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Sample records for biomass fast pyrolysis

  1. Catalytic fast pyrolysis of lignocellulosic biomass.

    PubMed

    Liu, Changjun; Wang, Huamin; Karim, Ayman M; Sun, Junming; Wang, Yong

    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 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 selectively 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 value, high corrosiveness, high viscosity, and instability; they also greatly 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.

  2. Catalytic fast pyrolysis of lignocellulosic biomass

    SciTech Connect

    Liu, Changjun; Wang, Huamin; Karim, Ayman M.; Sun, Junming; Wang, Yong

    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 selectively 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.

  3. Specialists' workshop on fast pyrolysis of biomass

    SciTech Connect

    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 as 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)

  4. Production and analysis of fast pyrolysis oils from proteinaceous biomass

    USDA-ARS?s Scientific Manuscript database

    Fast pyrolysis of lignocellulosic biomass is a facile method for producing high yields of liquid fuel intermediates. However, because most fast pyrolysis oils are highly oxygenated, acidic and unstable identification of feedstocks that produce higher quality pyrolysis liquids is desirable. Therefor...

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

    SciTech Connect

    Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.; Biddy, Mary J.; Knott, Brandon C.; Jarvis, Mark W.; Olstad, Jessica; Mante, Ofei D.; Dayton, David C.; Beckham, Gregg T.

    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, here 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

  6. 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

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

    SciTech Connect

    Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.; Biddy, Mary J.; Knott, Brandon C.; Jarvis, Mark W.; Olstad, Jessica; Mante, Ofei D.; Dayton, David C.; Beckham, Gregg T.

    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, here 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

  8. Acidity of biomass fast pyrolysis bio-oils

    SciTech Connect

    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 detection 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.

  9. 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...

  10. Fast pyrolysis of biomass thermally pretreated by torrefaction

    USDA-ARS?s Scientific Manuscript database

    Torrefied biomass samples were produced from hardwood and switchgrass pellets using the biochar experimenter’s kit (BEK) reactor and analyzed for their utility as pretreated feedstock for biofuels production via fast pyrolysis. The energy efficiency for the BEK torrefaction process with propane gas ...

  11. Transportation fuels from biomass via fast pyrolysis and hydroprocessing

    SciTech Connect

    Elliott, Douglas C.

    2013-09-21

    Biomass is a renewable source of carbon, which could provide a means to reduce the greenhouse gas impact from fossil fuels in the transportation sector. Biomass is the only renewable source of liquid fuels, which could displace petroleum-derived products. Fast pyrolysis is a method of direct thermochemical conversion (non-bioconversion) of biomass to a liquid product. Although the direct conversion product, called bio-oil, is liquid; it is not compatible with the fuel handling systems currently used for transportation. Upgrading the product via catalytic processing with hydrogen gas, hydroprocessing, is a means that has been demonstrated in the laboratory. By this processing the bio-oil can be deoxygenated to hydrocarbons, which can be useful replacements of the hydrocarbon distillates in petroleum. While the fast pyrolysis of biomass is presently commercial, the upgrading of the liquid product by hydroprocessing remains in development, although it is moving out of the laboratory into scaled-up process demonstration systems.

  12. 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.

  13. Biomass to hydrogen via fast pyrolysis and catalytic steam reforming

    SciTech Connect

    Chornet, E.; Wang, D.; Montane, D.

    1995-09-01

    Fast pyrolysis of biomass results in a pyrolytic oil which is a mixture of (a) carbohydrate-derived acids, aldehydes and polyols, (b) lignin-derived substituted phenolics, and (c) extractives-derived terpenoids and fatty acids. The conversion of this pyrolysis oil into H{sub 2} and CO{sub 2} is thermodynamically favored under appropriate steam reforming conditions. Our efforts have focused in understanding the catalysis of steam reforming which will lead to a successful process at reasonable steam/carbon ratios arid process severities. The experimental work, carried out at the laboratory and bench scale levels, has centered on the performance of Ni-based catalysts using model compounds as prototypes of the oxygenates present in the pyrolysis oil. Steam reforming of acetic acid, hydroxyacetaldehyde, furfural and syringol has been proven to proceed rapidly within a reasonable range of severities. Time-on-stream studies are now underway using a fixed bed barometric pressure reactor to ascertain the durability of the catalysts and thus substantiate the scientific and technical feasibility of the catalytic reforming option. Economic analyses are being carried out in parallel to determine the opportunity zones for the combined fast pyrolysis/steam reforming approach. A discussion on the current state of the project is presented.

  14. 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.

  15. 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...

