-derived phenols in existed refinery infrastructure. Examples of future investigation of HDO include significant challenges of improving catalysts and optimum operation conditions, further understanding of kinetics of complex bio-oils, and the availability of sustainable and cost-effective hydrogen source. Copyright © 2012 Elsevier Ltd. All rights reserved.

  7. Life cycle assessment of the production of hydrogen and transportation fuels from corn stover via fast pyrolysis

    NASA Astrophysics Data System (ADS)

    Zhang, Yanan; Hu, Guiping; Brown, Robert C.

    2013-06-01

    This life cycle assessment evaluates and quantifies the environmental impacts of the production of hydrogen and transportation fuels from the fast pyrolysis and upgrading of corn stover. Input data for this analysis come from Aspen Plus modeling, a GREET (Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation) model database and a US Life Cycle Inventory Database. SimaPro 7.3 software is employed to estimate the environmental impacts. The results indicate that the net fossil energy input is 0.25 MJ and 0.23 MJ per km traveled for a light-duty vehicle fueled by gasoline and diesel fuel, respectively. Bio-oil production requires the largest fossil energy input. The net global warming potential (GWP) is 0.037 kg CO2eq and 0.015 kg CO2eq per km traveled for a vehicle fueled by gasoline and diesel fuel, respectively. Vehicle operations contribute up to 33% of the total positive GWP, which is the largest greenhouse gas footprint of all the unit processes. The net GWPs in this study are 88% and 94% lower than for petroleum-based gasoline and diesel fuel (2005 baseline), respectively. Biomass transportation has the largest impact on ozone depletion among all of the unit processes. Sensitivity analysis shows that fuel economy, transportation fuel yield, bio-oil yield, and electricity consumption are the key factors that influence greenhouse gas emissions.

  8. Phenolic compounds containing/neutral fractions extract and products derived therefrom from fractionated fast-pyrolysis oils

    DOEpatents

    Chum, Helena L.; Black, Stuart K.; Diebold, James P.; Kreibich, Roland E.

    1993-01-01

    A process for preparing phenol-formaldehyde novolak resins and molding compositions in which portions of the phenol normally contained in said resins are replaced by a phenol/neutral fractions extract obtained from fractionating fast-pyrolysis oils. The fractionation consists of a neutralization stage which can be carried out with aqueous solutions of bases or appropriate bases in the dry state, followed by solvent extraction with an organic solvent having at least a moderate solubility parameter and good hydrogen bonding capacity. Phenolic compounds-containing/neutral fractions extracts obtained by fractionating fast-pyrolysis oils from a lignocellulosic material, is such that the oil is initially in the pH range of 2-4, being neutralized with an aqueous bicarbonate base, and extracted into a solvent having a solubility parameter of approximately 8.4-9.11 [cal/cm.sup.3 ].sup.1/2 with polar components in the 1.8-3.0 range and hydrogen bonding components in the 2-4.8 range and the recovery of the product extract from the solvent with no further purification being needed for use in adhesives and molding compounds. The product extract is characterized as being a mixture of very different compounds having a wide variety of chemical functionalities, including phenolic, carbonyl, aldehyde, methoxyl, vinyl and hydroxyl. The use of the product extract on phenol-formaldehyde thermosetting resins is shown to have advantages over the conventional phenol-formaldehyde resins.

  9. A comparative study on pyrolysis characteristic Indonesia biomassa and low grade coal

    NASA Astrophysics Data System (ADS)

    Adhityatama, G. I.; Hanif, F.; Cahyono, R. B.; Hidayat, M.; Akiyama, T.

    2017-05-01

    A comparative study on pyrolysis of biomass and low grade coal was conducted using a thermogravimetric analyzer. Each kind of biomass and coal has a characteristic pyrolysis behavior which is explained based on its individual component characteristics. All fuels experienced a small weight loss as temperatures approached 450K because of moisture evaporation. The coal had smallest total weight loss compared to biomass due to its high content of fixed carbon, suggesting that coal would produce high amounts of char and small amounts of volatile matter (e.g., tar and gas). The biomass exhibits similar tendency regarding the decomposition process which is the hemicelluloses break down first at temperatures of 470 to 530K, cellulose follows in the temperature range 510 to 620K, and lignin is the last component to pyrolyzer at temperatures of 550 to 770K. The thermal decomposition of biomass consisted of two predominant peaks corresponding first to the decomposition of cellulose and, second, to the decomposition of lignin. Meanwhile, the coal exhibited only single peak because these fuels were predominantly composed of carbon. Based on the kinetic analysis, coal have the smaller activation energy (55.32kJ/mol) compared to biomass (range from 89.80-172.86 kJ/mol). Pyrolysis process also created more pore material in the solid product. These results were important for the optimization of energy conversion from those solid fuels. Biomass resulted lower solid product and higher tar product, thus would be suitable for liquid and gas energy production.

  10. Lifecycle Assessment of Biofuel Production from Wood Pyrolysis Technology

    ERIC Educational Resources Information Center

    Manyele, S. V.

    2007-01-01

    Due to a stronger dependency on biomass for energy, there is a need for improved technologies in biomass-to-energy conversion in Tanzania. This paper presents a life cycle assessment (LCA) of pyrolysis technology used for conversion of wood and wood waste to liquid biofuel. In particular, a survey of environmental impacts of the process is…

  11. Dewatering and granulation of sewage sludge by biophysical drying and thermo-degradation performance of prepared sludge particles during succedent fast pyrolysis.

    PubMed

    Han, Rong; Liu, Jinwen; Zhang, Yuancheng; Fan, Xiaoqian; Lu, Wenjing; Wang, Hongtao

    2012-03-01

    A novel two-step technology, fast biophysical drying (BPD) coupling with fast pyrolysis (FP), was investigated for moisture removal and energy recovery from sewage sludge. For BPD, combined operations of extreme thermophilic amendment (with accelerated increasing and controllable maintenance of substrate temperature) and enhanced convective evaporation were conducted, both beneficial for moisture removal (moisture content reaching 23.1% for 7d) and organic preservation. Biophysical-dried sludge (BPDS) was characterized by homogeneous fine-particle morphology and well-developed porous microstructure. The synthesized BPDS particle preserved most organic components (92% volatile matters and 79% HHV of traditional thermal-dried sludge [TTDS]) attributable to the inhibitory effect of BPD adjustment, presenting considerable capacity for subsequent residue-derived energy. For FP, the distribution of products from BPDS pyrolysis indicated that syngas and char yields were higher than those of TTDS. The syngas from BPDS is a type of hydrogen-rich gas composed of 42.6 vol.% H(2) at 900°C. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Development of life cycle water footprints for the production of fuels and chemicals from algae biomass.

    PubMed

    Nogueira Junior, Edson; Kumar, Mayank; Pankratz, Stan; Oyedun, Adetoyese Olajire; Kumar, Amit

    2018-09-01

    This study develops life cycle water footprints for the production of fuels and chemicals via thermochemical conversion of algae biomass. This study is based on two methods of feedstock production - ponds and photobioreactors (PBRs) - and four conversion pathways - fast pyrolysis, hydrothermal liquefaction (HTL), conventional gasification, and hydrothermal gasification (HTG). The results show the high fresh water requirement for algae production and the necessity to recycle harvested water or use alternative water sources. To produce 1 kg of algae through ponds, 1564 L of water are required. When PBRs are used, only 372 L water are required; however, the energy requirements for PBRs are about 30 times higher than for ponds. From a final product perspective, the pathway based on the gasification of algae biomass was the thermochemical conversion method that required the highest amount of water per MJ produced (mainly due to its low hydrogen yield), followed by fast pyrolysis and HTL. On the other hand, HTG has the lowest water footprint, mainly because the large amount of electricity generated as part of the process compensates for the electricity used by the system. Performance in all pathways can be improved through recycling channels. Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Pyrolysis of cassava rhizome in a counter-rotating twin screw reactor unit.

    PubMed

    Sirijanusorn, Somsak; Sriprateep, Keartisak; Pattiya, Adisak

    2013-07-01

    A counter-rotating twin screw reactor unit was investigated for its behaviour in the pyrolysis of cassava rhizome biomass. Several parameters such as pyrolysis temperature in the range of 500-700°C, biomass particle size of <0.6mm, the use of sand as heat transfer medium, nitrogen flow rate of 4-10 L/min and nitrogen pressure of 1-3 bar were thoroughly examined. It was found that the pyrolysis temperature of 550°C could maximise the bio-oil yield (50 wt.%). The other optimum parameters for maximising the bio-oil yield were the biomass particle size of 0.250-0.425 mm, the nitrogen flow rate of 4 L/min and the nitrogen pressure of 2 bar. The use of the heat transfer medium could increase the bio-oil yield to a certain extent. Moreover, the water content of bio-oil produced with the counter-rotating twin screw reactor was relatively low, whereas the solids content was relatively high, compared to some other reactor configurations. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Total Acid Value Titration of Hydrotreated Biomass Fast Pyrolysis Oil: Determination of Carboxylic Acids and Phenolics with Multiple End-Point Detection

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Christensen, E.; Alleman, T. L.; McCormick, R. L.

    Total acid value titration has long been used to estimate corrosive potential of petroleum crude oil and fuel oil products. The method commonly used for this measurement, ASTM D664, utilizes KOH in isopropanol as the titrant with potentiometric end point determination by pH sensing electrode and Ag/AgCl reference electrode with LiCl electrolyte. A natural application of the D664 method is titration of pyrolysis-derived bio-oil, which is a candidate for refinery upgrading to produce drop in fuels. Determining the total acid value of pyrolysis derived bio-oil has proven challenging and not necessarily amenable to the methodology employed for petroleum products duemore » to the different nature of acids present. We presented an acid value titration for bio-oil products in our previous publication which also utilizes potentiometry using tetrabutylammonium hydroxide in place of KOH as the titrant and tetraethylammonium bromide in place of LiCl as the reference electrolyte to improve the detection of these types of acids. This method was shown to detect numerous end points in samples of bio-oil that were not detected by D664. These end points were attributed to carboxylic acids and phenolics based on the results of HPLC and GC-MS studies. Additional work has led to refinement of the method and it has been established that both carboxylic acids and phenolics can be determined accurately. Use of pH buffer calibration to determine half-neutralization potentials of acids in conjunction with the analysis of model compounds has allowed us to conclude that this titration method is suitable for the determination of total acid value of pyrolysis oil and can be used to differentiate and quantify weak acid species. The measurement of phenolics in bio-oil is subject to a relatively high limit of detection, which may limit the utility of titrimetric methodology for characterizing the acidic potential of pyrolysis oil and products.« less

  15. Biofuel Production from Jatropha Bio-Oil Derived Fast Pyrolysis: Effect and Mechanism of CoMoS Supported on Al2O3

    NASA Astrophysics Data System (ADS)

    Rodseanglung, T.; Ratana, T.; Phongaksorn, M.; Tungkamani, S.

    2018-03-01

    The aims of this research was to understand the CoMo/Al2O3 sulfide catalyst effect to remove oxygen-containing and nitrogen-containing molecules from Jatropha bio-oil derived fast pyrolysis converted to biofuels via hydrotreating process. The activity and selectivity of CoMo/γ-Al2O3 sulfided catalysts in hydrodeoxygenation (HDO) of Jatropha bio-oil derived fast pyrolysis was evaluated in a Parr batch reactor under 50 bar of H2 atmosphere for 2 h at 300 320 and 340 °C. It appeared that the CoMo/Al2O3 sulfide catalyst have high performance in activity for promoting the fatty acid, fatty ester, fatty amide and fatty nitrile compounds were converted to paraffin/olefin (Diesel range), this could be the CUS site on supported Al2O3 catalyst. The difference in selectivity products allowed us to propose a reaction scheme.

  16. Effects of Post-Pyrolysis Air Oxidation of Biomass Chars on Adsorption of Neutral and Ionizable Compounds.

    PubMed

    Xiao, Feng; Pignatello, Joseph J

    2016-06-21

    This study was conducted to understand the effects of thermal air oxidation of biomass chars experienced during formation or production on their adsorptive properties toward various compounds, including five neutral nonpolar and polar compounds and seven weak acids and bases (pKa = 3-5.2) selected from among industrial chemicals and the triazine and phenoxyacetic acid herbicide classes. Post-pyrolysis air oxidation (PPAO) at 400 °C of anoxically prepared wood and pecan shell chars for up to 40 min enhanced the mass-normalized adsorption at pH ∼ 7.4 of all test compounds, especially the weak acids and bases, by up to 100-fold. Both general and specific effects were identified. The general effect results from "reaming" of pores by the oxidative removal of pore wall matter and/or tarry deposits generated during the pyrolysis step. Reaming creates new surface area and enlarges nanopores, which helps relieve steric hindrance to adsorption. The specific effect results from creation of new acidic functionality that provides sites for the formation of very strong, charge-assisted hydrogen bonds (CAHB) with solutes having comparable pKa. The CAHB hypothesis was supported by competition experiments and the finding that weak acid anion adsorption increased with surface carboxyl content, despite electrostatic repulsion from the growing negative charge. The results provide insight into the effects of air oxidation on pollutant retention.

  17. Application of the 15N tracer method to study the effect of pyrolysis temperature and atmosphere on the distribution of biochar nitrogen in the biomass-biochar-plant system.

    PubMed

    Tan, Zhongxin; Ye, Zhixiong; Zhang, Limei; Huang, Qiaoyun

    2018-05-01

    Biochar nitrogen is key to improving soil fertility, but the distribution of biochar nitrogen in the biomass-biochar-plant system is still unclear. To provide clarity, the 15 N tracer method was utilised to study the distribution of biochar nitrogen in the biochar both before and after its addition to the soil. The results can be summarised as follows. 1) The retention rate of 15 N in biochar decreases from 45.23% to 20.09% with increasing pyrolysis temperature from 400 to 800°C in a CO 2 atmosphere. 2) The retention rate of 15 N in biochar prepared in a CO 2 atmosphere is higher than that prepared in a N 2 atmosphere when the pyrolysis temperature is below 600°C. 3) Not only can biochar N slowly facilitate the adsorption of N by plants but the addition of biochar to the soil can also promote the supply of soil nitrogen to the plant; in contrast, the direct return of wheat straw biomass to the soil inhibits the absorption of soil N by plants. 4) In addition, the distribution of nitrogen was clarified; that is, when biochar was prepared by the pyrolysis of wheat straw at 400°C in a CO 2 atmosphere, the biochar retained 45.23% N, and after the addition of this biochar to the soil, 39.99% of N was conserved in the biochar residue, 4.55% was released into the soil, and 0.69% was contained in the wheat after growth for 31days. Therefore, this study very clearly shows the distribution of nitrogen in the biomass-biochar-plant system. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Pyrolysis and co-pyrolysis of Laminaria japonica and polypropylene over mesoporous Al-SBA-15 catalyst

    PubMed Central

    2014-01-01

    The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N2 adsorption-desorption isotherms, and NH3 temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H2O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro-d-galactitol and 1,5-anhydro-d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H2O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis. PMID:25136282

  19. Pyrolysis and co-pyrolysis of Laminaria japonica and polypropylene over mesoporous Al-SBA-15 catalyst.

    PubMed

    Lee, Hyung Won; Choi, Suek Joo; Park, Sung Hoon; Jeon, Jong-Ki; Jung, Sang-Chul; Kim, Sang Chai; Park, Young-Kwon

    2014-01-01

    The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N2 adsorption-desorption isotherms, and NH3 temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H2O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro-d-galactitol and 1,5-anhydro-d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H2O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis.

  20. Pyrolysis and co-pyrolysis of Laminaria japonica and polypropylene over mesoporous Al-SBA-15 catalyst

    NASA Astrophysics Data System (ADS)

    Lee, Hyung Won; Choi, Suek Joo; Park, Sung Hoon; Jeon, Jong-Ki; Jung, Sang-Chul; Kim, Sang Chai; Park, Young-Kwon

    2014-08-01

    The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N2 adsorption-desorption isotherms, and NH3 temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H2O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro- d-galactitol and 1,5-anhydro- d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H2O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis.

  1. Bio-oils from biomass slow pyrolysis: a chemical and toxicological screening.

    PubMed

    Cordella, Mauro; Torri, Cristian; Adamiano, Alessio; Fabbri, Daniele; Barontini, Federica; Cozzani, Valerio

    2012-09-15

    Bio-oils were produced from bench-scale slow-pyrolysis of three different biomass samples (corn stalks, poplar and switchgrass). Experimental protocols were developed and applied in order to screen their chemical composition. Several hazardous compounds were detected in the bio-oil samples analysed, including phenols, furans and polycyclic aromatic hydrocarbons. A procedure was outlined and applied to the assessment of toxicological and carcinogenic hazards of the bio-oils. The following hazardous properties were considered: acute toxicity; ecotoxicity; chronic toxicity; carcinogenicity. Parameters related to these properties were quantified for each component identified in the bio-oils and overall values were estimated for the bio-oils. The hazard screening carried out for the three bio-oils considered suggested that: (i) hazards to human health could be associated with chronic exposures to the bio-oils; (ii) acute toxic effects on humans and eco-toxic effects on aquatic ecosystems could also be possible in the case of loss of containment; and (iii) bio-oils may present a marginal potential carcinogenicity. The approach outlined allows the collection of screening information on the potential hazards posed by the bio-oils. This can be particularly useful when limited time and analytical resources reduce the possibility to obtain detailed specific experimental data. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. A comparative study of nitrogen conversion during pyrolysis of coconut fiber, its corresponding biochar and their blends with lignite.

    PubMed

    Liu, Zhengang; Balasubramanian, Rajasekhar

    2014-01-01

    In the present study, the conversion of fuel-N to HCN and NH3 was investigated during rapid pyrolysis of raw biomass (coconut fiber), its corresponding biochar and their blends with lignite within a temperature range of 600-900°C. The results showed that the raw biomass and the biochar showed totally different nitrogen partitioning between NH3 and HCN. HCN was the dominant nitrogen pollutant from pyrolysis of raw biomass, while for the biochar pyrolysis the yield of NH3 was slightly higher than that of HCN. Synergistic interactions occurred within both raw biomass/lignite and biochar/lignite blends, especially for the biochar/lignite blend, and resulted in reduced yields of HCN and NH3, decreased the total nitrogen percentage retained in the char and promoted harmless N2 formation. These findings suggest that biochar/lignite co-firing for energy production may have the enhanced benefit of reduced emissions of nitrogen pollutants than raw biomass/lignite. Copyright © 2013 Elsevier Ltd. All rights reserved.

  3. A pyrolysis study for the thermal and kinetic characteristics of an agricultural waste with two different plastic wastes.

    PubMed

    Çepelioğullar, Özge; Pütün, Ayşe E

    2014-10-01

    In this study, thermochemical conversion of plastic wastes (PET and PVC) together with an agricultural waste (hazelnut shell) was investigated. In order to determine the thermal and kinetic behaviours, pyrolysis experiments were carried out from room temperature to 800 °C, with a heating rate of 10 °C min(-1) in the presence of a N2 atmosphere in a thermogravimetric analyzer. With the obtained thermogravimetric data, an appropriate temperature was specified for the pyrolysis of biomass-plastic wastes in a fixed-bed reactor. At the second step, pyrolysis experiments were carried out at the same conditions with the thermogravimetric analyzer, except the final temperature which was up to 500 °C in this case. After pyrolysis experiments, pyrolysis yields were calculated and characterization studies for bio-oil were investigated. Experimental results showed that co-pyrolysis has an important role in the determination of the pyrolysis mechanism and the process conditions while designing/implementing a thermochemical conversion method where biomass-plastic materials were preferred as raw materials. © The Author(s) 2014.

  4. Biomass torrefaction: A promising pretreatment technology for biomass utilization

    NASA Astrophysics Data System (ADS)

    Chen, ZhiWen; Wang, Mingfeng; Ren, Yongzhi; Jiang, Enchen; Jiang, Yang; Li, Weizhen

    2018-02-01

    Torrefaction is an emerging technology also called mild pyrolysis, which has been explored for the pretreatment of biomass to make the biomass more favorable for further utilization. Dry torrefaction (DT) is a pretreatment of biomass in the absence of oxygen under atmospheric pressure and in a temperature range of 200-300 degrees C, while wet torrrefaction (WT) is a method in hydrothermal or hot and high pressure water at the tempertures within 180-260 degrees C. Torrrefied biomass is hydrophobic, with lower moisture contents, increased energy density and higher heating value, which are more comparable to the characteristics of coal. With the improvement in the properties, torrefied biomass mainly has three potential applications: combustion or co-firing, pelletization and gasification. Generally, the torrefaction technology can accelerate the development of biomass utilization technology and finally realize the maximum applications of biomass energy.

  5. Biomass Direct Liquefaction Options. TechnoEconomic and Life Cycle Assessment

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tews, Iva J.; Zhu, Yunhua; Drennan, Corinne

    The purpose of this work was to assess the competitiveness of two biomass to transportation fuel processing routes, which were under development in Finland, the U.S. and elsewhere. Concepts included fast pyrolysis (FP), and hydrothermal liquefaction (HTL), both followed by hydrodeoxygenation, and final product refining. This work was carried out as a collaboration between VTT (Finland), and PNNL (USA). The public funding agents for the work were Tekes in Finland and the Bioenergy Technologies Office of the U.S. Department of Energy. The effort was proposed as an update of the earlier comparative technoeconomic assessment performed by the IEA Bioenergy Directmore » Biomass Liquefaction Task in the 1980s. New developments in HTL and the upgrading of the HTL biocrude product triggered the interest in reinvestigating this comparison of these biomass liquefaction processes. In addition, developments in FP bio-oil upgrading had provided additional definition of this process option, which could provide an interesting comparison.« less

  6. Unravelling the Chemical Complexity of Biomass Burning VOC Emissions via H3O+ ToF-CIMS: Separation of High- and Low-temperature Pyrolysis Products

    NASA Astrophysics Data System (ADS)

    Sekimoto, K.; Koss, A.; Gilman, J.; Selimovic, V.; Coggon, M.; Zarzana, K. J.; Yuan, B.; Lerner, B. M.; Brown, S. S.; Warneke, C.; Yokelson, R. J.; De Gouw, J. A.

    2017-12-01

    Biomass burning is a large source of volatile organic compounds (VOCs) and many other trace species to the atmosphere. These VOCs can act as precursors to formation of secondary pollutants such as ozone and fine particles, and some VOCs can also have direct effects on human and ecosystem health. Multiple different and complex processes take place in biomass burning, e.g., distillation, flaming, and smoldering combustion processes. In a given fire, most of these processes occur simultaneously, but the relative importance of each can change over the course of a fire. This gives rise to some of the variability in VOC emissions between different fires. To study gas-phase emissions from biomass burning, an H3O+ ToF-CIMS was deployed during the FIREX 2016 laboratory intensive at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. This instrument has a fast time response and the measurements in stack burns show the varying gas-phase emissions as the mix of distillation, flaming, and smoldering varies. We used positive matrix factorization (PMF) to reduce and explain the observed chemical complexity in the gas phase. Despite the complexity and variability of emissions, we found that a solution including just two emission profiles explained on average 85% of the VOC emissions across 15 different fuel types including pines, firs, spruce, grass, shrubs, chaparrals, and wood wool. We identified the two profiles as resulting from high-temperature and low-temperature pyrolysis processes, and found that the profiles were remarkably similar (correlation coefficient r > 0.9) across nearly all the fuel types described above. Some of the remaining differences in VOC emission profiles between fuel types, and exceptions to the two-profile solution, can be explained by differences in the chemical composition of the fuels.

  7. Oil production by entrained pyrolysis of biomass and processing of oil and char

    DOEpatents

    Knight, James A.; Gorton, Charles W.

    1990-01-02

    Entrained pyrolysis of lignocellulosic material proceeds from a controlled pyrolysis-initiating temperature to completion of an oxygen free environment at atmospheric pressure and controlled residence time to provide a high yield recovery of pyrolysis oil together with char and non-condensable, combustible gases. The residence time is a function of gas flow rate and the initiating temperature is likewise a function of the gas flow rate, varying therewith. A controlled initiating temperature range of about 400.degree. C. to 550.degree. C. with corresponding gas flow rates to maximize oil yield is disclosed.

  8. Supercritical Fluids Processing of Biomass to Chemicals and Fuels

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Olson, Norman K.

    2011-09-28

    The main objective of this project is to develop and/or enhance cost-effective methodologies for converting biomass into a wide variety of chemicals, fuels, and products using supercritical fluids. Supercritical fluids will be used both to perform reactions of biomass to chemicals and products as well as to perform extractions/separations of bio-based chemicals from non-homogeneous mixtures. This work supports the Biomass Program’s Thermochemical Platform Goals. Supercritical fluids are a thermochemical approach to processing biomass that, while aligned with the Biomass Program’s interests in gasification and pyrolysis, offer the potential for more precise and controllable reactions. Indeed, the literature with respect tomore » the use of water as a supercritical fluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”« less

  9. In-depth investigation on the pyrolysis kinetics of raw biomass. Part I: kinetic analysis for the drying and devolatilization stages.

    PubMed

    Chen, Dengyu; Zheng, Yan; Zhu, Xifeng

    2013-03-01

    An in-depth investigation was conducted on the kinetic analysis of raw biomass using thermogravimetric analysis (TGA), from which the activation energy distribution of the whole pyrolysis process was obtained. Two different stages, namely, drying stage (Stage I) and devolatilization stage (Stage II), were shown in the pyrolysis process in which the activation energy values changed with conversion. The activation energy at low conversions (below 0.15) in the drying stage ranged from 10 to 30 kJ/mol. Such energy was calculated using the nonisothermal Page model, known as the best model to describe the drying kinetics. Kinetic analysis was performed using the distributed activation energy model in a wide range of conversions (0.15-0.95) in the devolatilization stage. The activation energy first ranged from 178.23 to 245.58 kJ/mol and from 159.66 to 210.76 kJ/mol for corn straw and wheat straw, respectively, then increasing remarkably with an irregular trend. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Design of pyrolysis reactor for production of bio-oil and bio-char simultaneously

    NASA Astrophysics Data System (ADS)

    Aladin, Andi; Alwi, Ratna Surya; Syarif, Takdir

    2017-05-01

    The residues from the wood industry are the main contributors to biomass waste in Indonesia. The conventional pyrolysis process, which needs a large energy as well as to produce various toxic chemical to the environment. Therefore, a pyrolysis unit on the laboratory scale was designed that can be a good alternative to achieve zero-waste and low energy cost. In this paper attempts to discuss design and system of pyrolysis reactor to produce bio-oil and bio-char simultaneously.

  11. Bifunctional catalysts for upgrading of biomass-derived oxygenates: A review

    DOE PAGES

    Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will

    2016-06-21

    Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chemicals. A key route for biomass refining involves the production of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the differentmore » types of elementary reaction steps required to deoxygenate biomass-derived compounds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compounds for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via molecular-level mechanisms. Finally, these studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates.« less

  12. New applications of X-ray tomography in pyrolysis of biomass: Biochar imaging

    DOE PAGES

    Jones, Keith; Ramakrishnan, Girish; Uchimiya, Minori; ...

    2015-01-30

    We report on the first ever use of non-destructive micrometer-scale synchrotron-computed microtomography (CMT) for biochar material characterization as a function of pyrolysis temperature. This innovative approach demonstrated an increase in micron-sized marcropore fraction of the Cotton Hull (CH) sample, resulting in up to 29% sample porosity. We have also found that initial porosity development occurred at low temperatures (below 350°C) of pyrolysis, consistent with chemical composition of CH. This innovative technique can be highly complementary to traditional BET measurements, considering that Barrett–Joyner–Halenda (BJH) analysis of pore size distribution cannot detect these macropores. Such information can be of substantial relevance tomore » environmental applications, given that water retention by biochars added to soils is controlled by macropore characteristic among the other factors. In addition, complementing our data with SEM, EDX, and XRF characterization techniques allowed us to develop a better understanding of evolution of biochar properties during its production, such presence of metals and initial morphological features of biochar before pyrolysis. These results have significant implications for using biochar as a soil additive and for clarifying the mechanisms of biofuel production by pyrolysis.« less

  13. New applications of X-ray tomography in pyrolysis of biomass: Biochar imaging

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jones, Keith; Ramakrishnan, Girish; Uchimiya, Minori

    We report on the first ever use of non-destructive micrometer-scale synchrotron-computed microtomography (CMT) for biochar material characterization as a function of pyrolysis temperature. This innovative approach demonstrated an increase in micron-sized marcropore fraction of the Cotton Hull (CH) sample, resulting in up to 29% sample porosity. We have also found that initial porosity development occurred at low temperatures (below 350°C) of pyrolysis, consistent with chemical composition of CH. This innovative technique can be highly complementary to traditional BET measurements, considering that Barrett–Joyner–Halenda (BJH) analysis of pore size distribution cannot detect these macropores. Such information can be of substantial relevance tomore » environmental applications, given that water retention by biochars added to soils is controlled by macropore characteristic among the other factors. In addition, complementing our data with SEM, EDX, and XRF characterization techniques allowed us to develop a better understanding of evolution of biochar properties during its production, such presence of metals and initial morphological features of biochar before pyrolysis. These results have significant implications for using biochar as a soil additive and for clarifying the mechanisms of biofuel production by pyrolysis.« less

  14. Guayule (parthenium argentatum) pyrolysis biorefining: production of hydrocarbon compatible bio-oils from guayule bagasse via tail-gas reactive pyrolysis

    USDA-ARS?s Scientific Manuscript database

    Guayule (Parthenium argentatum) is a woody desert shrub grown in the southwestern United States as a source of natural rubber, organic resins, and high energy biofuel feedstock from crop residues. We used guayule bagasse, the residual biomass after latex extraction as feedstock in a pyrolysis proces...

  15. Frederick G. Baddour | NREL

    Science.gov Websites

    hydrodeoxygenation of guaiacol under ex situ catalytic fast pyrolysis conditions," Top. Catal. (2015) " ;Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A

  16. Combustion properties, water absorption and grindability of raw/torrefied biomass pellets and Silantek coal

    NASA Astrophysics Data System (ADS)

    Matali, Sharmeela; Rahman, Norazah Abdul; Idris, Siti Shawaliah; Yaacob, Nurhafizah

    2017-12-01

    Torrefaction, also known as mild pyrolysis, is proven to convert raw biomass into a value-added energy commodity particularly for application in combustion and co-firing systems with improved storage and handling properties. This paper aims to compare the characteristics of Malaysian bituminous coal i.e. Silantek coal with raw and torrefied biomass pellet originated from oil palm frond and fast growing tree species, Leucaena Leucocephala. Biomass samples were initially torrefied at 300 °C for 60 minutes. Resulting torrefied biomass pellets were analysed using a number of standard fuel characterisation analyses i.e. elemental analysis, proximate analysis and calorific content (high heating values) experiments. Investigations on combustion characteristics via dynamic thermogravimetric analysis (TGA), grindability and moisture uptake tests were also performed on the torrefied biomass pellets. Better quality bio-chars were produced as compared to its raw forms and with optimal process conditions, torrefaction may potentially produces a solid fuel with combustion reactivity and porosity equivalent to raw biomass while having compatible energy density and grindability to coal.

  17. Co-pyrolysis of rice straw and polypropylene using fixed-bed pyrolyzer

    NASA Astrophysics Data System (ADS)

    Izzatie, N. I.; Basha, M. H.; Uemura, Y.; Mazlan, M. A.; Hashim, M. S. M.; Amin, N. A. M.; Hamid, M. F.

    2016-11-01

    The present work encompasses the impact of temperature (450, 500, 550, 600 °C) on the properties of pyrolysis oil and on other product yield for the co-pyrolysis of Polypropylene (PP) plastics and rice straw. Co-pyrolysis of PP plastic and rice straw were conducted in a fixed-bed drop type pyrolyzer under an inert condition to attain maximum oil yield. Physically, the pyrolysis oil is dark-brown in colour with free flowing and has a strong acrid smell. Copyrolysis between these typically obtained in maximum pyrolysis oil yields up to 69% by ratio 1:1 at a maximum temperature of 550 °C. From the maximum yield of pyrolysis oil, characterization of pyrolysis product and effect of biomass type of the composition were evaluated. Pyrolysis oil contains a high water content of 66.137 wt.%. Furfural, 2- methylnaphthalene, tetrahydrofuran (THF), toluene and acetaldehyde were the major organic compounds found in pyrolysis oil of rice straw mixed with PP. Bio-char collected from co-pyrolysis of rice straw mixed with PP plastic has high calorific value of 21.190 kJ/g and also carbon content with 59.02 wt.% and could contribute to high heating value. The non-condensable gases consist of hydrogen, carbon monoxide, and methane as the major gas components.

  18. A Low-cost, High-yield Process for the Direct Productin of High Energy Density Liquid Fuel from Biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Agrawal, Rakesh; Delgass, W. N.; Ribeiro, F.

    2013-08-31

    The primary objective and outcome of this project was the development and validation of a novel, low-cost, high-pressure fast-hydropyrolysis/hydrodeoxygenation (HDO) process (H 2Bioil) using supplementary hydrogen (H 2) to produce liquid hydrocarbons from biomass. The research efforts under the various tasks of the project have culminated in the first experimental demonstration of the H 2Bioil process, producing 100% deoxygenated >C4+ hydrocarbons containing 36-40% of the carbon in the feed of pyrolysis products from biomass. The demonstrated H{sub 2}Bioil process technology (i.e. reactor, catalyst, and downstream product recovery) is scalable to a commercial level and is estimated to be economically competitivemore » for the cases when supplementary H 2 is sourced from coal, natural gas, or nuclear. Additionally, energy systems modeling has revealed several process integration options based on the H 2Bioilprocess for energy and carbon efficient liquid fuel production. All project tasks and milestones were completed or exceeded. Novel, commercially-scalable, high-pressure reactors for both fast-hydropyrolysis and hydrodeoxygenation were constructed, completing Task A. These reactors were capable of operation under a wide-range of conditions; enabling process studies that lead to identification of optimum process conditions. Model compounds representing biomass pyrolysis products were studied, completing Task B. These studies were critical in identifying and developing HDO catalysts to target specific oxygen functional groups. These process and model compound catalyst studies enabled identification of catalysts that achieved 100% deoxygenation of the real biomass feedstock, sorghum, to form hydrocarbons in high yields as part of Task C. The work completed during this grant has identified and validated the novel and commercially scalable H 2Bioil process for production of hydrocarbon fuels from biomass. Studies on model compounds as well as real biomass feedstocks

  19. Kinetics evaluation and thermal decomposition characteristics of co-pyrolysis of municipal sewage sludge and hazelnut shell.

    PubMed

    Zhao, Bing; Xu, Xinyang; Li, Haibo; Chen, Xi; Zeng, Fanqiang

    2018-01-01

    Hazelnut shell, as novel biomass, has lower ash content and abundant hydrocarbon, which can be utilized resourcefully with municipal sewage sludge (MSS) by co-pyrolyisis to decrease total content of pollution. The co-pyrolysis of MSS and hazelnut shell blend was analyzed by a method of multi-heating rates and different blend ratios with TG-DTG-MS under N 2 atmosphere. The apparent activation energy of co-pyrolysis was calculated by three iso-conversional methods. Satava-Sestak method was used to determine mechanism function G(α) of co-pyrolysis, and Lorentzian function was used to simulate multi-peaks curves. The results showed there were four thermal decomposition stages, and the biomass were cracked and evolved at different temperature ranges. The apparent activation energy increased from 123.99 to 608.15kJ/mol. The reaction mechanism of co-pyrolysis is random nucleation and nuclei growth. The apparent activation energy and mechanism function afford a theoretical groundwork for co-pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. A Review on Biomass Torrefaction Process and Product Properties

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jaya Shankar Tumuluru; Shahab Sokhansanj; Christopher T. Wright

    2011-08-01

    Biomass Torrefaction is gaining attention as an important preprocessing step to improve the quality of biomass in terms of physical properties and chemical composition. Torrefaction is a slow heating of biomass in an inert or reduced environment to a maximum temperature of approximately 300 C. Torrefaction can also be defined as a group of products resulting from the partially controlled and isothermal pyrolysis of biomass occurring in a temperature range of 200-280 C. Thus, the process can be called a mild pyrolysis as it occurs at the lower temperature range of the pyrolysis process. At the end of the torrefactionmore » process, a solid uniform product with lower moisture content and higher energy content than raw biomass is produced. Most of the smoke-producing compounds and other volatiles are removed during torrefaction, which produces a final product that will have a lower mass but a higher heating value. The present review work looks into (a) torrefaction process and different products produced during the process and (b) solid torrefied material properties which include: (i) physical properties like moisture content, density, grindability, particle size distribution and particle surface area and pelletability; (ii) chemical properties like proximate and ultimate composition; and (iii) storage properties like off-gassing and spontaneous combustion.« less

  1. Study on co-pyrolysis characteristics of rice straw and Shenfu bituminous coal blends in a fixed bed reactor.

    PubMed

    Li, Shuaidan; Chen, Xueli; Liu, Aibin; Wang, Li; Yu, Guangsuo

    2014-03-01

    Co-pyrolysis behaviors of rice straw and Shenfu bituminous coal were studied in a fixed bed reactor under nitrogen atmosphere. The pyrolysis temperatures were 700°C, 800°C and 900°C, respectively. Six different biomass ratios were used. Gas, tar components were analyzed by a gas chromatograph and a gas chromatography-mass spectrometry respectively. Under co-pyrolysis conditions, the gas volume yields are higher than the calculated values. Co-pyrolysis tar contains more phenolics, less oxygenate compounds than calculated values. The addition of biomass changes the atmosphere during the pyrolysis process and promotes tar decomposition. The SEM results show that the differences between the blended char and their parents char are not significant. The results of char yields and ultimate analysis also show that no significant interactions exist between the two kinds of particles. The changes of gas yield and components are caused by the secondary reactions and tar decomposition. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Biocrude oils from the fast pyrolysis of poultry litter and hardwood

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Agblevor, F.A., E-mail: Fagblevo@vt.ed; Beis, S.; Kim, S.S.

    2010-02-15

    The safe and economical disposal of poultry litter is becoming a major problem for the USA poultry industry. Current disposal methods such as land application and feeding to cattle are now under pressure because of pollution of water resources due to leaching, runoffs and concern for mad cow disease contamination of the food chain. Incineration or combustion is potentially applicable to large scale operations, but for small scale growers and EPA non-attainment areas, this is not a suitable option because of the high cost of operation. Thus, there is a need for developing appropriate technologies to dispose poultry litter. Poultrymore » litters from broiler chicken and turkey houses, as well as bedding material were converted into biocrude oil in a fast pyrolysis fluidized bed reactor. The biocrude oil yields were relatively low ranging from 36 wt% to 50 wt% depending on the age and bedding material content of the litter. The bedding material (which was mostly hardwood shavings) biocrude oil yield was 63 wt%. The higher heating value (HHV) of the poultry litter biocrude oils ranged from 26 MJ/kg to 29 MJ/kg while that of the bedding material was 24 MJ/kg. The oils had relatively high nitrogen content ranging from 4 wt% to 8 wt%, very low sulfur (<1 wt%) content and high viscosity. The viscosities of the oils appeared to be a function of both the source of litter and the pyrolysis temperature. The biochar yield ranged from 27 wt% to 40 wt% depending on the source, age and composition of the poultry litter. The biochar ash content ranged from 24 wt% to 54 wt% and was very rich in inorganic components such as potassium and phosphorous.« less

  3. Biocrude oils from the fast pyrolysis of poultry litter and hardwood.

    PubMed

    Agblevor, F A; Beis, S; Kim, S S; Tarrant, R; Mante, N O

    2010-02-01

    The safe and economical disposal of poultry litter is becoming a major problem for the USA poultry industry. Current disposal methods such as land application and feeding to cattle are now under pressure because of pollution of water resources due to leaching, runoffs and concern for mad cow disease contamination of the food chain. Incineration or combustion is potentially applicable to large scale operations, but for small scale growers and EPA non-attainment areas, this is not a suitable option because of the high cost of operation. Thus, there is a need for developing appropriate technologies to dispose poultry litter. Poultry litters from broiler chicken and turkey houses, as well as bedding material were converted into biocrude oil in a fast pyrolysis fluidized bed reactor. The biocrude oil yields were relatively low ranging from 36 wt% to 50 wt% depending on the age and bedding material content of the litter. The bedding material (which was mostly hardwood shavings) biocrude oil yield was 63 wt%. The higher heating value (HHV) of the poultry litter biocrude oils ranged from 26 MJ/kg to 29 MJ/kg while that of the bedding material was 24 MJ/kg. The oils had relatively high nitrogen content ranging from 4 wt% to 8 wt%, very low sulfur (<1 wt%) content and high viscosity. The viscosities of the oils appeared to be a function of both the source of litter and the pyrolysis temperature. The biochar yield ranged from 27 wt% to 40 wt% depending on the source, age and composition of the poultry litter. The biochar ash content ranged from 24 wt% to 54 wt% and was very rich in inorganic components such as potassium and phosphorous.

  4. Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions.

    PubMed

    Zhou, Hui; Wu, Chunfei; Onwudili, Jude A; Meng, Aihong; Zhang, Yanguo; Williams, Paul T

    2015-02-01

    The formation of 2-4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. The results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5

    DOE PAGES

    Yung, Matthew M.; Stanton, Alexander R.; Iisa, Kristiina; ...

    2016-10-07

    Metal-impregnated (Ni or Ga) ZSM-5 catalysts were studied for biomass pyrolysis vapor upgrading to produce hydrocarbons using three reactors constituting a 100 000x change in the amount of catalyst used in experiments. Catalysts were screened for pyrolysis vapor phase upgrading activity in two small-scale reactors: (i) a Pyroprobe with a 10 mg catalyst in a fixed bed and (ii) a fixed-bed reactor with 500 mg of catalyst. The best performing catalysts were then validated with a larger scale fluidized-bed reactor (using ~1 kg of catalyst) that produced measurable quantities of bio-oil for analysis and evaluation of mass balances. Despite somemore » inherent differences across the reactor systems (such as residence time, reactor type, analytical techniques, mode of catalyst and biomass feed) there was good agreement of reaction results for production of aromatic hydrocarbons, light gases, and coke deposition. Relative to ZSM-5, Ni or Ga addition to ZSM-5 increased production of fully deoxygenated aromatic hydrocarbons and light gases. In the fluidized bed reactor, Ga/ZSM-5 slightly enhanced carbon efficiency to condensed oil, which includes oxygenates in addition to aromatic hydrocarbons, and reduced oil oxygen content compared to ZSM-5. Ni/ZSM-5, while giving the highest yield of fully deoxygenated aromatic hydrocarbons, gave lower overall carbon efficiency to oil but with the lowest oxygen content. Reaction product analysis coupled with fresh and spent catalyst characterization indicated that the improved performance of Ni/ZSM-5 is related to decreasing deactivation by coking, which keeps the active acid sites accessible for the deoxygenation and aromatization reactions that produce fully deoxygenated aromatic hydrocarbons. The addition of Ga enhances the dehydrogenation activity of the catalyst, which leads to enhanced olefin formation and higher fully deoxygenated aromatic hydrocarbon yields compared to unmodified ZSM-5. Catalyst characterization by ammonia

  6. Biomass [updated

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Turhollow Jr, Anthony F

    2016-01-01

    Biomass resources and conversion technologies are diverse. Substantial biomass resources exist including woody crops, herbaceous perennials and annuals, forest resources, agricultural residues, and algae. Conversion processes available include fermentation, gasification, pyrolysis, anaerobic digestion, combustion, and transesterification. Bioderived products include liquid fuels (e.g. ethanol, biodiesel, and gasoline and diesel substitutes), gases, electricity, biochemical, and wood pellets. At present the major sources of biomass-derived liquid fuels are from first generation biofuels; ethanol from maize and sugar cane (89 billion L in 2013) and biodiesel from vegetable oils and fats (24 billion liters in 2011). For other than traditional uses, policy in themore » forms of mandates, targets, subsidies, and greenhouse gas emission targets has largely been driving biomass utilization. Second generation biofuels have been slow to take off.« less

  7. Review of the Pyrolysis Platform for Producing Bio-oil and Biochar: Technology, Logistics, and Potential Impacts on Greenhouse Gas Emissions, Water Quality, Soil Quality, and Agricultural Productivity

    USDA-ARS?s Scientific Manuscript database

    Pyrolysis is a relatively simple, inexpensive, and robust thermochemical technology for transforming biomass into bio-oil, biochar, and syngas. The robust nature of the pyrolysis technology, which allows considerable flexibility in both the type and quality of the biomass feedstock, combined with a ...

  8. Time scale dependent negative emission potential of forests and biomass plantations via wood burial, torrefied biomass, biochar and pyrogas condensate sequestration in soil

    NASA Astrophysics Data System (ADS)

    Schmidt, Hans-Peter; Kammann, Claudia; Lucht, Wolfgang; Gerten, Dieter; Foidl, Nikolaus

    2017-04-01

    The efficiency of Negative Emission Technologies (NET) is dependent on (1) the transformation of the biomass carbon into a form that can be sequestered, (2) the mean residence time of the sequestered carbon, (3) the regrowth and thus carbon re-accumulation of the harvested biomass, and (4) the positive or negative priming of soil carbon. These four parameters define the time scale dependent C-balance of various NET-Systems and permit a global economic and environmental evaluation. As far as geologic CO2 storage is considered to be feasible with close to zero losses and if the energy for transport, transformation and disposal is taken from the process bioenergy, conventional BE-CCS has a C sequestration potential of 50 - 70 % depending on the type of biomass and the technology used. Beside unknown risks of deep stored CO2 and high costs, regrowth of C-accumulating biomass is hampered in the long-term as not only carbon but also essential soil nutrients are mined. Under this scenario, biomass regrowth is expected to slow down and soil carbon content to decrease. These factors enlarge the time horizon until a BE-CCS system becomes carbon neutral and eventual carbon negative (when biomass regrowth exceeds the difference between the harvested biomass carbon and BE-CCS stored carbon). Thermal treatment of biomass under a low oxygen regime (torrefaction, pyrolysis, gasification) can transform up to 85% of biomass carbon into various solid and liquid forms of recalcitrant carbon that can be sequestered. Depending on the process parameters and temperature, the mean residence time of the torrefied or pyrolysed biomass can last from several decennials to centennials when applied to the soil of the biomass production site. The carbon can thus be stored at comparatively low costs within the ecosystem itself. As the thermal treatment preserves most of the biomass-accumulated nutrients (except N), natural nutrient cycles are maintained within the biomass system. Depending on the

  9. Valorization of pyrolysis water: a biorefinery side stream, for 1,2-propanediol production with engineered Corynebacterium glutamicum.

    PubMed

    Lange, Julian; Müller, Felix; Bernecker, Kerstin; Dahmen, Nicolaus; Takors, Ralf; Blombach, Bastian

    2017-01-01

    A future bioeconomy relies on the efficient use of renewable resources for energy and material product supply. In this context, biorefineries have been developed and play a key role in converting lignocellulosic residues. Although a holistic use of the biomass feed is desired, side streams evoke in current biorefinery approaches. To ensure profitability, efficiency, and sustainability of the overall conversion process, a meaningful valorization of these materials is needed. Here, a so far unexploited side stream derived from fast pyrolysis of wheat straw-pyrolysis water-was used for production of 1,2-propanediol in microbial fermentation with engineered Corynebacterium glutamicum . A protocol for pretreatment of pyrolysis water was established and enabled growth on its major constituents, acetate and acetol, with rates up to 0.36 ± 0.04 h -1 . To convert acetol to 1,2-propanediol, the plasmid pJUL gldA expressing the glycerol dehydrogenase from Escherichia coli was introduced into C. glutamicum . 1,2-propanediol was formed in a growth-coupled biotransformation and production was further increased by construction of C. glutamicum Δ pqo Δ aceE Δ ldhA Δ mdh pJUL gldA . In a two-phase aerobic/microaerobic fed-batch process with pyrolysis water as substrate, this strain produced 18.3 ± 1.2 mM 1,2-propanediol with a yield of 0.96 ± 0.05 mol 1,2-propanediol per mol acetol and showed an overall volumetric productivity of 1.4 ± 0.1 mmol 1,2-propanediol L -1  h -1 . This study implements microbial fermentation into a biorefinery based on pyrolytic liquefaction of lignocellulosic biomass and accesses a novel value chain by valorizing the side stream pyrolysis water for 1,2-PDO production with engineered C. glutamicum . The established bioprocess operated at maximal product yield and accomplished the so far highest overall volumetric productivity for microbial 1,2-PDO production with an engineered producer strain. Besides, the results highlight the

  10. Modeling of biomass to hydrogen via the supercritical water pyrolysis process

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Divilio, R.J.

    1998-08-01

    A heat transfer model has been developed to predict the temperature profile inside the University of Hawaii`s Supercritical Water Reactor. A series of heat transfer tests were conducted on the University of Hawaii`s apparatus to calibrate the model. Results of the model simulations are shown for several of the heat transfer tests. Tests with corn starch and wood pastes indicated that there are substantial differences between the thermal properties of the paste compared to pure water, particularly near the pseudo critical temperature. The assumption of constant thermal diffusivity in the temperature range of 250 to 450 C gave a reasonablemore » prediction of the reactor temperatures when paste is being fed. A literature review is presented for pyrolysis of biomass in water at elevated temperatures up to the supercritical range. Based on this review, a global reaction mechanism is proposed. Equilibrium calculations were performed on the test results from the University of Hawaii`s Supercritical Water Reactor when corn starch and corn starch and wood pastes were being fed. The calculations indicate that the data from the reactor falls both below and above the equilibrium hydrogen concentrations depending on test conditions. The data also indicates that faster heating rates may be beneficial to the hydrogen yield. Equilibrium calculations were also performed to examine the impact of wood concentration on the gas mixtures produced. This calculation showed that increasing wood concentrations favors the formation of methane at the expense of hydrogen.« less

  11. Solar coal gasification reactor with pyrolysis gas recycle

    DOEpatents

    Aiman, William R.; Gregg, David W.

    1983-01-01

    Coal (or other carbonaceous matter, such as biomass) is converted into a duct gas that is substantially free from hydrocarbons. The coal is fed into a solar reactor (10), and solar energy (20) is directed into the reactor onto coal char, creating a gasification front (16) and a pyrolysis front (12). A gasification zone (32) is produced well above the coal level within the reactor. A pyrolysis zone (34) is produced immediately above the coal level. Steam (18), injected into the reactor adjacent to the gasification zone (32), reacts with char to generate product gases. Solar energy supplies the energy for the endothermic steam-char reaction. The hot product gases (38) flow from the gasification zone (32) to the pyrolysis zone (34) to generate hot char. Gases (38) are withdrawn from the pyrolysis zone (34) and reinjected into the region of the reactor adjacent the gasification zone (32). This eliminates hydrocarbons in the gas by steam reformation on the hot char. The product gas (14) is withdrawn from a region of the reactor between the gasification zone (32) and the pyrolysis zone (34). The product gas will be free of tar and other hydrocarbons, and thus be suitable for use in many processes.

  12. Performance of rotary kiln reactor for the elephant grass pyrolysis.

    PubMed

    De Conto, D; Silvestre, W P; Baldasso, C; Godinho, M

    2016-10-01

    The influence of process conditions (rotary speed/temperature) on the performance of a rotary kiln reactor for non-catalytic pyrolysis of a perennial grass (elephant grass) was investigated. The product yields, the production of non-condensable gases as well as the biochar properties were evaluated. The maximum H2 yield was close to that observed for catalytic pyrolysis processes, while the bio-oil yield was higher than reported for pyrolysis of other biomass in rotary kiln reactors. A H2/CO ratio suitable for Fischer-Tropsch synthesis (FTS) was obtained. The biochars presented an alkaline pH (above 10) and interesting contents of nutrients, as well as low electrical conductivity, indicating a high potential as soil amendment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Adding nickel formate in alkali lignin to increase contents of alkylphenols and aromatics during fast pyrolysis.

    PubMed

    Geng, Jing; Wang, Wen-Liang; Yu, Yu-Xiang; Chang, Jian-Min; Cai, Li-Ping; Shi, Sheldon Q

    2017-03-01

    The composition of pyrolysis vapors obtained from alkali lignin pyrolysis with the additive of nickel formate was examined using the pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). Characterization of bio-chars was performed using X-ray diffraction (XRD). Results showed that the nickel formate significantly increased liquid yield, simplified the types of alkali lignin pyrolysis products and increased individual component contents. The additive of nickel formate increased contents of alkylphenols and aromatics from alkali lignin pyrolysis. With an increase in temperature, a greater amount of the relative contents can be achieved. The nickel formate was thermally decomposed to form hydrogen, resulting in hydrodeoxygenation of alkali lignin during pyrolysis. It was also found that Ni is in favor of producing alkylphenols. The analysis based on the experimental result provided evidences used to propose reaction mechanism for pyrolysis of nickel formate-assisted alkali lignin. Copyright © 2016. Published by Elsevier Ltd.

  14. Kristiina Iisa | NREL

    Science.gov Websites

    ," Topics in Catalysis (2016) "Hydrotreating the Organic Fraction of Biomass Pyrolysis Oil to a Biomass via Hot-Vapor-Filtered Fast Pyrolysis and Catalytic Hydroprocessing of the Bio-oil," Energy & Fuels (2014) "Evaluate Impact of Catalyst Type on Oil Yield and Hydrogen Consumption from

  15. Maximizing the stability of pyrolysis oil/diesel fuel emulsions

    USDA-ARS?s Scientific Manuscript database

    Several emulsions consisting of biomass pyrolysis oil (bio-oil) in diesel fuel were produced and analyzed for stability over time. An ultrasonic probe was used to generate microscopic droplets of bio-oil suspended in diesel fuel, and this emulsion was stabilized using surfactant chemicals. The most...

  16. Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst.

    PubMed

    Liu, Shiyu; Xie, Qinglong; Zhang, Bo; Cheng, Yanling; Liu, Yuhuan; Chen, Paul; Ruan, Roger

    2016-03-01

    This study investigated fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst. Effects of reaction temperature, CaO/HZSM-5 ratio, and corn stover/scum ratio on co-pyrolysis product fractional yields and selectivity were investigated. Results showed that co-pyrolysis temperature was selected as 550°C, which provides the maximum bio-oil and aromatic yields. Mixed CaO and HZSM-5 catalyst with the weight ratio of 1:4 increased the aromatic yield to 35.77 wt.% of feedstock, which was 17% higher than that with HZSM-5 alone. Scum as the hydrogen donor, had a significant synergistic effect with corn stover to promote the production of bio-oil and aromatic hydrocarbons when the H/C(eff) value exceeded 1. The maximum yield of aromatic hydrocarbons (29.3 wt.%) were obtained when the optimal corn stover to scum ratio was 1:2. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Chemical Characterization and Water Content Determination of Bio-Oils Obtained from Various Biomass Species using 31P NMR Spectroscopy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    David, K.; Ben, H.; Muzzy, J.

    2012-03-01

    Pyrolysis is a promising approach to utilize biomass for biofuels. One of the key challenges for this conversion is how to analyze complicated components in the pyrolysis oils. Water contents of pyrolysis oils are normally analyzed by Karl Fischer titration. The use of 2-chloro-4,4,5,5,-tetramethyl-1,3,2-dioxaphospholane followed by {sup 31}P NMR analysis has been used to quantitatively analyze the structure of hydroxyl groups in lignin and whole biomass. Results: {sup 31}P NMR analysis of pyrolysis oils is a novel technique to simultaneously characterize components and analyze water contents in pyrolysis oils produced from various biomasses. The water contents of various pyrolysis oilsmore » range from 16 to 40 wt%. The pyrolysis oils obtained from Loblolly pine had higher guaiacyl content, while that from oak had a higher syringyl content. Conclusion: The comparison with Karl Fischer titration shows that {sup 31}P NMR could also reliably be used to measure the water content of pyrolysis oils. Simultaneously with analysis of water content, quantitative characterization of hydroxyl groups, including aliphatic, C-5 substituted/syringyl, guaiacyl, p-hydroxyl phenyl and carboxylic hydroxyl groups, could also be provided by {sup 31}P NMR analysis.« less

  18. Reinforcement of the bio-gas conversion from pyrolysis of wheat straw by hot caustic pre-extraction.

    PubMed

    Zhang, Lilong; Chen, Keli; He, Liang; Peng, Lincai

    2018-01-01

    Pyrolysis has attracted growing interest as a versatile means to convert biomass into valuable products. Wheat straw has been considered to be a promising biomass resource due to its low price and easy availability. However, most of the products obtained from wheat straw pyrolysis are usually of low quality. Hot soda extraction has the advantage of selective dissolution of lignin whilst retaining the carbohydrates. This can selectively convert biomass into high-quality desired products and suppress the formation of undesirable products. The aim of this study was to investigate the pyrolysis properties of wheat straw under different hot caustic pretreatment conditions. Compared with the untreated straw, a greater amount of gas was released and fewer residues were retained in the extracted wheat straw, which was caused by an increase in porosity. When the NaOH loading was 14%, the average pore size of the extracted straw increased by 12% and the cumulative pore volume increased by 157% compared with the untreated straw. The extracted straw obtained from the 14% NaOH extraction was clearly selective for pyrolysis products. On one hand, many lignin pyrolysis products disappeared, and only four main lignin-unit-pyrolysis products were retained. On the other hand, polysaccharide pyrolysis products were enriched. Both propanone and furfural have outstanding peak intensities that could account for approximately 30% of the total pyrolysis products. However, with the excessive addition of NaOH (i.e. > 22% w/w) during pretreatment, the conversion of bio-gas products decreased. Thermogravimetric and low-temperature nitrogen-adsorption analysis showed that the pore structure had been seriously destroyed, leading to the closing of the release paths of the bio-gas and thus increasing the re-polymerisation of small bio-gas molecules. After suitable extraction (14% NaOH loading extraction), a considerable amount (25%) of the soluble components dissolved out of the straw. This

  19. Improvement of bio-oil yield and quality in co-pyrolysis of corncobs and high density polyethylene in a fixed bed reactor at low heating rate

    NASA Astrophysics Data System (ADS)

    Supramono, D.; Lusiani, S.

    2016-11-01

    Over the past few decades, interest in developing biomass-derived fuel has been increasing rapidly due to the decrease in fossil fuel reserves. Bio-oil produced by biomass pyrolysis however contains high oxygen compounds resulting in low calorific-value fuel and therefore requiring upgrading. In co-pyrolysis of the feed blend of plastics of High Density Polyethylene (HDPE) and biomass of com cob particles, at some compositions free radicals from plastic decomposition containing more hydrogen radicals are able to bond oxygen radicals originating from biomass to reduce oxygenate compounds in the bio-oil thus increasing bio-oil quality. This phenomenon is usually called synergetic effect. In addition to that, the pattern of heating of the feed blend in the pyrolysis reactor is predicted to affect biooil quality and yield. In a batch reactor, co-pyrolysis of corncobs and HDPE requires low heating rate to reach a peak temperature at temperature rise period followed by heating for some time at peak temperature called holding time at constant temperature period. No research has been carried out to investigate how long holding time is set in co-pyrolysis of plastic and biomass to obtain high yield of bio-oil. Holding time may affect either crosslinking of free radicals in gas phase, which increases char product, or secondary pyrolysis in the gas phase, which increases non-condensable gas in the gas phase of pyrolysis reactor, both of which reduce bio-oil yield. Therefore, holding time of co-pyrolysis affects the mass rate of bio-oil formation as the pyrolysis proceeds and quality of the bio-oil. In the present work, effects of holding time on the yield and quality of bio-oil have been investigated using horizontal fixed bed of the feed blends at heating rate of 5°C, peak temperature of 500°C and N2 flow rate of 700 ml/minute. Holding time was varied from 0 to 70 minutes with 10 minutes interval. To investigate the effects of holding time, the composition of HDPE in the

  20. Catalytic conversion of biomass pyrolysis-derived compounds with chemical liquid deposition (CLD) modified ZSM-5.

    PubMed

    Zhang, Huiyan; Luo, Mengmeng; Xiao, Rui; Shao, Shanshan; Jin, Baosheng; Xiao, Guomin; Zhao, Ming; Liang, Junyu

    2014-03-01

    Chemical liquid deposition (CLD) with KH550, TEOS and methyl silicone oil as the modifiers was used to modify ZSM-5 and deposit its external acid sites. The characteristics of modified catalysts were tested by catalytic conversion of biomass pyrolysis-derived compounds. The effects of different modifying conditions (deposited amount, temperature, and time) on the product yields and selectivities were investigated. The results show KH550 modified ZSM-5 (deposited amount of 4%, temperature of 20°C and time of 6h) produced the maximum yields of aromatics (24.5%) and olefins (16.5%), which are much higher than that obtained with original ZSM-5 catalyst (18.8% aromatics and 9.8% olefins). The coke yield decreased from 44.1% with original ZSM-5 to 26.7% with KH550 modified ZSM-5. The selectivities of low-molecule-weight hydrocarbons (ethylene and benzene) decreased, while that of higher molecule-weight hydrocarbons (propylene, butylene, toluene, and naphthalene) increased comparing with original ZSM-5. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Characterization of primary thermal degradation features of lignocellulosic biomass after removal of inorganic metals by diverse solvents.

    PubMed

    Eom, In-Yong; Kim, Kwang-Ho; Kim, Jae-Young; Lee, Soo-Min; Yeo, Hwan-Myung; Choi, In-Gyu; Choi, Joon-Weon

    2011-02-01

    Poplar wood powders were treated with distilled water, tap water, HCl and HF, respectively, to remove inorganics from the biomass and to investigate effect of demineralization processes on pyrolysis behavior of the biomass. TG and DTG revealed that maximum degradation temperatures rose slightly from 362°C for control to 372°C, 366°C and 368°C after demineralization with distilled water, HCl and HF, respectively. Maximum degradation rates also increased from 0.96%/°C for control to 1.15%/°C for HF-biomass, 1.23%/°C for DI-H(2)O-biomass, and 1.55%/°C for HCl-biomass. Analytical pyrolysis-GC/MS of demineralized biomasses produced approximately 45 pyrolysis compounds. Total amount of low molecular weight compounds, such as acetic acid, acetol, and 3-hydroxypropanal, was significantly lowered in the demineralized biomasses. But levoglucosan increased 2-10-folds in the demineralized biomasses. One of the features regarding lignin derivatives was the reduction of the amount of C6-type phenols, such as phenol, guaiacol, and syringol after demineralization. Copyright © 2010 Elsevier Ltd. All rights reserved.

  2. Estimation of Antarctic Land-Fast Sea Ice Algal Biomass and Snow Thickness From Under-Ice Radiance Spectra in Two Contrasting Areas

    NASA Astrophysics Data System (ADS)

    Wongpan, P.; Meiners, K. M.; Langhorne, P. J.; Heil, P.; Smith, I. J.; Leonard, G. H.; Massom, R. A.; Clementson, L. A.; Haskell, T. G.

    2018-03-01

    Fast ice is an important component of Antarctic coastal marine ecosystems, providing a prolific habitat for ice algal communities. This work examines the relationships between normalized difference indices (NDI) calculated from under-ice radiance measurements and sea ice algal biomass and snow thickness for Antarctic fast ice. While this technique has been calibrated to assess biomass in Arctic fast ice and pack ice, as well as Antarctic pack ice, relationships are currently lacking for Antarctic fast ice characterized by bottom ice algae communities with high algal biomass. We analyze measurements along transects at two contrasting Antarctic fast ice sites in terms of platelet ice presence: near and distant from an ice shelf, i.e., in McMurdo Sound and off Davis Station, respectively. Snow and ice thickness, and ice salinity and temperature measurements support our paired in situ optical and biological measurements. Analyses show that NDI wavelength pairs near the first chlorophyll a (chl a) absorption peak (≈440 nm) explain up to 70% of the total variability in algal biomass. Eighty-eight percent of snow thickness variability is explained using an NDI with a wavelength pair of 648 and 567 nm. Accounting for pigment packaging effects by including the ratio of chl a-specific absorption coefficients improved the NDI-based algal biomass estimation only slightly. Our new observation-based algorithms can be used to estimate Antarctic fast ice algal biomass and snow thickness noninvasively, for example, by using moored sensors (time series) or mapping their spatial distributions using underwater vehicles.

  3. Pyrolysis and Matrix-Isolation FTIR of Acetoin

    NASA Astrophysics Data System (ADS)

    Cole, Sarah; Ellis, Martha; Sowards, John; McCunn, Laura R.

    2017-06-01

    Acetoin, CH_3C(O)CH(OH)CH_3, is an additive used in foods and cigarettes as well as a common component of biomass pyrolysate during the production of biofuels, yet little is known about its thermal decomposition mechanism. In order to identify thermal decomposition products of acetoin, a gas-phase mixture of approximately 0.3% acetoin in argon was subject to pyrolysis in a resistively heated SiC microtubular reactor at 1100-1500 K. Matrix-isolation FTIR spectroscopy was used to identify pyrolysis products. Many products were observed in analysis of the spectra, including acetylene, propyne, ethylene, and vinyl alcohol. These results provide clues to the overall mechanism of thermal decomposition and are important for predicting emissions from many industrial and residential processes.

  4. Fast microwave-assisted catalytic co-pyrolysis of lignin and low-density polyethylene with HZSM-5 and MgO for improved bio-oil yield and quality.

    PubMed

    Fan, Liangliang; Chen, Paul; Zhang, Yaning; Liu, Shiyu; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Ruan, Roger

    2017-02-01

    Fast microwave-assisted catalytic co-pyrolysis of lignin and low-density polyethylene (LDPE) with HZSM-5 and MgO was investigated. Effects of pyrolysis temperature, lignin to LDPE ratio, MgO to HZSM-5 ratio, and feedstock to catalyst ratio on the products yields and chemical profiles were examined. 500°C was the optimal co-pyrolysis temperature in terms of the maximum bio-oil yield. The proportion of aromatics increased with increasing LDPE content. In addition, with the addition of LDPE (lignin/LDPE=1/2), methoxyl group in the phenols was completely removed. A synergistic effect was found between lignin and LDPE. The proportion of aromatics increased and alkylated phenols decreased with increasing HZSM-5 to MgO ratio. The bio-oil yield increased with the addition of appropriate amount of catalyst and the proportion of alkylated phenols increased with increasing catalyst to feedstock ratio. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Dielectric properties of biomass and biochar mixtures for bioenergy applications

    USDA-ARS?s Scientific Manuscript database

    Biomass is an abundant and renewable energy resource, which may be converted into energy-dense products through thermochemical processes such as pyrolysis and gasification. Since microwave heating depends on the dielectric properties of the biomass material, these properties were measured at freque...

  6. Catalytic cracking of fast and tail gas reactive pyrolysis bio-oils over HZSM-5

    USDA-ARS?s Scientific Manuscript database

    While hydrodeoxygenation (HDO) of pyrolysis oil is well understood as an upgrading method, the high processing pressures associated with it alone justify the exploration of alternative upgrading solutions, especially those that could adapt pyrolysis oils into the existing refinery infrastructure. Ca...

  7. Techno-economic and uncertainty analysis of in situ and ex situ fast pyrolysis for biofuel production.

    PubMed

    Li, Boyan; Ou, Longwen; Dang, Qi; Meyer, Pimphan; Jones, Susanne; Brown, Robert; Wright, Mark

    2015-11-01

    This study evaluates the techno-economic uncertainty in cost estimates for two emerging technologies for biofuel production: in situ and ex situ catalytic pyrolysis. The probability distributions for the minimum fuel-selling price (MFSP) indicate that in situ catalytic pyrolysis has an expected MFSP of $1.11 per liter with a standard deviation of 0.29, while the ex situ catalytic pyrolysis has a similar MFSP with a smaller deviation ($1.13 per liter and 0.21 respectively). These results suggest that a biorefinery based on ex situ catalytic pyrolysis could have a lower techno-economic uncertainty than in situ pyrolysis compensating for a slightly higher MFSP cost estimate. Analysis of how each parameter affects the NPV indicates that internal rate of return, feedstock price, total project investment, electricity price, biochar yield and bio-oil yield are parameters which have substantial impact on the MFSP for both in situ and ex situ catalytic pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Kinetics of the pyrolysis of arundo, sawdust, corn stover and switch grass biomass by thermogravimetric analysis using a multi-stage model.

    PubMed

    Biney, Paul O; Gyamerah, Michael; Shen, Jiacheng; Menezes, Bruna

    2015-03-01

    A new multi-stage kinetic model has been developed for TGA pyrolysis of arundo, corn stover, sawdust and switch grass that accounts for the initial biomass weight (W0). The biomass were decomposed in a nitrogen atmosphere from 23°C to 900°C in a TGA at a single 20°C/min ramp rate in contrast with the isoconversion technique. The decomposition was divided into multiple stages based on the absolute local minimum values of conversion derivative, (dx/dT), obtained from DTG curves. This resulted in three decomposition stages for arundo, corn stover and sawdust and four stages for switch grass. A linearized multi-stage model was applied to the TGA data for each stage to determine the pre-exponential factor, activation energy, and reaction order. The activation energies ranged from 54.7 to 60.9 kJ/mol, 62.9 to 108.7 kJ/mol, and 18.4 to 257.9 kJ/mol for the first, second and the third decomposition stages respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Microwave-assisted co-pyrolysis of brown coal and corn stover for oil production.

    PubMed

    Zhang, Yaning; Fan, Liangliang; Liu, Shiyu; Zhou, Nan; Ding, Kuan; Peng, Peng; Anderson, Erik; Addy, Min; Cheng, Yanling; Liu, Yuhuan; Li, Bingxi; Snyder, John; Chen, Paul; Ruan, Roger

    2018-07-01

    The controversial synergistic effect between brown coal and biomass during co-pyrolysis deserves further investigation. This study detailed the oil production from microwave-assisted co-pyrolysis of brown coal (BC) and corn stover (CS) at different CS/BC ratios (0, 0.33, 0.50, 0.67, and 1) and pyrolysis temperatures (500, 550, and 600 °C). The results showed that a higher CS/BC ratio resulted in higher oil yield, and a higher pyrolysis temperature increased oil yield for brown coal and coal/corn mixtures. Corn stover and brown coal showed different pyrolysis characteristics, and positive synergistic effect on oil yield was observed only at CS/BC ratio of 0.33 and pyrolysis temperature of 600 °C. Oils from brown coal mainly included hydrocarbons and phenols whereas oils from corn stover and coal/corn mixtures were dominated by ketones, phenols, and aldehydes. Positive synergistic effects were observed for ketones, aldehydes, acids, and esters whereas negative synergistic effects for hydrocarbons, phenols and alcohols. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Bio-oil production of softwood and hardwood forest industry residues through fast and intermediate pyrolysis and its chromatographic characterization.

    PubMed

    Torri, Isadora Dalla Vecchia; Paasikallio, Ville; Faccini, Candice Schmitt; Huff, Rafael; Caramão, Elina Bastos; Sacon, Vera; Oasmaa, Anja; Zini, Claudia Alcaraz

    2016-01-01

    Bio-oils were produced through intermediate (IP) and fast pyrolysis (FP), using Eucalyptus sp. (hardwood) and Picea abies (softwood), wood wastes produced in large scale in Pulp and Paper industries. Characterization of these bio-oils was made using GC/qMS and GC×GC/TOFMS. The use of GC×GC provided a broader characterization of bio-oils and it allowed tracing potential markers of hardwood bio-oil, such as dimethoxy-phenols, which might co-elute in 1D-GC. Catalytic FP increased the percentage of aromatic hydrocarbons in P. abies bio-oil, indicating its potential for fuel production. However, the presence of polyaromatic hydrocarbons (PAH) draws attention to the need of a proper management of pyrolysis process in order to avoid the production of toxic compounds and also to the importance of GC×GC/TOFMS use to avoid co-elutions and consequent inaccuracies related to identification and quantification associated with GC/qMS. Ketones and phenols were the major bio-oil compounds and they might be applied to polymer production. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating

    DOE PAGES

    Olarte, Mariefel V.; Padmaperuma, Asanga B.; Ferrell, III, Jack R.; ...

    2017-04-06

    We consider catalytic hydroprocessing of pyrolysis oils from biomass which produces hydrocarbons for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. Here, we present in this paper the characterization of a group of five distillate fractions from each of two types of hydroprocessed oils from oak pyrolysis oil: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. The LOC oil was generated using a sulfided hydrotreating system consistingmore » of RuS/C and xMoS/Al 2O 3 while the MOC was produced using non-sulfided catalysts, Ru/C and Pd/C. Elemental analysis and 13C NMR (nuclear magnetic resonance) results suggest that the distillate fractions from both oils become more aromatic/unsaturated as they become heavier. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. Paraffin, iso-paraffin, olefin, naphthene, aromatic (PIONA) analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. Sulfur analysis showed the comparative concentration of sulfur in the different fractions as well as the surprising similarity in content in some sulfided and non-sulfided fractions. Our results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.« less

  12. Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Olarte, Mariefel V.; Padmaperuma, Asanga B.; Ferrell, III, Jack R.

    We consider catalytic hydroprocessing of pyrolysis oils from biomass which produces hydrocarbons for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. Here, we present in this paper the characterization of a group of five distillate fractions from each of two types of hydroprocessed oils from oak pyrolysis oil: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. The LOC oil was generated using a sulfided hydrotreating system consistingmore » of RuS/C and xMoS/Al 2O 3 while the MOC was produced using non-sulfided catalysts, Ru/C and Pd/C. Elemental analysis and 13C NMR (nuclear magnetic resonance) results suggest that the distillate fractions from both oils become more aromatic/unsaturated as they become heavier. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. Paraffin, iso-paraffin, olefin, naphthene, aromatic (PIONA) analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. Sulfur analysis showed the comparative concentration of sulfur in the different fractions as well as the surprising similarity in content in some sulfided and non-sulfided fractions. Our results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.« less

  13. Study on vacuum pyrolysis of coffee industrial residue for bio-oil production

    NASA Astrophysics Data System (ADS)

    Chen, Nanwei; Ren, Jie; Ye, Ziwei; Xu, Qizhi; Liu, Jingyong; Sun, Shuiyu

    2017-03-01

    Coffee industrial residue (CIR) is a biomass with high volatile content (64.94 wt.%) and heating value (21.3 MJ·kg-1). This study was carried out to investigate the pyrolysis condition and products of CIR using thermogravimetric analyser (TGA) and vacuum tube furnace. The influence of pyrolysis temperature, time, pressure and heating rate on the yield of pyrolysis products were discussed. There was an optimal pyrolysis condition: CIR was heated from normal temperature to 400 °C for 60 min, with 10 °C·min-1 heating rate and a pressure of 30 kPaabs. In this condition, the yields of bio-oil, char and non-condensable gas were 42.29, 33.14 and 24.57 wt.%, respectively. The bio-oil contained palmitic acid (47.48 wt.%), oleic acid (17.45 wt.%), linoleic acid (11.34 wt.%), octadecanoic acid (7.62 wt.%) and caffeine (5.18 wt.%).

  14. Effects of mass transfer and hydrogen pressure on the fixed-bed pyrolysis of sunflower bagasse

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Putun, E.; Kockar, O.M.; Gercel, F.

    1994-12-31

    There are a number of waste and biomass sources being considered as potential sources of fuels and chemical feedstocks. The economics for biomass pyrolysis are generally considered to be most favourable for (1) plants which grow abundantly and require little cultivation in and lands and (2) wastes available in relatively large quantities from agricultural plants, for example, sunflower and hazel nuts. For the former, one such group of plants is Euphorbiaceae which are characterised by their ability to produce a milky latex, an emulsion of about 30% w/w terpenoids in water. One species in the family, Euphorbia Rigida from Southwesternmore » Anatolia, Turkey is cultivated in close proximity to the sunflower growing regions and their oil extraction plants. The Turkish sunflower oil industry generates 800,000 tons of extraction residue (bagasse) per annum. Thus, both sunflower wastes and latex-producing plants are being considered as feedstocks for a future thermochemical demonstration unit in Turkey. Pyrolysis at relatively high hydrogen pressures (hydropyrolysis) has not been widely investigated for biomass. A potential advantage of hydropyrolysis is the ability to upgrade tar vapours over hydroprocessing catalysts. Fixed-bed pyrolysis and hydropyrolysis experiments have been conducted on sunflower bagasse to assess the effects of mass transfer and hydrogen pressure on oil yield and quality.« less

  15. Synergistic dye adsorption by biochar from co-pyrolysis of spent mushroom substrate and Saccharina japonica.

    PubMed

    Sewu, Divine Damertey; Boakye, Patrick; Jung, Hwansoo; Woo, Seung Han

    2017-11-01

    The potential of activating terrestrial biomass (spent mushroom substrate, SMS) with ash-laden marine biomass [kelp seaweed, KE] via co-pyrolysis in the field of adsorption was first investigated. KE biochar (KBC), SMS biochar (SMSBC), biochar (SK10BC) from 10%-KE added SMS, and biochar (ESBC) from KE-extract added SMS were used for the adsorption of cationic dye crystal violet (CV). ESBC had highest fixed carbon content (70.60%) and biochar yield (31.6%). SK10BC exhibited high ash content, abundant functional groups, coarser surface morphology and Langmuir maximum adsorptive capacity (610.1mg/g), which is 2.2 times higher than that of SMSBC (282.9mg/g). Biochar activated by a small amount of high ash-containing biomass such as seaweed via co-pyrolysis can serve as viable alternative adsorbent for cationic dye removal. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Lignin-rich biomass of cotton by-products for biorefineries via pyrolysis.

    PubMed

    Chen, Jiao; Liang, Jiajin; Wu, Shubin

    2016-10-01

    Pyrolysis was demonstrated to investigate the thermal decomposition characteristics and potential of lignin-rich cotton by-products cotton exocarp (CE) and spent mushroom substrate consisted of cotton by-products (MSC) for biorefineries. The chemical component and structure alteration of CE and MSC was found to affect their thermochemical behaviors. The bio-oil yield from CE was 58.13wt% while the maximum yield from MSC was 45.01% at 600°C. The phenolic compounds obtained from CE and MSC were 33.9% and 39.2%, respectively. The yield of acetic acid from MSC between 400 and 600°C was about 30-38% lower than that from CE, which suggests the high quality of bio-oil was obtained. Biochar from MSC via slow pyrolysis had a high mass yield (44.38wt%) with well-developed pore structure. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Techno-economic and uncertainty analysis of in situ and ex situ fast pyrolysis for biofuel production

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Boyan; Ou, Longwen; Dang, Qi

    This study evaluates the techno-economic uncertainty in cost estimates for two emerging biorefinery technologies for biofuel production: in situ and ex situ catalytic pyrolysis. Stochastic simulations based on process and economic parameter distributions are applied to calculate biorefinery performance and production costs. The probability distributions for the minimum fuel-selling price (MFSP) indicate that in situ catalytic pyrolysis has an expected MFSP of $4.20 per gallon with a standard deviation of 1.15, while the ex situ catalytic pyrolysis has a similar MFSP with a smaller deviation ($4.27 per gallon and 0.79 respectively). These results suggest that a biorefinery based on exmore » situ catalytic pyrolysis could have a lower techno-economic risk than in situ pyrolysis despite a slightly higher MFSP cost estimate. Analysis of how each parameter affects the NPV indicates that internal rate of return, feedstock price, total project investment, electricity price, biochar yield and bio-oil yield are significant parameters which have substantial impact on the MFSP for both in situ and ex situ catalytic pyrolysis.« less

  18. Pyrolysis of Woody Residue Feedstocks: Upgrading of Bio-Oils from Mountain-Pine-Beetle-Killed Trees and Hog Fuel

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zacher, Alan H.; Elliott, Douglas C.; Olarte, Mariefel V.

    Liquid transportation fuel blend-stocks were produced by pyrolysis and catalytic upgrading of woody residue biomass. Mountain pine beetle killed wood and hog fuel from a saw mill were pyrolyzed in a 1 kg/h fluidized bed reactor and subsequently upgraded to hydrocarbons in a continuous fixed bed hydrotreater. Upgrading was performed by catalytic hydrotreatment in a two-stage bed at 170°C and 405°C with a per bed LHSV between 0.17 and 0.19. The overall yields from biomass to upgraded fuel were similar for both feeds: 24-25% despite the differences in bio-oil (intermediate) mass yield. Pyrolysis bio-oil mass yield was 61% from MPBKmore » wood, and subsequent upgrading of the bio-oil gave an average mass yield of 41% to liquid fuel blend stocks. Hydrogen was consumed at an average of 0.042g/g of bio-oil fed, with final oxygen content in the product fuel ranging from 0.31% to 1.58% over the course of the test. Comparatively for hog fuel, pyrolysis bio-oil mass yield was lower at 54% due to inorganics in the biomass, but subsequent upgrading of that bio-oil had an average mass yield of 45% to liquid fuel, resulting in a similar final mass yield to fuel compared to the cleaner MPBK wood. Hydrogen consumption for the hog fuel upgrading averaged 0.041 g/g of bio-oil fed, and the final oxygen content of the product fuel ranged from 0.09% to 2.4% over the run. While it was confirmed that inorganic laded biomass yields less bio-oil, this work demonstrated that the resultant bio-oil can be upgraded to hydrocarbons at a higher yield than bio-oil from clean wood. Thus the final hydrocarbon yield from clean or residue biomass pyrolysis/upgrading was similar.« less

  19. Chapter 8: Pyrolysis Mechanisms of Lignin Model Compounds Using a Heated Micro-Reactor

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Robichaud, David J.; Nimlos, Mark R.; Ellison, G. Barney

    2015-10-03

    Lignin is an important component of biomass, and the decomposition of its thermal deconstruction products is important in pyrolysis and gasification. In this chapter, we investigate the unimolecular pyrolysis chemistry through the use of singly and doubly substituted benzene molecules that are model compounds representative of lignin and its primary pyrolysis products. These model compounds are decomposed in a heated micro-reactor, and the products, including radicals and unstable intermediates, are measured using photoionization mass spectrometry and matrix isolation infrared spectroscopy. We show that the unimolecular chemistry can yield insight into the initial decomposition of these species. At pyrolysis and gasificationmore » severities, singly substituted benzenes typically undergo bond scission and elimination reactions to form radicals. Some require radical-driven chain reactions. For doubly substituted benzenes, proximity effects of the substituents can change the reaction pathways.« less

  20. The structure evolution of biochar from biomass pyrolysis and its correlation with gas pollutant adsorption performance.

    PubMed

    Chen, Yingquan; Zhang, Xiong; Chen, Wei; Yang, Haiping; Chen, Hanping

    2017-12-01

    Biochar is carbon-rich, porous and with a great potential in gas pollutant controlling. The physical-chemical structure of biochar is important for the application. This paper firstly reviewed the evolution behavior of physical-chemical structure for biochar during pyrolysis. At lower temperature (<500°C), biomass firstly transformed to "3D network of benzene rings" with abundant functional groups. With temperature increasing (500-700°C), it converted to "2D structure of fused rings" with abundant porosity. As temperature increasing further (>700°C), it may transit into a "graphite microcrystalline structure", the porosity and functional groups were diminished correspondingly. The modification of biochar and its application as sorbent for gas pollutant were also reviewed. Activation and doping can significantly increase the porosity and special functional groups in biochar, which is favorable for gas pollutant adsorption. With a higher porosity, the adsorption capacity of gas pollutant is bigger, however, the functional groups determined the sorption stability of gas pollutant. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Scrap tyre pyrolysis: Modified chemical percolation devolatilization (M-CPD) to describe the influence of pyrolysis conditions on product yields.

    PubMed

    Tan, Vincent; De Girolamo, Anthony; Hosseini, Tahereh; Alhesan, Jameel Aljariri; Zhang, Lian

    2018-03-16

    This paper attempts to develop a modified chemical percolation devolatilization (M-CPD) model that can include heat transfer, primary pyrolysis and the secondary cracking reactions of volatiles together to describe the pyrolysis of waste scrap tyre chip, as well as to examine the influence of operating conditions on the scrap tyre pyrolysis product yields. Such a study has yet to be conducted in the past, thereby leading to a large knowledge gap failing to understand the pyrolysis of the coarse feedstock appropriately. To validate the developed model, a number of operating parameters including reactor configurations, carrier gas compositions (argon and argon blended with CO 2 and/or steam), scrap tyre chip size (0.5-15.0 mm), terminal pyrolysis temperature (400-800 °C) and heating rate (10 °C/min and 110 °C/min) were examined in a lab-scale fixed-bed pyrolyser, with a particular focus on the secondary cracking extents of the liquid tar. Through both experimental investigation and modelling approach, it was found that significant secondary cracking extent occurred upon the increase in the feedstock size, heating rate and residence time. Upon the fast pyrolysis, the average temperature gap between the centres of the coarse particle and reactor wall could reach a maximum of 115 °C for the tyre chips of 6-15 mm. Consequently, its primary volatiles underwent the secondary cracking reaction at an overall extent of 17% at a terminal temperature of 600 °C and a fast heating rate of 110 °C/min. Consequently, the yield of light gases including methane was increased remarkably. The flow rate of inert carrier gas was also influential in the secondary cracking, in which a maximum tar yield (54 wt%) was reached at a carrier gas flow rate of 1.5  L/min. This indicates the occurrence of secondary cracking has been largely minimised. At a pyrolysis temperature of 600 °C, the addition of CO 2 in the carrier gas had an insignificant effect on the product

  2. Preliminary investigation on the production of fuels and bio-char from Chlamydomonas reinhardtii biomass residue after bio-hydrogen production.

    PubMed

    Torri, Cristian; Samorì, Chiara; Adamiano, Alessio; Fabbri, Daniele; Faraloni, Cecilia; Torzillo, Giuseppe

    2011-09-01

    The aim of this work was to investigate the potential conversion of Chlamydomonas reinhardtii biomass harvested after hydrogen production. The spent algal biomass was converted into nitrogen-rich bio-char, biodiesel and pyrolysis oil (bio-oil). The yield of lipids (algal oil), obtained by solvent extraction, was 15 ± 2% w/w(dry-biomass). This oil was converted into biodiesel with a 8.7 ± 1% w/w(dry-biomass) yield. The extraction residue was pyrolysed in a fixed bed reactor at 350 °C obtaining bio-char as the principal fraction (44 ± 1% w/w(dry-biomass)) and 28 ± 2% w/w(dry-biomass) of bio-oil. Pyrolysis fractions were characterized by elemental analysis, while the chemical composition of bio-oil was fully characterized by GC-MS, using various derivatization techniques. Energy outputs resulting from this approach were distributed in hydrogen (40%), biodiesel (12%) and pyrolysis fractions (48%), whereas bio-char was the largest fraction in terms of mass. Copyright © 2011 Elsevier Ltd. All rights reserved.

  3. Effect of temperature on pyrolysis product of empty fruit bunches

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Rahman, Aizuddin Abdul; Sulaiman, Fauziah; Abdullah, Nurhayati

    2015-04-24

    Pyrolysis of empty fruit bunches (EFB) was performed in a fixed bed reactor equipped with liquid collecting system. Pyrolysis process was conducted by varying the terminal pyrolysis temperature from 300 to 500°C under heating rate of 10°C/min for at least 2 hours. Char yield was obtained highest at 300°C around 55.88 wt%, and started to decrease as temperature increase. The maximum yield of pyrolysis liquid was obtained around 54.75 wt% as pyrolysis temperature reach 450°C. For gas yield percentage, the yield gained as temperature was increased from 300 to 500°C, within the range between 8.44 to 19.32 wt%. The charmore » obtained at 400°C has great potential as an alternative solid fuel, due to its high heating value of 23.37 MJ/kg, low in volatile matter and ash content which are approximately around 40.32 and 11.12 wt%, respectively. The collected pyrolysis liquid within this temperature range found to have high water content of around 16.15 to 18.20 wt%. The high aqueous fraction seemed to cause the pyrolysis liquid to have low HHV which only ranging from 10.81 to 12.94 MJ/kg. These trends of results showed that necessary enhancement should be employ either on the raw biomass or pyrolysis products in order to approach at least the minimum quality of common hydrocarbon solid or liquid fuel. For energy production, both produced bio-char and pyrolysis liquid are considered as sustainable sources of bio-energy since they contained low amounts of nitrogen and sulphur, which are considered as environmental friendly solid and liquid fuel.« less

  4. Pressurized entrained-flow pyrolysis of microalgae: Enhanced production of hydrogen and nitrogen-containing compounds.

    PubMed

    Maliutina, Kristina; Tahmasebi, Arash; Yu, Jianglong

    2018-05-01

    Pressurized entrained-flow pyrolysis of Chlorella vulgaris microalgae was investigated. The impact of pressure on the yield and composition of pyrolysis products were studied. The results showed that the concentration of H 2 in bio-gas increased sharply with increasing pyrolysis pressure, while those of CO, CO 2 , CH 4 , and C 2 H 6 were dramatically decreased. The concentration of H 2 reached 88.01 vol% in bio-gas at 900 °C and 4 MPa. Higher pressures promoted the hydrogen transfer to bio-gas. The bio-oils derived from pressurized pyrolysis were rich in nitrogen-containing compounds and PAHs. The highest concentration of nitrogen-containing compounds in bio-oil was achieved at 800 °C and 1 MPa. Increasing pyrolysis pressure promoted the formation of nitrogen-containing compounds such as indole, quinoline, isoquinoline and phenanthridine. Higher pyrolysis pressures led to increased sphericity, enhanced swelling, and higher carbon order of bio-chars. Pressurized pyrolysis of biomass has a great potential for poly-generation of H 2 , nitrogen containing compounds and bio-char. Copyright © 2018 Elsevier Ltd. All rights reserved.

  5. Biofuel from jute stick by pyrolysis technology

    NASA Astrophysics Data System (ADS)

    Ferdous, J.; Parveen, M.; Islam, M. R.; Haniu, H.; Takai, K.

    2017-06-01

    In this study the conversion of jute stick into biofuels and chemicals by externally heated fixed-bed pyrolysis reactor have been taken into consideration. The solid jute stick was characterized through proximate and ultimate analysis, gross calorific values and thermo-gravimetric analysis to investigate their suitability as feedstock for this consideration. The solid biomass particles were fed into the reactor by gravity feed type reactor feeder. The products were oil, char and gases. The liquid and char products were collected separately while the gas was flared into the atmosphere. The process conditions were varied by fixed-bed temperature; feed stock particle size, N2 gas flow rate and running time. All parameters were found to influence the product yields significantly. The maximum liquid yields were 50 wt% of solid jute stick at reactor temperature 425°C for N2 gas flow rate 6 l/min, feed particle size 1180-1700 µm and running time 30 min. Liquid products obtained at these conditions were characterized by physical properties, chemical analysis and GC-MS techniques. The results show that it is possible to obtained liquid products that are comparable to petroleum fuels and valuable chemical feedstock from the selected biomass if the pyrolysis conditions are chosen accordingly.

  6. Co-processing of olive bagasse with crude rapeseed oil via pyrolysis.

    PubMed

    Uçar, Suat; Karagöz, Selhan

    2017-05-01

    The co-pyrolysis of olive bagasse with crude rapeseed oil at different blend ratios was investigated at 500ºC in a fixed bed reactor. The effect of olive bagasse to crude rapeseed oil ratio on the product distributions and properties of the pyrolysis products were comparatively investigated. The addition of crude rapeseed oil into olive bagasse in the co-pyrolysis led to formation of upgraded biofuels in terms of liquid yields and properties. While the pyrolysis of olive bagasse produced a liquid yield of 52.5 wt %, the highest liquid yield of 73.5 wt % was obtained from the co-pyrolysis of olive bagasse with crude rapeseed oil at a blend ratio of 1:4. The bio-oil derived from olive bagasse contained 5% naphtha, 10% heavy naphtha, 30% gas oil, and 55% heavy gas oil. In the case of bio-oil obtained from the co-pyrolysis of olive bagasse with crude rapeseed oil at a blend ratio of 1:4, the light naphtha, heavy naphtha, and light gas oil content increased. This is an indication of the improved characteristics of the bio-oil obtained from the co-processing. The heating value of bio-oil from the pyrolysis of olive bagasse alone was 34.6 MJ kg -1 and the heating values of bio-oils obtained from the co-pyrolysis of olive bagasse with crude rapeseed oil ranged from 37.6 to 41.6 MJ kg -1 . It was demonstrated that the co-processing of waste biomass with crude plant oil is a good alternative to improve bio-oil yields and properties.

  7. Integration of decentralized torrefaction with centralized catalytic pyrolysis to produce green aromatics from coffee grounds.

    PubMed

    Chai, Li; Saffron, Christopher M; Yang, Yi; Zhang, Zhongyu; Munro, Robert W; Kriegel, Robert M

    2016-02-01

    The aim of this work was to integrate decentralized torrefaction with centralized catalytic pyrolysis to convert coffee grounds into the green aromatic precursors of terephthalic acid, namely benzene, toluene, ethylbenzene, and xylenes (BTEX). An economic analysis of this bioproduct system was conducted to examine BTEX yields, biomass costs and their sensitivities. Model predictions were verified experimentally using pyrolysis GC/MS to quantify BTEX yields for raw and torrefied biomass. The production cost was minimized when the torrefier temperature and residence time were 239°C and 34min, respectively. This optimization study found conditions that justify torrefaction as a pretreatment for making BTEX, provided that starting feedstock costs are below $58 per tonne. Copyright © 2015. Published by Elsevier Ltd.

  8. Development of a modified independent parallel reactions kinetic model and comparison with the distributed activation energy model for the pyrolysis of a wide variety of biomass fuels.

    PubMed

    Sfakiotakis, Stelios; Vamvuka, Despina

    2015-12-01

    The pyrolysis of six waste biomass samples was studied and the fuels were kinetically evaluated. A modified independent parallel reactions scheme (IPR) and a distributed activation energy model (DAEM) were developed and their validity was assessed and compared by checking their accuracy of fitting the experimental results, as well as their prediction capability in different experimental conditions. The pyrolysis experiments were carried out in a thermogravimetric analyzer and a fitting procedure, based on least squares minimization, was performed simultaneously at different experimental conditions. A modification of the IPR model, considering dependence of the pre-exponential factor on heating rate, was proved to give better fit results for the same number of tuned kinetic parameters, comparing to the known IPR model and very good prediction results for stepwise experiments. Fit of calculated data to the experimental ones using the developed DAEM model was also proved to be very good. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Phase separation of bio-oil produced by co-pyrolysis of corn cobs and polypropylene

    NASA Astrophysics Data System (ADS)

    Supramono, D.; Julianto; Haqqyana; Setiadi, H.; Nasikin, M.

    2017-11-01

    In co-pyrolysis of biomass-plastics, bio-oil produced contains both oxygenated and non-oxygenated compounds. High oxygen composition is responsible for instability and low heating value of bio-oil and high acid content for corrosiveness. Aims of the present work are to evaluate possibilities of achieving phase separation between oxygenated and non-oxygenated compounds in bio-oil using a proposed stirred tank reactor and to achieve synergistic effects on bio-oil yield and non-oxygenated compound layer yield. Separation of bio-oil into two layers, i.e. that containing oxygenated compounds (polar phase) and non-oxygenated compounds (non-polar phase) is important to obtain pure non-polar phase ready for the next processing of hydrogenation and used directly as bio-fuel. There has been no research work on co-pyrolysis of biomass-plastic considering possibility of phase separation of bio-oil. The present work is proposing a stirred tank reactor for co-pyrolysis with nitrogen injection, which is capable of tailoring co-pyrolysis conditions leading to low viscosity and viscosity asymmetry, which induce phase separation between polar phase and non-polar phase. The proposed reactor is capable of generating synergistic effect on bio-oil and non-polar yields as the composition of PP in feed is more than 25% weight in which non-polar layers contain only alkanes, alkenes, cycloalkanes and cycloalkenes.

  10. Pyrolysis of forest residues: An approach to techno-economics for bio-fuel production

    DOE PAGES

    Carrasco, Jose L.; Gunukula, Sampath; Boateng, Akwasi A.; ...

    2017-04-01

    Here, the techno-economics for producing liquid fuels from Maine forest residues were determined from a combination of: (1) laboratory experiments at USDA-ARS’s Eastern Regional Research Center using hog fuel (a secondary woody residue produced from mill byproducts such as sawdust, bark and shavings) as a feedstock for pyrolysis to establish product yields and composition, and (2) Aspen Plus® process simulation for a feed rate of 2000 dry metric tons per day to estimate energy requirements and equipment sizes. The simulated plant includes feedstock sizing and drying, pyrolysis, hydrogen production and hydrotreatment of pyrolysis oils. The biomass is converted into bio-oilmore » (61% yield), char (24%) and gases (15%) in the pyrolysis reactor, with an energy demand of 17%. The bio-oil is then hydrotreated to remove oxygen, thereby producing hydrocarbon fuels. The final mass yield of gasoline/diesel hydrocarbons is 16% with a 40% energy yield based on the dry biomass fed, this yield represents a fuel production of 51.9 gallons per dry metric ton of feedstock. A unique aspect of the process simulated herein is that pyrolysis char and gases are used as sources for both thermal energy and hydrogen, greatly decreasing the need to input fossil energy. The total capital investment for a grass-roots plant was estimated to be US$427 million with an annual operational cost of US$154 million. With a 30 year project life, a minimum fuel selling price was determined to be US$6.25 per gallon. The economic concerns are related to high capital costs, high feedstock costs and short hydrotreating catalyst lifetimes.« less

  11. Pyrolysis of forest residues: An approach to techno-economics for bio-fuel production

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Carrasco, Jose L.; Gunukula, Sampath; Boateng, Akwasi A.

    Here, the techno-economics for producing liquid fuels from Maine forest residues were determined from a combination of: (1) laboratory experiments at USDA-ARS’s Eastern Regional Research Center using hog fuel (a secondary woody residue produced from mill byproducts such as sawdust, bark and shavings) as a feedstock for pyrolysis to establish product yields and composition, and (2) Aspen Plus® process simulation for a feed rate of 2000 dry metric tons per day to estimate energy requirements and equipment sizes. The simulated plant includes feedstock sizing and drying, pyrolysis, hydrogen production and hydrotreatment of pyrolysis oils. The biomass is converted into bio-oilmore » (61% yield), char (24%) and gases (15%) in the pyrolysis reactor, with an energy demand of 17%. The bio-oil is then hydrotreated to remove oxygen, thereby producing hydrocarbon fuels. The final mass yield of gasoline/diesel hydrocarbons is 16% with a 40% energy yield based on the dry biomass fed, this yield represents a fuel production of 51.9 gallons per dry metric ton of feedstock. A unique aspect of the process simulated herein is that pyrolysis char and gases are used as sources for both thermal energy and hydrogen, greatly decreasing the need to input fossil energy. The total capital investment for a grass-roots plant was estimated to be US$427 million with an annual operational cost of US$154 million. With a 30 year project life, a minimum fuel selling price was determined to be US$6.25 per gallon. The economic concerns are related to high capital costs, high feedstock costs and short hydrotreating catalyst lifetimes.« less

  12. Robert M. Baldwin | NREL

    Science.gov Websites

    , upgrading of bio-oil, and advanced biofuels. His interests include: Catalytic fast pyrolysis and bio-oil co Oil," U.S. Patent No. 4,576,708 (1986) Featured Publications "Improving Biomass Pyrolysis of Pyrolysis Oil in Existing Refineries, Part 2," Hydrocarbon Processing (2017) "

  13. Mission analysis for the federal fuels from biomass program. Volume IV. Termochemical conversion of biomass to fuels and chemicals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kohan, S.M.; Barkhordar, P.M.

    1979-01-01

    The thermochemical conversion of biomass feedstocks generally denotes technologies that use elevated temperatures to convert the fixed carbon content of biomass materials to produce other, more useful energy forms. Examples are combustion to produce heat, steam, electricity, or combinations of these; pyrolysis to produce gas (low- or intermediate-Btu), pyrolytic liquids and chemicals, and char; gasification to produce low or intermediate Btu gas (and, from IBG, additional products such as SNG, ammonia, methanol, or Fischer-Tropsch liquids); and liquefaction to produce heavy fuel oil or, with upgrading, lighter-boiling liquid products such as distillates, light fuel oils, or gasoline. This section discusses themore » selection of the feedstock used in the analysis of thermochemical conversion technologies. The following sections present detailed technical and economic evaluations of biomass conversion to electricity and steam by combustion, SNG by gasification and methanation, methanol by gasification and synthesis, oil by catalytic liquefaction, oil and char by pyrolysis, and ammonia by gasification and synthesis. The conversion options were reviewed with DOE for approval at the start of the project.« less

  14. Clean fuels from biomass. [feasibility of converting plant systems to fuels

    NASA Technical Reports Server (NTRS)

    Hsu, Y. Y.

    1974-01-01

    The feasibility of converting biomass to portable fuels is studied. Since plants synthesize biomass from H2O and CO2 with the help of solar energy, the conversion methods of pyrolysis, anaerobic fermentation, and hydrogenation are considered. Cost reduction methods and cost effectiveness are emphasized.

  15. Thermochemical Process Integration, Scale-Up, and Piloting Publications |

    Science.gov Websites

    -Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility, Topics in Catalysis Image of a schematic of hot gas filter and ex situ Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors, NREL Technical Report Image

  16. Effect of carbon dioxide on the thermal degradation of lignocellulosic biomass.

    PubMed

    Kwon, Eilhann E; Jeon, Eui-Chan; Castaldi, Marco J; Jeon, Young Jae

    2013-09-17

    Using biomass as a renewable energy source via currently available thermochemical processes (i.e., pyrolysis and gasification) is environmentally advantageous owing to its intrinsic carbon neutrality. Developing methodologies to enhance the thermal efficiency of these proven technologies is therefore imperative. This study aimed to investigate the use of CO2 as a reaction medium to increase not only thermal efficiency but also environmental benefit. The influence of CO2 on thermochemical processes at a fundamental level was experimentally validated with the main constituents of biomass (i.e., cellulose and xylan) to avoid complexities arising from the heterogeneous matrix of biomass. For instance, gaseous products including H2, CH4, and CO were substantially enhanced in the presence of CO2 because CO2 expedited thermal cracking behavior (i.e., 200-1000%). This behavior was then universally observed in our case study with real biomass (i.e., corn stover) during pyrolysis and steam gasification. However, further study is urgently needed to optimize these experimental findings.

  17. Natural Catalysts for Molten Cellulose Pyrolysis to Targeted Bio-Oils

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dauenhauer, Paul J.

    2017-06-02

    Catalysis of biomass biopolymer cellulose by alkaline earth metals is a fundamental chemistry relevant to energy processes including combustion, pyrolysis and gasification. In this work, the catalytic decomposition of cellulose by calcium ions was evaluated at high temperature (400-500°C) to elucidate the chemical mechanisms leading to the formation of volatile organic compounds.

  18. What limits the yield of levoglucosan during fast pyrolysis of cellulose?

    NASA Astrophysics Data System (ADS)

    Proano-Aviles, Juan

    The pyrolysis of cellulose to form levoglucosan is investigated in this study. Although the stoichiometric yield of levoglucosan from the pyrolysis of cellulose is expected to be 100%, only about 60 wt.% yields are reported in the literature. Several possible reasons for this limitation are investigated through experiments in micropyrolyzers and computational studies on the depolymerization of cellulose. Heat and mass transfer limitations in an experimental apparatus is one possible limitation on the yield of levoglucosan. Repolymerization of condensed phase reaction intermediates could prevent the formation and release of volatile levoglucosan. Thermohydrolysis of pyrolyzing cellulose to form non-volatile and thermally unstable glucose has also been proposed as a mechanism that reduces levoglucosan yields. Secondary reactions in the gas phase were also investigated to explain limitations on levoglucosan yields. Population balance models were developed to test ideas on how cellulose depolymerized to form levoglucosan at less than stoichiometric yields. These models were supported with chemical kinetic data obtained from transient pyrolysis experiments. Under carefully controlled experimental conditions, no evidence was found for heat and mass transfer effects limiting levoglucosan yields to 60 wt.% nor do secondary reactions in the condensed- or gas-phases appear to offer a satisfactory explanation. Based on modeling results, it appears levoglucosan-forming reaction rates that decrease as oligosaccharide chain length decreases is the most plausible explanation for limitations on levoglucosan yield from cellulose.

  19. Chemical and ecotoxicological characterization of solid residues produced during the co-pyrolysis of plastics and pine biomass.

    PubMed

    Bernardo, Maria S; Lapa, N; Barbosa, R; Gonçalves, M; Mendes, B; Pinto, F; Gulyurtlu, I

    2009-07-15

    A mixture of 70% (w/w) pine biomass and 30% (w/w) plastics (mixture of polypropylene, polyethylene, and polystyrene) was subjected to pyrolysis at 400 degrees C, for 15 min, with an initial pressure of 40 MPa. Part of the solid residue produced was subjected to extraction with dichloromethane (DCM). The extracted residue (residue A) and raw residue (residue B) were analyzed by weight loss combustion and submitted to the leaching test ISO/TS 21268-2 using two different leachants: DCM (0.2%, v/v) and calcium chloride (0.001 mol/L). The concentrations of the heavy metals Cd, Cr, Ni, Zn, Pb and Cu were determined in the eluates and in the two residues. The eluates were further characterized by determining their pH and the concentrations of benzene, toluene, ethylbenzene and xylenes (BTEX). The presence of other organic contaminants in the eluates was qualitatively evaluated by gas chromatography, coupled with mass spectrometry. An ecotoxicological characterization was also performed by using the bio-indicator Vibrio fischeri. The chemical and ecotoxicological results were analyzed according to the French proposal of Criteria on the Evaluation Methods of Waste Ecotoxicity (CEMWE). Residue A was not considered to be ecotoxic by the ecotoxicological criterion (EC(50) (30 min) >or=10%), but it was considered to be ecotoxic by the chemical criterion (Ni>or=0.5mg/L). Residue B was considered to be ecotoxic by the ecotoxicological criterion: EC(50) (30 min)pyrolysis residue with DCM was an efficient method for removing lighter organic contaminants.

  20. Co-pyrolysis mechanism of seaweed polysaccharides and cellulose based on macroscopic experiments and molecular simulations.

    PubMed

    Wang, Shuang; Xia, Zhen; Hu, Yamin; He, Zhixia; Uzoejinwa, Benjamin Bernard; Wang, Qian; Cao, Bin; Xu, Shanna

    2017-03-01

    Co-pyrolysis conversion of seaweed (Enteromorpha clathrat and Sargassum fusiforme) polysaccharides and cellulose has been investigated. From the Py-GC/MS results, Enteromorpha clathrata (EN) polysaccharides pyrolysis mainly forms furans; while the products of Sargassum fusiforme (SA) polysaccharides pyrolysis are mainly acid esters. The formation mechanisms of H 2 O, CO 2 , and SO 2 during the pyrolysis of seaweed polysaccharides were analyzed using the thermogravimetric-mass spectrometry. Meanwhile the pyrolysis of seaweed polysaccharide based on the Amber and the ReaxFF force fields, has also been proposed and simulated respectively. The simulation results coincided with the experimental results. During the fast pyrolysis, strong synergistic effects among cellulose and seaweed polysaccharide molecules have been simulated. By comparing the experimental and simulation value, it has been found that co-pyrolysis could increase the number of molecular fragments, increase the pyrolysis conversion rate, and increase gas production rate at the middle temperature range. Copyright © 2016 Elsevier Ltd. All rights reserved.

  1. Kinetics and evolved gas analysis for pyrolysis of food processing wastes using TGA/MS/FT-IR.

    PubMed

    Özsin, Gamzenur; Pütün, Ayşe Eren

    2017-06-01

    The objective of this study was to identify the pyrolysis of different bio-waste produced by food processing industry in a comprehensible manner. For this purpose, pyrolysis behaviors of chestnut shells (CNS), cherry stones (CS) and grape seeds (GS) were investigated by thermogravimetric analysis (TGA) combined with a Fourier-transform infrared (FT-IR) spectrometer and a mass spectrometer (MS). In order to make available theoretical groundwork for biomass pyrolysis, activation energies were calculated with the help of four different model-free kinetic methods. The results are attributed to the complex reaction schemes which imply parallel, competitive and complex reactions during pyrolysis. During pyrolysis, the evolution of volatiles was also characterized by FT-IR and MS. The main evolved gases were determined as H 2 O, CO 2 and hydrocarbons such as CH 4 and temperature dependent profiles of the species were obtained. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Electrochemical and/or microbiological treatment of pyrolysis wastewater.

    PubMed

    Silva, José R O; Santos, Dara S; Santos, Ubiratan R; Eguiluz, Katlin I B; Salazar-Banda, Giancarlo R; Schneider, Jaderson K; Krause, Laiza C; López, Jorge A; Hernández-Macedo, Maria L

    2017-10-01

    Electrochemical oxidation may be used as treatment to decompose partially or completely organic pollutants (wastewater) from industrial processes such as pyrolysis. Pyrolysis is a thermochemical process used to obtain bio-oil from biomasses, generating a liquid waste rich in organic compounds including aldehydes and phenols, which can be submitted to biological and electrochemical treatments in order to minimize its environmental impact. Thus, electrochemical systems employing dimensionally stable anodes (DSAs) have been proposed to enable biodegradation processes in subsurface environments. In order to investigate the organic compound degradation from residual coconut pyrolysis wastewater, ternary DSAs containing ruthenium, iridium and cerium synthetized by the 'ionic liquid method' at different calcination temperatures (500, 550, 600 and 700 °C) for the pretreatment of these compounds, were developed in order to allow posterior degradation by Pseudomonas sp., Bacillus sp. or Acinetobacter sp. bacteria. The electrode synthesized applying 500 °C displayed the highest voltammetric charge and was used in the pretreatment of pyrolysis effluent prior to microbial treatment. Regarding biological treatment, the Pseudomonas sp. exhibited high furfural degradation in wastewater samples electrochemically pretreated at 2.0 V. On the other hand, the use of Acinetobacter efficiently degraded phenolic compounds such as phenol, 4-methylphenol, 2,5-methylphenol, 4-ethylphenol and 3,5-methylphenol in both wastewater samples, with and without electrochemical pretreatment. Overall, the results indicate that the combination of both processes used in this study is relevant for the treatment of pyrolysis wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Catalytic pyrolysis of waste furniture sawdust for bio-oil production.

    PubMed

    Uzun, Başak B; Kanmaz, Gülin

    2014-07-01

    In this study, the catalytic pyrolysis of waste furniture sawdust in the presence of ZSM-5, H-Y and MCM-41 (10 wt % of the biomass sample) was carried out in order to increase the quality of the liquid product at the various pyrolysis temperatures of 400, 450, 500 and 550(o)C. In the non-catalytic work, the maximum oil yield was obtained as 42% at 500(o)C in a fixed-bed reactor system. In the catalytic work, the maximum oil yield was decreased to 37.48, 30.04 and 29.23% in the presence of ZSM-5, H-Y and MCM-41, respectively. The obtained pyrolysis oils were analyzed by various spectroscopic and chromatographic techniques. It was determined that the use of a catalyst decreased acids and increased valuable organics found in the bio-oil. The removal of oxygen from bio-oil was confirmed with the results of the elemental analysis and gas chromatography-mass spectrometry. © The Author(s) 2014.

  4. A life cycle assessment of options for producing synthetic fuel via pyrolysis.

    PubMed

    Vienescu, D N; Wang, J; Le Gresley, A; Nixon, J D

    2018-02-01

    The aim of this study was to investigate the sustainability of producing synthetic fuels from biomass using thermochemical processing and different upgrading pathways. Life cycle assessment (LCA) models consisting of biomass collection, transportation, pre-treatment, pyrolysis and upgrading stages were developed. To reveal the environmental impacts associated with greater post-processing to achieve higher quality fuels, six different bio-oil upgrading scenarios were analysed and included esterification, ketonisation, hydrotreating and hydrocracking. Furthermore, to take into account the possible ranges in LCA inventory data, expected, optimistic and pessimistic values for producing and upgrading pyrolysis oils were evaluated. We found that the expected carbon dioxide equivalent emissions could be as high as 6000 gCO 2e /kg of upgraded fuel, which is greater than the emissions arising from the use of diesel fuel. Other environmental impacts occurring from the fuel production process are outlined, such as resource depletion, acidification and eutrophication. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Investigation of thermodynamic parameters in the pyrolysis conversion of biomass and manure to biochars using thermogravimetric analysis.

    PubMed

    Xu, Yiliang; Chen, Baoliang

    2013-10-01

    The thermodynamic parameters of the conversion of two companion pair materials, i.e., rice straw vs dairy manure, and rice bran vs chicken manure, to biochars were characterized by thermogravimetric analysis. The overall changes of activation energy (Ea) were well described by the Flynn-Wall method. The Ea values increased steeply from about 120 to 180 kJ/mol at the mass conversion (α) at 0.2-0.4, followed by a relatively steady change at 0.4<α<0.65, thereafter showed a quick increase at α>0.65. The higher contents of minerals in manures resulted in the larger Ea. The individual conversion of hemicellulose, cellulose and lignin in the feedstocks was identified and their thermodynamic parameters (ΔH°, ΔG° and ΔS°) were calculated. The yields of biochars calculated from TG curve were compared with the determined yields of biochars using muffle pyrolysis. Along with Fourier transform infrared spectra data, the distinct decompositions of biomasses and manures were evaluated. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Pyrolysis of polystyrene - polyphenylene oxide to recover styrene and useful products

    DOEpatents

    Evans, Robert J.; Chum, Helena L.

    1995-01-01

    A process of using fast pyrolysis in a carrier gas to convert a polystyrene and polyphenylene oxide plastic waste to a given polystyrene and polyphenylene oxide prior to pyrolysis of other plastic components therein comprising: selecting a first temperature range to cause pyrolysis of given polystyrene and polyphenylene oxide and its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and a support and treating the feed stream with the catalyst to affect acid or base catalyzed reaction pathways to maximize yield or enhance separation of high value monomeric constituent of styrene from polystyrene and polyphenylene oxide in the first temperature range; differentially heating the feed stream at a heat rate within the first temperature range to provide differential pyrolysis for selective recovery of the high value monomeric constituent of styrene from polystyrene and polyphenylene oxide prior to pyrolysis of other plastic components; separating the high value monomer constituent of styrene; selecting a second higher temperature range to cause pyrolysis to a different derived high value product of polyphenylene oxide from the plastic waste and differentially heating the feed stream at the higher temperature range to cause pyrolysis of the plastic into a polyphenylene oxide derived product; and separating the different derived high value polyphenylene oxide product.

  7. New applications of x-ray tomography in pyrolysis of biomass: biochar imaging

    USDA-ARS?s Scientific Manuscript database

    We report on the first ever use of non-destructive micrometer-scale synchrotron computed microtomography for characterization of biochar materials as a function of pyrolysis temperature. Using this innovative approach we have observed an increase in marcropore fraction of the sample, resulting in 29...

  8. Online study on the co-pyrolysis of coal and corn with vacuum ultraviolet photoionization mass spectrometry.

    PubMed

    Weng, Jun-Jie; Liu, Yue-Xi; Zhu, Ya-Nan; Pan, Yang; Tian, Zhen-Yu

    2017-11-01

    With the aim to support the experimental tests in a circulating fluidized bed pilot plant, the pyrolysis processes of coal, corn, and coal-corn blend have been studied with an online pyrolysis photoionization time-of-flight mass spectrometry (Py-PI-TOFMS). The mass spectra at different temperatures (300-800°C) as well as time-evolved profiles of selected species were measured. The pyrolysis products such as alkanes, alkenes, phenols, aromatics, as well as nitrogen- and sulfur-containing species were detected. As temperature rises, the relative ion intensities of high molecular weight products tend to decrease, while those of aromatics increase significantly. During the co-pyrolysis, coal can promote the reaction temperature of cellulose in corn. Time-evolved profiles demonstrate that coal can affect pyrolysis rate of cellulose, hemicellulose, and lignin of corn in blend. This work shows that Py-PI-TOFMS is a powerful approach to permit a better understanding of the mechanisms underlying the co-pyrolysis of coal and biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Effect of torrefaction pretreatment on the pyrolysis of rubber wood sawdust analyzed by Py-GC/MS.

    PubMed

    Chen, Wei-Hsin; Wang, Chao-Wen; Kumar, Gopalakrishnan; Rousset, Patrick; Hsieh, Tzu-Hsien

    2018-07-01

    The aim of this study was to investigate the effect of torrefaction on the pyrolysis of rubber wood sawdust (RWS) using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Three typical torrefaction temperatures (200, 250, and 300 °C) and pyrolysis temperatures (450, 500, and 550 °C) were considered. The results suggested that only diethyl phthalate, belonging to esters, was detected at the torrefaction temperatures of 200 and 250 °C, revealing hemicellulose degradation. With the torrefaction temperature of 300 °C, esters, aldehydes, and phenols were detected, suggesting the predominant decomposition of hemicellulose and lignin. The double-shot pyrolysis indicated that the contents of oxy-compounds such as acids and aldehydes in pyrolysis bio-oil decreased with rising torrefaction temperature, implying that increasing torrefaction severity abated oxygen content in the bio-oil. With the torrefaction temperature of 300 °C, relatively more cellulose was retained in the biomass because the carbohydrate content in the pyrolysis bio-oil increased significantly. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Microwave pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lei, Hanwu; Ren, Shoujie; Wang, Lu

    2011-05-01

    Microwave pyrolysis of distillers dried grain with solubles (DDGS) was investigated to determine the effects of pyrolytic conditions on the yields of bio-oil, syngas, and biochar. Pyrolysis process variables included reaction temperature, time, and power input. Microwave pyrolysis of DDGS was analyzed using response surface methodology to find out the effect of process variables on the biofuel (bio-oil and syn- gas) conversion yield and establish prediction models. Bio-oil recovery was in the range of 26.5–50.3 wt.% of the biomass. Biochar yields were 23.5–62.2% depending on the pyrolysis conditions. The energy con- tent of DDGS bio-oils was 28 MJ/kg obtained atmore » the 650 oC and 8 min, which was about 66.7% of the heat- ing value of gasoline. GC/MS analysis indicated that the biooil contained a series of important and useful chemical compounds: aliphatic and aromatic hydrocarbons. At least 13% of DDGS bio-oil was the same hydrocarbon compounds found in regular unleaded gasoline.« less

  11. Effect of high-pressure on pine sawdust pyrolysis: Products distribution and characteristics

    NASA Astrophysics Data System (ADS)

    Xu, Baiqing; Li, Aimin

    2017-08-01

    In this work, the pressurized pyrolysis of pine sawdust was performed with a self-made pressurized pyrolysis reactor to investigatethe influence of pyrolysis pressure in the range of 0-5 MPa on products distribution and characteristics. The combustion feature and microstructure of bio-char had analyzed by thermogravimetric (TG) and scanning electron microscopy (SEM), respectively. Elemental analyzer and Fourier transform infrared spectroscopy (FTIR) were used to confirm the identities of bio-oil. The results indicated the pressure had a notable impact on the biomass pyrolysis, which promoted the secondary cracking of bio-oil to produce more gaseous products and bio-char. The minimum bio-oil yield of 20.24% was obtained at the pressure of 5 MPa. Furthermore, the pressure improved the products characteristics. The increasing of pressure was favour to the deoxygenation and dehydrogenation reactions of bio-oil, which led to the increase of CH4, H2 and CO2 in gas. At the same time, under the influence of pressure, the surface structure and compactedness of the bio-char were obviously improved.

  12. Microwave pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production.

    PubMed

    Lei, Hanwu; Ren, Shoujie; Wang, Lu; Bu, Quan; Julson, James; Holladay, John; Ruan, Roger

    2011-05-01

    Microwave pyrolysis of distillers dried grain with solubles (DDGS) was investigated to determine the effects of pyrolytic conditions on the yields of bio-oil, syngas, and biochar. Pyrolysis process variables included reaction temperature, time, and power input. Microwave pyrolysis of DDGS was analyzed using response surface methodology to find out the effect of process variables on the biofuel (bio-oil and syngas) conversion yield and establish prediction models. Bio-oil recovery was in the range of 26.5-50.3 wt.% of the biomass. Biochar yields were 23.5-62.2% depending on the pyrolysis conditions. The energy content of DDGS bio-oils was 28 MJ/kg obtained at the 650°C and 8 min, which was about 66.7% of the heating value of gasoline. GC/MS analysis indicated that the biooil contained a series of important and useful chemical compounds: aliphatic and aromatic hydrocarbons. At least 13% of DDGS bio-oil was the same hydrocarbon compounds found in regular unleaded gasoline. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors

    DOE PAGES

    Engtrakul, Chaiwat; Mukarakate, Calvin; Starace, Anne K.; ...

    2015-11-14

    The impact of catalyst acidity on the selectivity of upgraded biomass pyrolysis products was studied by passing pine pyrolysis vapors over five ZSM-5 catalysts of varying acidity at 500 degrees C. The SiO 2-to-Al 2O 3 ratio (SAR) of the ZSM-5 zeolite was varied from 23 to 280 to control the acidity of the catalyst and the composition of upgraded products. The upgraded product stream was analyzed by GCMS. Additionally, catalysts were characterized using temperature programmed desorption, diffuse-reflectance FTIR spectroscopy, N 2 physisorption, and X-ray diffraction. The results showed that the biomass pyrolysis vapors were highly deoxygenated to form amore » slate of aromatic hydrocarbons over all of the tested ZSM-5 catalysts. As the overall acidity of the ZSM-5 increased the selectivity toward alkylated (substituted) aromatics (e.g., xylene, dimethyl-naphthalene, and methyl-anthracene) decreased while the selectivity toward unsubstituted aromatics (e.g., benzene, naphthalene, and anthracene) increased. Additionally, the selectivity toward polycyclic aromatic compounds (2-ring and 3-ring) increased as catalyst acidity increased, corresponding to a decrease in acid site spacing. The increased selectivity toward less substituted polycyclic aromatic compounds with increasing acidity is related to the relative rates of cyclization and alkylation reactions within the zeolite structure. As the acid site concentration increases and sites become closer to each other, the formation of additional cyclization products occurs at a greater rate than alkylated products. The ability to adjust product selectivity within 1-, 2-, and 3-ring aromatic families, as well as the degree of substitution, by varying ZSM-5 acidity could have significant benefits in terms creating a slate of upgraded biomass pyrolysis products to meet specific target market demands.« less

  14. Aromatics and phenols from catalytic pyrolysis of Douglas fir pellets in microwave with ZSM-5 as a catalyst

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Lu; Lei, Hanwu; Ren, Shoujie

    Microwave assisted catalytic pyrolysis was investigated to convert Douglas fir pellets to bio-oils by a ZSM-5 Zeolite catalyst. A central composite experimental design (CCD) was used to optimize the catalytic pyrolysis process. The effects of reaction time, temperature and catalyst to biomass ratio on the bio-oil, syngas, and biochar yields were determined. GC/MS analysis results showed that the bio-oil contained a series of important and useful chemical compounds. Phenols, guaiacols, and aromatic hydrocarbons were the most abundant compounds which were about 50-82 % in bio-oil depending on the pyrolysis conditions. Comparison between the bio-oils from microwave pyrolysis with and withoutmore » catalyst showed that the catalyst increased the content of aromatic hydrocarbons and phenols. A reaction pathway was proposed for microwave assisted catalyst pyrolysis of Douglas fir pellets.« less

  15. Enhanced thermal destruction of toxic microalgal biomass by using CO2.

    PubMed

    Jung, Jong-Min; Lee, Jechan; Kim, Jieun; Kim, Ki-Hyun; Kim, Hyung-Wook; Jeon, Young Jae; Kwon, Eilhann E

    2016-10-01

    This work confirmed that dominant microalgal strain in the eutrophic site (the Han River in Korea) was Microcystis aeruginosa (M. aeruginosa) secreting toxins. Collected and dried microalgal biomass had an offensive odor due to microalgal lipid, of which the content reached up to 2±0.2wt.% of microalgal biomass (dry basis). This study has validated that the offensive odor is attributed to the C3-6 range of volatile fatty acids (VFAs), which was experimentally identified by the non-catalytic transformation of triglycerides (TGs) and free fatty acids (FFAs) in microalgal biomass into fatty acid methyl esters (FAMEs). In particular, this study mechanistically investigated the influence of CO2 in the thermal destruction (i.e., pyrolysis) of hazardous microalgal biomass in order to achieve dual purposes (i.e., thermal disposal of hazardous microalgal biomass and energy recovery). The influence of CO2 in pyrolysis of microalgal biomass was identified as 1) the enhanced thermal cracking behaviors of volatile organic compounds (VOCs) from the thermal degradation of microalgal biomass and 2) the direct gas phase reaction between CO2 and VOCs. These identified influences of CO2 in pyrolysis of microalgal biomass significantly enhanced the generation of CO: the enhanced generation of CO in the presence of CO2 was 590% at 660°C, 1260% at 690°C, and 3200% at 720°C. In addition, two identified influences of CO2 (i.e., enhanced thermal cracking and direct gas phase reaction) occurred simultaneously and independently. The identified gas phase reaction in the presence of CO2 was only initiated at temperatures higher than 500°C, which was different from the Boudouard reaction. Lastly, the experimental work justified that exploiting CO2 as a reaction medium and/or chemical feedstock will provide new technical approaches for controlling syngas ratio and in-situ air pollutant control without using catalysts. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Derivation of hydrous pyrolysis kinetic parameters from open-system pyrolysis

    NASA Astrophysics Data System (ADS)

    Tseng, Yu-Hsin; Huang, Wuu-Liang

    2010-05-01

    Kinetic information is essential to predict the temperature, timing or depth of hydrocarbon generation within a hydrocarbon system. The most common experiments for deriving kinetic parameters are mainly by open-system pyrolysis. However, it has been shown that the conditions of open-system pyrolysis are deviant from nature by its low near-ambient pressure and high temperatures. Also, the extrapolation of heating rates in open-system pyrolysis to geological conditions may be questionable. Recent study of Lewan and Ruble shows hydrous-pyrolysis conditions can simulate the natural conditions better and its applications are supported by two case studies with natural thermal-burial histories. Nevertheless, performing hydrous pyrolysis experiment is really tedious and requires large amount of sample, while open-system pyrolysis is rather convenient and efficient. Therefore, the present study aims at the derivation of convincing distributed hydrous pyrolysis Ea with only routine open-system Rock-Eval data. Our results unveil that there is a good correlation between open-system Rock-Eval parameter Tmax and the activation energy (Ea) derived from hydrous pyrolysis. The hydrous pyrolysis single Ea can be predicted from Tmax based on the correlation, while the frequency factor (A0) is estimated based on the linear relationship between single Ea and log A0. Because the Ea distribution is more rational than single Ea, we modify the predicted single hydrous pyrolysis Ea into distributed Ea by shifting the pattern of Ea distribution from open-system pyrolysis until the weight mean Ea distribution equals to the single hydrous pyrolysis Ea. Moreover, it has been shown that the shape of the Ea distribution is very much alike the shape of Tmax curve. Thus, in case of the absence of open-system Ea distribution, we may use the shape of Tmax curve to get the distributed hydrous pyrolysis Ea. The study offers a new approach as a simple method for obtaining distributed hydrous pyrolysis

  17. Biochar enables anaerobic digestion of aqueous phase from intermediate pyrolysis of biomass.

    PubMed

    Torri, Cristian; Fabbri, Daniele

    2014-11-01

    Intermediate pyrolysis produces a two-phase liquid whose aqueous phase is characterized by low heating value and high water content (aqueous pyrolysis liquid, APL). Anaerobic digestion can be the straightest way to produce a fuel (methane) from this material. Batch tests showed poor performance in anaerobic digestion of APL, which underlined the inhibition of biological process. Nutrient supplementation was ineffective, whereas biochar addition increased yield of methane (60±15% of theoretical) with respect to pure APL (34±6% of theoretical) and improved the reaction rate. On the basis of batch results, a semi-continuous biomethanation test was set up, by adding an increasingly amount of APL in a 30ml reactor preloaded with biochar (0.8gml(-1)). With a daily input of 5gd(-1)l(-1) of APL (corresponding to overall amount of 0.1kgl(-1) added before the end of the study) the yield of methane was 65±5% of the theoretical. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Universal model of slow pyrolysis technology producing biochar and heat from standard biomass needed for the techno-economic assessment.

    PubMed

    Klinar, Dušan

    2016-04-01

    Biochar as a soil amendment and carbon sink becomes in last period one of the vast, interesting product of slow pyrolysis. Simplest and most used industrial process arrangement is a production of biochar and heat at the same time. Proposed mass and heat balance model consist of heat consumers (heat demand side) and heat generation-supply side. Direct burning of all generated uncondensed volatiles from biomass provides heat. Calculation of the mass and heat balance of both sides reveals the internal distribution of masses and energy inside process streams and units. Thermodynamic calculations verified not only the concept but also numerical range of the results. The comparisons with recent published scientific and vendors data prove its general applicability and reliability. The model opens the possibility for process efficiency innovations. Finally, the model was adapted to give more investors favorable results and support techno-economic assessments entirely. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Producing liquid fuels from biomass

    NASA Astrophysics Data System (ADS)

    Solantausta, Yrjo; Gust, Steven

    The aim of this survey was to compare, on techno-economic criteria, alternatives of producing liquid fuels from indigenous raw materials in Finland. Another aim was to compare methods under development and prepare a proposal for steering research related to this field. Process concepts were prepared for a number of alternatives, as well as analogous balances and production and investment cost assessments for these balances. Carbon dioxide emissions of the alternatives and the price of CO2 reduction were also studied. All the alternatives for producing liquid fuels from indigenous raw materials are utmost unprofitable. There are great differences between the alternatives. While the production cost of ethanol is 6 to 9 times higher than the market value of the product, the equivalent ratio for substitute fuel oil produced from peat by pyrolysis is 3 to 4. However, it should be borne in mind that the technical uncertainties related to the alternatives are of different magnitude. Production of ethanol from barley is of commercial technology, while biomass pyrolysis is still under development. If the aim is to reach smaller carbon dioxide emissions by using liquid biofuels, the most favorable alternative is pyrolysis oil produced from wood. Fuels produced from cultivated biomass are more expensive ways of reducing CO2 emissions. Their potential of reducing CO2 emissions in Finland is insignificant. Integration of liquid fuel production to some other production line is more profitable.

  20. Catalysis Meets Nonthermal Separation for the Production of (Alkyl)phenols and Hydrocarbons from Pyrolysis Oil.

    PubMed

    Cao, Zhengwen; Engelhardt, Jan; Dierks, Michael; Clough, Matthew T; Wang, Guang-Hui; Heracleous, Eleni; Lappas, Angelos; Rinaldi, Roberto; Schüth, Ferdi

    2017-02-20

    A simple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass. The overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoC x /C is a promising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired Ar-OH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography, serving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass, no further synthetic steps, and no input of additional (e.g., petrochemical) platform molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Hydrogen production from switchgrass via an integrated pyrolysis-microbial electrolysis process.

    PubMed

    Lewis, A J; Ren, S; Ye, X; Kim, P; Labbe, N; Borole, A P

    2015-11-01

    A new approach to hydrogen production using an integrated pyrolysis-microbial electrolysis process is described. The aqueous stream generated during pyrolysis of switchgrass was used as a substrate for hydrogen production in a microbial electrolysis cell, achieving a maximum hydrogen production rate of 4.3 L H2/L anode-day at a loading of 10 g COD/L-anode-day. Hydrogen yields ranged from 50±3.2% to 76±0.5% while anode Coulombic efficiency ranged from 54±6.5% to 96±0.21%, respectively. Significant conversion of furfural, organic acids and phenolic molecules was observed under both batch and continuous conditions. The electrical and overall energy efficiency ranged from 149-175% and 48-63%, respectively. The results demonstrate the potential of the pyrolysis-microbial electrolysis process as a sustainable and efficient route for production of renewable hydrogen with significant implications for hydrocarbon production from biomass. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Hydrogen production from switchgrass via a hybrid pyrolysis-microbial electrolysis process

    DOE PAGES

    Lewis, Alex J.; Ren, Shoujie; Ye, Philip; ...

    2015-06-30

    A new approach to hydrogen production using a hybrid pyrolysis-microbial electrolysis process is described. The aqueous stream generated during pyrolysis of switchgrass was used as a substrate for hydrogen production in a microbial electrolysis cell, achieving a maximum hydrogen production rate of 4.3 L H2/L-day at a loading of 10 g COD/L-anode-day. Hydrogen yields ranged from 50 3.2% to76 0.5% while anode coulombic efficiency ranged from 54 6.5% to 96 0.21%, respectively. Significant conversion of furfural, organic acids and phenolic molecules was observed under both batch and continuous conditions. The electrical and overall energy efficiency ranged from 149-175% and 48-63%,more » respectively. The results demonstrate the potential of the pyrolysis-microbial electrolysis process as a sustainable and efficient route for production of renewable hydrogen with significant implications for hydrocarbon production from biomass.« less

  3. Energy potential from rice husk through direct combustion and fast pyrolysis: A review.

    PubMed

    Quispe, Isabel; Navia, Rodrigo; Kahhat, Ramzy

    2017-01-01

    Rapid population growth and consumption of goods and services imply that demand for energy and resources increases continuously. Energy consumption linked to non-renewable resources contributes to greenhouse gas emissions and enhances resource depletion. In this context, the use of agricultural solid residues such as rice husk, coffee husk, wheat straw, sugar cane bagasse, among others, has been widely studied as an alternative energy source in order to decrease the use of fossil fuels. However, rice husk is among those agricultural residues that are least used to obtain energy in developing countries. Approximately 134 million tonnes of rice husk are produced annually in the world, of which over 90% are burned in open air or discharged into rivers and oceans in order to dispose of them. This review examines the energetic potential of agricultural residues, focused on rice husk. The review describes direct combustion and fast pyrolysis technologies to transform rice husk into energy considering its physical and chemical properties. In addition, a review of existing studies analyzing these technologies from an environmental life cycle thinking perspective, contributing to their sustainable use, is performed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. ASPEN+ and economic modeling of equine waste utilization for localized hot water heating via fast pyrolysis

    USDA-ARS?s Scientific Manuscript database

    ASPEN Plus based simulation models have been developed to design a pyrolysis process for the on-site production and utilization of pyrolysis oil from equine waste at the Equine Rehabilitation Center at Morrisville State College (MSC). The results indicate that utilization of all available Equine Reh...

  5. Sources of biomass feedstock variability and the potential impact on biofuels production

    DOE PAGES

    Williams, C. Luke; Westover, Tyler L.; Emerson, Rachel M.; ...

    2015-11-23

    In this study, terrestrial lignocellulosic biomass has the potential to be a carbon neutral and domestic source of fuels and chemicals. However, the innate variability of biomass resources, such as herbaceous and woody materials, and the inconsistency within a single resource due to disparate growth and harvesting conditions, presents challenges for downstream processes which often require materials that are physically and chemically consistent. Intrinsic biomass characteristics, including moisture content, carbohydrate and ash compositions, bulk density, and particle size/shape distributions are highly variable and can impact the economics of transforming biomass into value-added products. For instance, ash content increases by anmore » order of magnitude between woody and herbaceous feedstocks (from ~0.5 to 5 %, respectively) while lignin content drops by a factor of two (from ~30 to 15 %, respectively). This increase in ash and reduction in lignin leads to biofuel conversion consequences, such as reduced pyrolysis oil yields for herbaceous products as compared to woody material. In this review, the sources of variability for key biomass characteristics are presented for multiple types of biomass. Additionally, this review investigates the major impacts of the variability in biomass composition on four conversion processes: fermentation, hydrothermal liquefaction, pyrolysis, and direct combustion. Finally, future research processes aimed at reducing the detrimental impacts of biomass variability on conversion to fuels and chemicals are proposed.« less

  6. An Environmental and Economic Evaluation of Pyrolysis for Energy Generation in Taiwan with Endogenous Land Greenhouse Gases Emissions

    PubMed Central

    Kung, Chih-Chun; McCarl, Bruce A.; Chen, Chi-Chung

    2014-01-01

    Taiwan suffers from energy insecurity and the threat of potential damage from global climate changes. Finding ways to alleviate these forces is the key to Taiwan’s future social and economic development. This study examines the economic and environmental impacts when ethanol, conventional electricity and pyrolysis-based electricity are available alternatives. Biochar, as one of the most important by-product from pyrolysis, has the potential to provide significant environmental benefits. Therefore, alternative uses of biochar are also examined in this study. In addition, because planting energy crops would change the current land use pattern, resulting in significant land greenhouse gases (GHG) emissions, this important factor is also incorporated. Results show that bioenergy production can satisfy part of Taiwan’s energy demand, but net GHG emissions offset declines if ethanol is chosen. Moreover, at high GHG price conventional electricity and ethanol will be driven out and pyrolysis will be a dominant technology. Fast pyrolysis dominates when ethanol and GHG prices are low, but slow pyrolysis is dominant at high GHG price, especially when land GHG emissions are endogenously incorporated. The results indicate that when land GHG emission is incorporated, up to 3.8 billion kWh electricity can be produced from fast pyrolysis, while up to 2.2 million tons of CO2 equivalent can be offset if slow pyrolysis is applied. PMID:24619159

  7. An environmental and economic evaluation of pyrolysis for energy generation in Taiwan with endogenous land greenhouse gases emissions.

    PubMed

    Kung, Chih-Chun; McCarl, Bruce A; Chen, Chi-Chung

    2014-03-11

    Taiwan suffers from energy insecurity and the threat of potential damage from global climate changes. Finding ways to alleviate these forces is the key to Taiwan's future social and economic development. This study examines the economic and environmental impacts when ethanol, conventional electricity and pyrolysis-based electricity are available alternatives. Biochar, as one of the most important by-product from pyrolysis, has the potential to provide significant environmental benefits. Therefore, alternative uses of biochar are also examined in this study. In addition, because planting energy crops would change the current land use pattern, resulting in significant land greenhouse gases (GHG) emissions, this important factor is also incorporated. Results show that bioenergy production can satisfy part of Taiwan's energy demand, but net GHG emissions offset declines if ethanol is chosen. Moreover, at high GHG price conventional electricity and ethanol will be driven out and pyrolysis will be a dominant technology. Fast pyrolysis dominates when ethanol and GHG prices are low, but slow pyrolysis is dominant at high GHG price, especially when land GHG emissions are endogenously incorporated. The results indicate that when land GHG emission is incorporated, up to 3.8 billion kWh electricity can be produced from fast pyrolysis, while up to 2.2 million tons of CO2 equivalent can be offset if slow pyrolysis is applied.

  8. Pyrolysis and hydrolysis of mixed polymer waste comprising polyethyleneterephthalate and polyethylene to sequentially recover

    DOEpatents

    Evans, Robert J.; Chum, Helena L.

    1998-01-01

    A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.

  9. Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC.

    PubMed

    Negahdar, Leila; Gonzalez-Quiroga, Arturo; Otyuskaya, Daria; Toraman, Hilal E; Liu, Li; Jastrzebski, Johann T B H; Van Geem, Kevin M; Marin, Guy B; Thybaut, Joris W; Weckhuysen, Bert M

    2016-09-06

    Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13 C nuclear magnetic resonance ( 13 C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. 13 C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (≈30%) and carbohydrate (≈27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (≈35%) and aromatic (≈30%) carbons, while rapeseed cake-based bio-oil had great portions of alkyl carbons (≈82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil.

  10. Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC

    PubMed Central

    2016-01-01

    Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13C nuclear magnetic resonance (13C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. 13C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (≈30%) and carbohydrate (≈27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (≈35%) and aromatic (≈30%) carbons, while rapeseed cake-based bio-oil had great portions of alkyl carbons (≈82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil. PMID:27668136

  11. Techno Economic Analysis of Hydrogen Production by gasification of biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Francis Lau

    Biomass represents a large potential feedstock resource for environmentally clean processes that produce power or chemicals. It lends itself to both biological and thermal conversion processes and both options are currently being explored. Hydrogen can be produced in a variety of ways. The majority of the hydrogen produced in this country is produced through natural gas reforming and is used as chemical feedstock in refinery operations. In this report we will examine the production of hydrogen by gasification of biomass. Biomass is defined as organic matter that is available on a renewable basis through natural processes or as a by-productmore » of processes that use renewable resources. The majority of biomass is used in combustion processes, in mills that use the renewable resources, to produce electricity for end-use product generation. This report will explore the use of hydrogen as a fuel derived from gasification of three candidate biomass feedstocks: bagasse, switchgrass, and a nutshell mix that consists of 40% almond nutshell, 40% almond prunings, and 20% walnut shell. In this report, an assessment of the technical and economic potential of producing hydrogen from biomass gasification is analyzed. The resource base was assessed to determine a process scale from feedstock costs and availability. Solids handling systems were researched. A GTI proprietary gasifier model was used in combination with a Hysys(reg. sign) design and simulation program to determine the amount of hydrogen that can be produced from each candidate biomass feed. Cost estimations were developed and government programs and incentives were analyzed. Finally, the barriers to the production and commercialization of hydrogen from biomass were determined. The end-use of the hydrogen produced from this system is small PEM fuel cells for automobiles. Pyrolysis of biomass was also considered. Pyrolysis is a reaction in which biomass or coal is partially vaporized by heating. Gasification is a

  12. Use of Biochar from the Pyrolysis of Waste Organic Material as a Soil Amendment

    USDA-ARS?s Scientific Manuscript database

    Biochar is a charcoal-like material produced by the thermochemical pyrolysis of biomass materials. It is being considered as a potentially significant means of storing carbon for long periods to mitigate greenhouse gases. Much of the interest comes from studies of Amazonian soils that appear to have...

  13. Rapid co-pyrolysis of rice straw and a bituminous coal in a high-frequency furnace and gasification of the residual char.

    PubMed

    Yuan, Shuai; Dai, Zheng-hua; Zhou, Zhi-jie; Chen, Xue-li; Yu, Guang-suo; Wang, Fu-chen

    2012-04-01

    Rapid pyrolysis of rice straw (RS) and Shenfu bituminous coal (SB) separately, and rapid co-pyrolysis of RS/SB blends (mass ratio 1:4, 1:4, and 4:1), were carried out in a high-frequency furnace which can ensure both high heating rate and satisfying contact of fuel particles. Synergies between RS and SB during rapid co-pyrolysis were investigated. Intrinsic and morphological structures of residual char from co-pyrolysis, and their effects on gasification characteristics were also studied. Synergies occurred during rapid co-pyrolysis of RS and SB (RS/SB=1:4) resulting in decreasing char yields and increasing volatile yields. Synergies also happened during gasification of the char derived from co-pyrolysis of RS and SB with mass ratio of 1:4. The increased mass ratio of RS to SB did not only weaken synergies during co-pyrolysis, but significantly reduced the gasification rates of the co-pyrolysis char compared to the calculated values. Results can help to optimize co-conversion process of biomass/coal. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Bioenergy potential of Wolffia arrhiza appraised through pyrolysis, kinetics, thermodynamics parameters and TG-FTIR-MS study of the evolved gases.

    PubMed

    Ahmad, Muhammad Sajjad; Mehmood, Muhammad Aamer; Liu, Chen-Guang; Tawab, Abdul; Bai, Feng-Wu; Sakdaronnarong, Chularat; Xu, Jianren; Rahimuddin, Sawsan Abdulaziz; Gull, Munazza

    2018-04-01

    This study evaluated the bioenergy potential of Wolffia arrhiza via pyrolysis. The biomass was collected from the pond receiving city wastewater. Oven dried powdered biomass was exposed to thermal degradation at three heating rates (10, 30 and 50° C min -1 ) using Thermogravimetry-Differential Scanning Calorimetry analyzer in an inert environment. Data obtained were subjected to the isoconversional models of Kissenger-Akahira-Sunose (KSA) and Flynn-Wall-Ozawa (FWO) to elucidate the reaction chemistry. Kinetic parameters including, E a (136-172 kJmol -1 ) and Gibb's free energy (171 kJmol -1 ) showed the remarkable bioenergy potential of the biomass. The average enthalpies indicated that the product formation is favored during pyrolysis. Advanced coupled TG-FTIR-MS analyses showed the evolved gases to contain the compounds containing CO functional groups (aldehydes, ketones), aromatic and aliphatic hydrocarbons as major pyrolytic products. This low-cost abundant biomass may be used to produce energy and chemicals in a cost-efficient and environmentally friendly way. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Improving hydrocarbon yield from catalytic fast co-pyrolysis of hemicellulose and plastic in the dual-catalyst bed of CaO and HZSM-5.

    PubMed

    Ding, Kuan; Zhong, Zhaoping; Wang, Jia; Zhang, Bo; Fan, Liangliang; Liu, Shiyu; Wang, Yunpu; Liu, Yuhuan; Zhong, Daoxu; Chen, Paul; Ruan, Roger

    2018-08-01

    The high concentration of oxygenated compounds in pyrolytic products prohibits the conversion of hemicellulose to important biofuels and chemicals via fast pyrolysis. Herein a dual-catalyst bed of CaO and HZSM-5 was developed to convert acids in the pyrolytic products of xylan to valuable hydrocarbons. Meanwhile, LLDPE was co-pyrolyzed with xylan to supplement hydrogen during the catalysis of HZSM-5. The results showed that CaO could effectively transform acids into ketones. A minimum yield of acids (2.74%) and a maximum yield of ketones (42.93%) were obtained at a catalyst to feedstock ratio of 2:1. The dual-catalyst bed dramatically increased the yield of aromatics. Moreover, hydrogen-rich fragments derived from LLDPE promoted the Diels-Alder reactions of furans and participated in the hydrocarbon pool reactions of non-furanic compounds. As a result, a higher yield of hydrocarbons was achieved. This study provides a fundamental for recovering energy and chemicals from pyrolysis of hemicellulose. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. Copyrolysis of Biomass and Coal: A Review of Effects of Copyrolysis Parameters, Product Properties, and Synergistic Mechanisms

    PubMed Central

    2016-01-01

    Concerns in the last few decades regarding the environmental and socioeconomic impacts of the dependence on fossil fuels have resulted in calls for more renewable and alternative energy sources. This has led to recent interest in copyrolysis of biomass and coal. Numerous reviews have been found related to individual pyrolysis of coal and biomass. This review deals mainly with the copyrolysis of coal and biomass and then compares their results with those obtained using coal and biomass pyrolysis in detail. It is controversial whether there are synergistic or additive behaviours when coal and biomass are blended during copyrolysis. In this review, the effects of reaction parameters such as feedstock types, blending ratio, heating rate, temperature, and reactor types on the occurrence of synergy are discussed. Also, the main properties of the copyrolytic products are pointed out. Some possible synergistic mechanisms are also suggested. Additionally, several outlooks based on studies in the literature are also presented in this paper. PMID:27722171

  17. Kinetic and isothermal adsorption-desorption of PAEs on biochars: effect of biomass feedstock, pyrolysis temperature, and mechanism implication of desorption hysteresis.

    PubMed

    Jing, Fanqi; Pan, Minjun; Chen, Jiawei

    2018-04-01

    Biochar has the potential to sequester biomass carbon efficiently into land, simultaneously while improving soil fertility and crop production. Biochar has also attracted attention as a potential sorbent for good performance on adsorption and immobilization of many organic pollutants such as phthalic acid esters (PAEs), a typical plasticizer in plastic and presenting a current environmental issue. Due to lack of investigation on the kinetic and thermodynamic adsorption-desorption of PAEs on biochar, we systematically assessed adsorption-desorption for two typical PAEs, dimethyl phthalate (DMP) and diethyl phthalate (DEP), using biochar derived from peanut hull and wheat straw at different pyrolysis temperatures (450, 550, and 650 °C). The aromaticity and specific surface area of biochars increased with the pyrolysis temperature, whereas the total amount of surface functional groups decreased. The quasi-second-order kinetic model could better describe the adsorption of DMP/DEP, and the adsorption capacity of wheat straw biochars was higher than that of peanut hull biochars, owing to the O-bearing functional groups of organic matter on exposed minerals within the biochars. The thermodynamic analysis showed that DMP/DEP adsorption on biochar is physically spontaneous and endothermic. The isothermal desorption and thermodynamic index of irreversibility indicated that DMP/DEP is stably adsorbed. Sorption of PAEs on biochar and the mechanism of desorption hysteresis provide insights relevant not only to the mitigation of plasticizer mobility but also to inform on the effect of biochar amendment on geochemical behavior of organic pollutants in the water and soil.

  18. Fuels and chemicals from equine-waste-derived tail gas reactive pyrolysis oil: technoeconomic analysis, environmental and exergetic life cycle assessment

    USDA-ARS?s Scientific Manuscript database

    Horse manure, whose improper disposal imposes considerable environmental costs, constitutes an apt feedstock for conversion to renewable fuels and chemicals when tail gas reactive pyrolysis (TGRP) is employed. TGRP is a modification of fast pyrolysis that recycles its non-condensable gases and produ...

  19. Scalable and Tunable Carbide-Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Regmi, Yagya; Rogers, Bridget; Labbe, Nicole

    We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method comprised of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon increasing the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates usingmore » pyrolysis gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized to tune the composition of the bio-oil downstream.« less

  20. Scalable and Tunable Carbide-Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

    DOE PAGES

    Regmi, Yagya; Rogers, Bridget; Labbe, Nicole; ...

    2017-07-13

    We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method comprised of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon increasing the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates usingmore » pyrolysis gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized to tune the composition of the bio-oil downstream.« less

  1. Biomass energy: a monograph

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hiler, E.A.; Stout, B.A.

    1985-01-01

    This monograph presents a review of the status of biomass as an alternative energy source, with particular emphasis on the energy research programs of the Texas A and M University System. Eight chapters include joint research efforts in thermochemical conversion (combustion, gasification, pyrolysis), biological conversion (anaerobic digestion, fermentation), and plant oil extraction (physical expelling, solvent extraction). Six chapters are indexed separately for inclusion in the Energy Data Base and in Energy Abstracts for Policy Analysis.

  2. Fast Pyrolysis Oil Stabilization: An Integrated Catalytic and Membrane Approach for Improved Bio-oils. Final Report

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    George W. Huber; Upadhye, Aniruddha A.; Ford, David M.

    This University of Massachusetts, Amherst project, "Fast Pyrolysis Oil Stabilization: An Integrated Catalytic and Membrane Approach for Improved Bio-oils" started on 1st February 2009 and finished on August 31st 2011. The project consisted following tasks: Task 1.0: Char Removal by Membrane Separation Technology The presence of char particles in the bio-oil causes problems in storage and end-use. Currently there is no well-established technology to remove char particles less than 10 micron in size. This study focused on the application of a liquid-phase microfiltration process to remove char particles from bio-oil down to slightly sub-micron levels. Tubular ceramic membranes of nominalmore » pore sizes 0.5 and 0.8m were employed to carry out the microfiltration, which was conducted in the cross-flow mode at temperatures ranging from 38 to 45 C and at three different trans-membrane pressures varying from 1 to 3 bars. The results demonstrated the removal of the major quantity of char particles with a significant reduction in overall ash content of the bio-oil. The results clearly showed that the cake formation mechanism of fouling is predominant in this process. Task 2.0 Acid Removal by Membrane Separation Technology The feasibility of removing small organic acids from the aqueous fraction of fast pyrolysis bio-oils using nanofiltration (NF) and reverse osmosis (RO) membranes was studied. Experiments were carried out with a single solute solutions of acetic acid and glucose, binary solute solutions containing both acetic acid and glucose, and a model aqueous fraction of bio-oil (AFBO). Retention factors above 90% for glucose and below 0% for acetic acid were observed at feed pressures near 40 bar for single and binary solutions, so that their separation in the model AFBO was expected to be feasible. However, all of the membranes were irreversibly damaged when experiments were conducted with the model AFBO due to the presence of guaiacol in the feed solution

  3. Production of bio-oil rich in acetic acid and phenol from fast pyrolysis of palm residues using a fluidized bed reactor: Influence of activated carbons.

    PubMed

    Jeong, Jae-Yong; Lee, Uen-Do; Chang, Won-Seok; Jeong, Soo-Hwa

    2016-11-01

    In this study, palm residues were pyrolyzed in a bench-scale (3kg/h) fast pyrolysis plant equipped with a fluidized bed reactor and bio-oil separation system for the production of bio-oil rich in acetic acid and phenol. Pyrolysis experiments were performed to investigate the effects of reaction temperature and the types and amounts of activated carbon on the bio-oil composition. The maximum bio-oil yield obtained was approximately 47wt% at a reaction temperature of 515°C. The main compounds produced from the bio-oils were acetic acid, hydroxyacetone, phenol, and phenolic compounds such as cresol, xylenol, and pyrocatechol. When coal-derived activated carbon was applied, the acetic acid and phenol yields in the bio-oils reached 21 and 19wt%, respectively. Finally, bio-oils rich in acetic acid and phenol could be produced separately by using an in situ bio-oil separation system and activated carbon as an additive. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. High Pressure Biomass Gasification

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Agrawal, Pradeep K

    2016-07-29

    According to the Billion Ton Report, the U.S. has a large supply of biomass available that can supplement fossil fuels for producing chemicals and transportation fuels. Agricultural waste, forest residue, and energy crops offer potential benefits: renewable feedstock, zero to low CO 2 emissions depending on the specific source, and domestic supply availability. Biomass can be converted into chemicals and fuels using one of several approaches: (i) biological platform converts corn into ethanol by using depolymerization of cellulose to form sugars followed by fermentation, (ii) low-temperature pyrolysis to obtain bio-oils which must be treated to reduce oxygen content via HDOmore » hydrodeoxygenation), and (iii) high temperature pyrolysis to produce syngas (CO + H 2). This last approach consists of producing syngas using the thermal platform which can be used to produce a variety of chemicals and fuels. The goal of this project was to develop an improved understanding of the gasification of biomass at high pressure conditions and how various gasification parameters might affect the gasification behavior. Since most downstream applications of synags conversion (e.g., alcohol synthesis, Fischer-Tropsch synthesis etc) involve utilizing high pressure catalytic processes, there is an interest in carrying out the biomass gasification at high pressure which can potentially reduce the gasifier size and subsequent downstream cleaning processes. It is traditionally accepted that high pressure should increase the gasification rates (kinetic effect). There is also precedence from coal gasification literature from the 1970s that high pressure gasification would be a beneficial route to consider. Traditional approach of using thermogravimetric analyzer (TGA) or high-pressure themogravimetric analyzer (PTGA) worked well in understanding the gasification kinetics of coal gasification which was useful in designing high pressure coal gasification processes. However, similar approach

  5. Compositional and thermal evaluation of lignocellulosic and poultry litter chars via high and low temperature pyrolysis

    USDA-ARS?s Scientific Manuscript database

    Inorganic elements in biomass feedstocks can influence thermochemical reactions as well as the resultant chars elemental, compositional, and thermal characteristics. Chars were produced using slow pyrolysis at less than 400 and at higher than 500 degree Celsius from sugarcane bagasse, peanut hulls,...

  6. Aspen Plus® and economic modeling of equine waste utilization for localized hot water heating via fast pyrolysis.

    PubMed

    Hammer, Nicole L; Boateng, Akwasi A; Mullen, Charles A; Wheeler, M Clayton

    2013-10-15

    Aspen Plus(®) based simulation models have been developed to design a pyrolysis process for on-site production and utilization of pyrolysis oil from equine waste at the Equine Rehabilitation Center at Morrisville State College (MSC). The results indicate that utilization of all the available waste from the site's 41 horses requires a 6 oven dry metric ton per day (ODMTPD) pyrolysis system but it will require a 15 ODMTPD system for waste generated by an additional 150 horses at the expanded area including the College and its vicinity. For this a dual fluidized bed combustion reduction integrated pyrolysis system (CRIPS) developed at USDA's Agricultural Research Service (ARS) was identified as the technology of choice for pyrolysis oil production. The Aspen Plus(®) model was further used to consider the combustion of the produced pyrolysis oil (bio-oil) in the existing boilers that generate hot water for space heating at the Equine Center. The model results show the potential for both the equine facility and the College to displace diesel fuel (fossil) with renewable pyrolysis oil and alleviate a costly waste disposal problem. We predict that all the heat required to operate the pyrolyzer could be supplied by non-condensable gas and about 40% of the biochar co-produced with bio-oil. Techno-economic Analysis shows neither design is economical at current market conditions; however the 15 ODMTPD CRIPS design would break even when diesel prices reach $11.40/gal. This can be further improved to $7.50/gal if the design capacity is maintained at 6 ODMTPD but operated at 4950 h per annum. Published by Elsevier Ltd.

  7. Sulfur-Tolerant Molybdenum Carbide Catalysts Enabling Low-Temperature Stabilization of Fast Pyrolysis Bio-oil

    DOE PAGES

    Li, Zhenglong; Choi, Jae-Soon; Wang, Huamin; ...

    2017-08-18

    Low-temperature hydrogenation of carbonyl fractions can greatly improve the thermal stability of fast pyrolysis bio-oil which is crucial to achieve long-term operation of high-temperature upgrading reactors. The current state of the art, precious metals such as ruthenium, although highly effective in carbonyl hydrogenation, rapidly loses performance due to sulfur sensitivity. The present work showed that molybdenum carbides were active and sulfur-tolerant in low-temperature conversion carbonyl compounds. Furthermore, due to surface bifunctionality (presence of both metallic and acid sites), carbides catalyzed both C=O bond hydrogenation and C-C coupling reactions retaining most of carbon atoms in liquid products as more stable andmore » higher molecular weight oligomeric compounds while consuming less hydrogen than ruthenium. The carbides proved to be resistant to other deactivation mechanisms including hydrothermal aging, oxidation, coking and leaching. These properties enabled carbides to achieve and maintain good catalytic performance in both aqueous-phase furfural conversion and real bio-oil stabilization with sulfur present. This finding strongly suggests that molybdenum carbides can provide a catalyst solution necessary for the development of commercially viable bio-oil stabilization technology.« less

  8. Sulfur-Tolerant Molybdenum Carbide Catalysts Enabling Low-Temperature Stabilization of Fast Pyrolysis Bio-oil

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Zhenglong; Choi, Jae-Soon; Wang, Huamin

    Low-temperature hydrogenation of carbonyl fractions can greatly improve the thermal stability of fast pyrolysis bio-oil which is crucial to achieve long-term operation of high-temperature upgrading reactors. The current state of the art, precious metals such as ruthenium, although highly effective in carbonyl hydrogenation, rapidly loses performance due to sulfur sensitivity. The present work showed that molybdenum carbides were active and sulfur-tolerant in low-temperature conversion carbonyl compounds. Furthermore, due to surface bifunctionality (presence of both metallic and acid sites), carbides catalyzed both C=O bond hydrogenation and C-C coupling reactions retaining most of carbon atoms in liquid products as more stable andmore » higher molecular weight oligomeric compounds while consuming less hydrogen than ruthenium. The carbides proved to be resistant to other deactivation mechanisms including hydrothermal aging, oxidation, coking and leaching. These properties enabled carbides to achieve and maintain good catalytic performance in both aqueous-phase furfural conversion and real bio-oil stabilization with sulfur present. This finding strongly suggests that molybdenum carbides can provide a catalyst solution necessary for the development of commercially viable bio-oil stabilization technology.« less

  9. Hydrogen-Rich Syngas Production from Gasification and Pyrolysis of Solar Dried Sewage Sludge: Experimental and Modeling Investigations

    PubMed Central

    Ghrib, Amina; Friaa, Athar; Ouerghi, Aymen; Naoui, Slim; Belayouni, Habib

    2017-01-01

    Solar dried sewage sludge (SS) conversion by pyrolysis and gasification processes has been performed, separately, using two laboratory-scale reactors, a fixed-bed pyrolyzer and a downdraft gasifier, to produce mainly hydrogen-rich syngas. Prior to SS conversion, solar drying has been conducted in order to reduce moisture content (up to 10%). SS characterization reveals that these biosolids could be appropriate materials for gaseous products production. The released gases from SS pyrolysis and gasification present relatively high heating values (up to 9.96 MJ/kg for pyrolysis and 8.02  9.96 MJ/kg for gasification) due to their high contents of H2 (up to 11 and 7 wt%, resp.) and CH4 (up to 17 and 5 wt%, resp.). The yields of combustible gases (H2 and CH4) show further increase with pyrolysis. Stoichiometric models of both pyrolysis and gasification reactions were determined based on the global biomass formula, CαHβOγNδSε, in order to assist in the products yields optimization. PMID:28856162

  10. Biomass energy production. Citations from the International Aerospace Abstracts data base

    NASA Technical Reports Server (NTRS)

    Moore, P. W.

    1980-01-01

    These 210 citations from the international literature describe the production and/or utilization of most forms of biomass as a source of energy, fuel, food, and chemical intermediates or feedstocks. Biomass conversion by incineration, gasification, pyrolysis, hydrolysis, anaerobic digestion, or fermentation, as well as by catalytic, photosynthetic, chemosynthetic, and bio-electrochemical means are among the conversion processes considered. Discussions include biomass plantation and material productivity, transportation and equipment requirements, effects, comparisons of means and efficiencies of utilization and conversion, assessments of limitations, and evaluations of economic potential.

  11. The effects of feedstock pre-treatment and pyrolysis temperature on the production of biochar from the green seaweed Ulva.

    PubMed

    Roberts, David A; de Nys, Rocky

    2016-03-15

    Green seaweeds from the genus Ulva are a promising feedstock for the production of biochar for carbon (C) sequestration and soil amelioration. Ulva can be cultivated in waste water from land-based aquaculture and Ulva blooms ("green tides") strand millions of tons of biomass on coastal areas of Europe and China each year. The conversion of Ulva into biochar could recycle C and nutrients from eutrophic water into agricultural production. We produce biochar from Ulva ohnoi, cultivated in waste water from an aquaculture facility, and characterize its suitability for C sequestration and soil amelioration through bio-chemical analyses and plant growth experiments. Two biomass pre-treatments (fresh water rinsing to reduce salt, and pelletisation to increase density) were crossed with four pyrolysis temperatures (300-750 °C). Biomass rinsing decreased the ash and increased the C content of the resulting biochar. However, biochar produced from un-rinsed biomass had a higher proportion of fixed C and a higher yield. C sequestration decreased with increasing pyrolysis temperatures due to the combination of lower yield and lower total C content of biochar produced at high temperatures. Biochar produced from un-rinsed biomass at 300 °C had the greatest gravimetric C sequestration (110-120 g stable C kg(-1) seaweed). Biochar produced from un-pelletised Ulva enhanced plant growth three-fold in low fertility soils when the temperature of pyrolysis was less than 450 °C. The reduced effectiveness of the high-temperature biochars (>450 °C) was due to a lower N and higher salt content. Soil ameliorated with biochar produced from pelletised biomass had suppressed plant germination and growth. The most effective biochar for C sequestration and soil amelioration was produced from un-rinsed and un-pelletised Ulva at 300 °C. The green tide that occurs annually along the Shandong coastline in China generates sufficient biomass (200,000 tons dry weight) to ameliorate 12,500

  12. Biomass, Bioenergy and the Sustainability of Soils and Climate: What Role for Biochar?

    NASA Astrophysics Data System (ADS)

    Sohi, Saran

    2013-04-01

    Biochar is the solid, carbon rich product of heating biomass with the exclusion of air (pyrolysis). Whereas charcoal is derived from wood, biochar is a co-product of energy capture and can derive from waste or non-waste, virgin or non-virgin biomass resources. But also, biochar is not a fuel - rather it is intended for the beneficial amendment of soil in agriculture, forestry and horticulture. This results in long-term storage of plant-derived carbon that could improve yield or efficiency of crop production, and/or mitigate trace gas emissions from the land. Life cycle analysis (LCA) shows that pyrolysis bioenergy with biochar production should offer considerably more carbon abatement than combustion, or gasification of the same feedstock. This has potential to link climate change mitigation to bioenergy and sustainable use of soil. But, in economic terms, the opportunity cost of producing biochar (reflecting the calorific value of its stored carbon) is inflated by bioenergy subsidies. This, combined with a lack of clear regulatory position and no mature pyrolysis technologies at large scale, means that pyrolysis-biochar systems (PBS) remain largely conceptual at the current time. Precise understanding of its function and an ability to predict its impact on different soils and crops with certainty, biochar should acquire a monetary value. Combining such knowledge with a system that monetizes climate change mitigation potential (such as carbon markets), could see schemes for producing and using biochar escalate - including a context for its deployment in biomass crops, or through pyrolysis of residues from other bioenergy processes. This talk explores the opportunity, challenges and risks in pursuing biochar production in various bioenergy contexts including enhanced sustainability of soil use in biomass crop production, improving the carbon balance and value chain in biofuel production, and using organic waste streams more effectively (including the processing of

  13. Pyrolysis and hydrolysis of mixed polymer waste comprising polyethylene-terephthalate and polyethylene to sequentially recover [monomers

    DOEpatents

    Evans, R.J.; Chum, H.L.

    1998-10-13

    A process is described for using fast pyrolysis in a carrier gas to convert a plastic waste feed stream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feed stream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent. 83 figs.

  14. Kinetic analysis of manure pyrolysis and combustion processes.

    PubMed

    Fernandez-Lopez, M; Pedrosa-Castro, G J; Valverde, J L; Sanchez-Silva, L

    2016-12-01

    Due to the depletion of fossil fuel reserves and the environmental issues derived from their use, biomass seems to be an excellent source of renewable energy. In this work, the kinetics of the pyrolysis and combustion of three different biomass waste samples (two dairy manure samples before (Pre) and after (Dig R) anaerobic digestion and one swine manure sample (SW)) was studied by means of thermogravimetric analysis. In this work, three iso-conversional methods (Friedman, Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS)) were compared with the Coats-Redfern method. The E a values of devolatilization stages were in the range of 152-170kJ/mol, 148-178kJ/mol and 156-209kJ/mol for samples Pre, Dig R and SW, respectively. Concerning combustion process, char oxidation stages showed lower E a values than that obtained for the combustion devolatilization stage, being in the range of 140-175kJ/mol, 178-199kJ/mol and 122-144kJ/mol for samples Pre, Dig R and SW, respectively. These results were practically the same for samples Pre and Dig R, which means that the kinetics of the thermochemical processes were not affected by anaerobic digestion. Finally, the distributed activation energy model (DAEM) and the pseudo-multi component stage model (PMSM) were applied to predict the weight loss curves of pyrolysis and combustion. DAEM was the best model that fitted the experimental data. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Combustion performance of pyrolysis oil/ethanol blends in a residential-scale oil-fired boiler

    USDA-ARS?s Scientific Manuscript database

    A 40 kWth oil-fired commercial boiler was fueled with blends of biomass pyrolysis oil (py-oil) and ethanol to determine the feasibility of using these blends as a replacement for fuel oil in home heating applications. An optimal set of test parameters was determined for the combustion of these blend...

  16. Use of Biochar from the Pyrolysis of Woody and Herbaceous Organic Matter as Soil Amendments

    USDA-ARS?s Scientific Manuscript database

    “Biochar”, a typical by-product of biomass pyrolysis is being promoted for its potential large-scale and low-cost carbon sequestration in soil. Much of the knowledge regarding biochar derives from studies of Terra Preta soils in the Amazonian basin, where biochar-like materials appear to have subst...

  17. Evolution of soil organic matter changes using pyrolysis and metabolic indices: a comparison between organic and mineral fertilization.

    PubMed

    Marinari, S; Masciandaro, G; Ceccanti, B; Grego, S

    2007-09-01

    The aim of this study was to evaluate chemical and biochemical changes of organic matter in fertilized (ammonium nitrate) and amended (vermicompost and manure) soils using pyrolysis and metabolic indices. The metabolic potential [dehydrogenase (DH-ase)/water soluble organic carbon (WSOC)], the metabolic quotient (qCO2) and the microbial quotient (Cmic:Corg) were calculated as indices of soil organic matter evolution. Pyrolysis-gas chromatography (Py-GC) was used to study structural changes in the organic matter. Carbon forms and microbial biomass have been measured by dichromate oxidation and fumigation-extraction methods, respectively. Dehydrogenase activity has been tested using INT (p-Iodonitrotetrazolium violet) as substrate. The results showed that organic amendment increased soil microbial biomass and its activity which were strictly related to pyrolytic mineralization and humification indices (N/O, B/E3). Mineral fertilization caused a greater alteration of native soil organic matter than the organic amendments, in that a high release of WSOC and relatively large amounts of aliphatic pyrolytic products, were observed. Therefore, the pyrolysis and metabolic indices provided similar and complementary information on soil organic matter changes after mineral and organic fertilization.

  18. Corn stalks char from fast pyrolysis as precursor material for preparation of activated carbon in fluidized bed reactor.

    PubMed

    Wang, Zhiqi; Wu, Jingli; He, Tao; Wu, Jinhu

    2014-09-01

    Corn stalks char from fast pyrolysis was activated by physical and chemical activation process in a fluidized bed reactor. The structure and morphology of the carbons were characterized by N2 adsorption and SEM. Effects of activation time and activation agents on the structure of activation carbon were investigated. The physically activated carbons with CO2 have BET specific surface area up to 880 m(2)/g, and exhibit microporous structure. The chemically activated carbons with H3PO4 have BET specific surface area up to 600 m(2)/g, and exhibit mesoporous structure. The surface morphology shows that physically activated carbons exhibit fibrous like structure in nature with long ridges, resembling parallel lines. Whereas chemically activated carbons have cross-interconnected smooth open pores without the fibrous like structure. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Upgrading of bio-oil from the pyrolysis of biomass over the rice husk ash catalysts

    NASA Astrophysics Data System (ADS)

    Sutrisno, B.; Hidayat, A.

    2016-11-01

    The pyrolysis oils are complex mixtures of organic compounds that exhibit a wide spectrum of chemical functionality, and generally contain some water. Their direct use as fuels may present some difficulties due to their high viscosity, poor heating value, corrosiveness and instability. For possible future use as replacements for hydrocarbon chemical feedstocks and fuels, the liquids will require considerable upgrading to improve its characteristics. By esterification of the bio oil as the upgrading method, the properties of the bio-oil could be improved. In the paper, the upgrading of a bio-oil obtained by pyrolysis was studied over rice husk ash catalysts. The raw bio-oil was produced by pyrolysis of rice husk.From the experiment results, it can be concluded that the densities of upgraded bio-oil were reduced from 1.24 to 0.95 g.cm-3, and the higherheating value increased from 16.0 to 27.2 MJ/kg and the acidity of upgraded bio-oil was also alleviated from 2.3 to 4.4. The results of gas chromatography-mass spectrometry (GC-MS) and FT-IR analysis showed that the ester compounds in the upgraded bio-oil increased. It is possible to improve the properties of bio-oil by esterifying the raw bio-oil.

  20. A thermochemical-biochemical hybrid processing of lignocellulosic biomass for producing fuels and chemicals.

    PubMed

    Shen, Yanwen; Jarboe, Laura; Brown, Robert; Wen, Zhiyou

    2015-12-01

    Thermochemical-biological hybrid processing uses thermochemical decomposition of lignocellulosic biomass to produce a variety of intermediate compounds that can be converted into fuels and chemicals through microbial fermentation. It represents a unique opportunity for biomass conversion as it mitigates some of the deficiencies of conventional biochemical (pretreatment-hydrolysis-fermentation) and thermochemical (pyrolysis or gasification) processing. Thermochemical-biological hybrid processing includes two pathways: (i) pyrolysis/pyrolytic substrate fermentation, and (ii) gasification/syngas fermentation. This paper provides a comprehensive review of these two hybrid processing pathways, including the characteristics of fermentative substrates produced in the thermochemical stage and microbial utilization of these compounds in the fermentation stage. The current challenges of these two biomass conversion pathways include toxicity of the crude pyrolytic substrates, the inhibition of raw syngas contaminants, and the mass-transfer limitations in syngas fermentation. Possible approaches for mitigating substrate toxicities are discussed. The review also provides a summary of the current efforts to commercialize hybrid processing. Copyright © 2015 Elsevier Inc. All rights reserved.