  16. Gluconic acid from biomass fast pyrolysis oils: specialty chemicals from the thermochemical conversion of biomass.

    PubMed

    Santhanaraj, Daniel; Rover, Marjorie R; Resasco, Daniel E; Brown, Robert C; Crossley, Steven

    2014-11-01

    Fast pyrolysis of biomass to produce a bio-oil followed by catalytic upgrading is a widely studied approach for the potential production of fuels from biomass. Because of the complexity of the bio-oil, most upgrading strategies focus on removing oxygen from the entire mixture to produce fuels. Here we report a novel method for the production of the specialty chemical, gluconic acid, from the pyrolysis of biomass. Through a combination of sequential condensation of pyrolysis vapors and water extraction, a solution rich in levoglucosan is obtained that accounts for over 30% of the carbon in the bio-oil produced from red oak. A simple filtration step yields a stream of high-purity levoglucosan. This stream of levoglucosan is then hydrolyzed and partially oxidized to yield gluconic acid with high purity and selectivity. This combination of cost-effective pyrolysis coupled with simple separation and upgrading could enable a variety of new product markets for chemicals from biomass. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Design Case Summary: Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating, and Hydrocracking

    SciTech Connect

    Jones, S. B.; Valkenburg, C.; Walkton, C. W.; Elliott, D. C.; Holladay, J. E.; Stevens, D. J.; Kinchin, C.; Czernik, S.

    2010-02-01

    The Biomass Program develops design cases to understand the current state of conversion technologies and to determine where improvements need to take place in the future. This design case is the first to establish detailed cost targest for the production of diesel and gasoline blendstock from biomass via a fast pyrolysis process.

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

    SciTech Connect

    Carpenter, Daniel; Westover, Tyler; Howe, Daniel; Deutch, Steve; Starace, Anne; Emerson, Rachel; Hernandez, Sergio; Santosa, Daniel; Lukins, Craig; Kutnyakov, Igor

    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, for 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 (CP8OSB2). 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.

  19. 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 (CP8OSB2). 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

  20. 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

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

    SciTech Connect

    Neupane, Sneha; Adhikari, Sushil; Wang, Zhouhong; Ragauskas, Arthur; Pu, Yunqiao

    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 aryl 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.

  2. 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 aryl ethermore » 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

  3. Computational fluid dynamics modelling of biomass fast pyrolysis in fluidised bed reactors, focusing different kinetic schemes.

    PubMed

    Ranganathan, Panneerselvam; Gu, Sai

    2016-08-01

    The present work concerns with CFD modelling of biomass fast pyrolysis in a fluidised bed reactor. Initially, a study was conducted to understand the hydrodynamics of the fluidised bed reactor by investigating the particle density and size, and gas velocity effect. With the basic understanding of hydrodynamics, the study was further extended to investigate the different kinetic schemes for biomass fast pyrolysis process. The Eulerian-Eulerian approach was used to model the complex multiphase flows in the reactor. The yield of the products from the simulation was compared with the experimental data. A good comparison was obtained between the literature results and CFD simulation. It is also found that CFD prediction with the advanced kinetic scheme is better when compared to other schemes. With the confidence obtained from the CFD models, a parametric study was carried out to study the effect of biomass particle type and size and temperature on the yield of the products.

  4. 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

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

    PubMed

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

    2016-09-09

    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.

  6. Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case

    SciTech Connect

    Jones, Susanne B.; Valkenburt, Corinne; Walton, Christie W.; Elliott, Douglas C.; Holladay, Johnathan E.; Stevens, Don J.; Kinchin, Christopher; Czernik, Stefan

    2009-02-25

    The purpose of this study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels. This study has been conducted using similar methodology and underlying basis assumptions as the previous design cases for ethanol. The overall concept and specific processing steps were selected because significant data on this approach exists in the public literature. The analysis evaluates technology that has been demonstrated at the laboratory scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at an early stage of commercialization, while upgrading bio-oil to transportation fuels has only been demonstrated in the laboratory and at small engineering development scale. Advanced methods of pyrolysis, which are under development, are not evaluated in this study. These may be the subject of subsequent analysis by OBP. The plant is designed to use 2000 dry metric tons/day of hybrid poplar wood chips to produce 76 million gallons/year of gasoline and diesel. The processing steps include: 1.Feed drying and size reduction 2.Fast pyrolysis to a highly oxygenated liquid product 3.Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen 4.Hydrocracking of the heavy portion of the stable hydrocarbon oil 5.Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks 6. Hydrogen production to support the hydrotreater reactors. The "as received" feedstock to the pyrolysis plant will be "reactor ready". This development will likely further decrease the cost of producing the fuel. An important sensitivity is the possibility of co-locating the plant with an existing refinery. In this case, the plant consists only of the first three steps: feed

  7. Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case

    SciTech Connect

    Jones, Susanne B.; Valkenburt, Corinne; Walton, Christie W.; Elliott, Douglas C.; Holladay, Johnathan E.; Stevens, Don J.; Kinchin, Christopher; Czernik, Stefan

    2009-02-28

    The purpose of this study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels. This study has been conducted using the same methodology and underlying basis assumptions as the previous design cases for ethanol. The overall concept and specific processing steps were selected because significant data on this approach exists in the public literature. The analysis evaluates technology that has been demonstrated at the laboratory scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at an early stage of commercialization, while upgrading bio-oil to transportation fuels has only been demonstrated in the laboratory and at small engineering development scale. Advanced methods of pyrolysis, which are under development, are not evaluated in this study. These may be the subject of subsequent analysis by OBP. The plant is designed to use 2000 dry metric tons/day of hybrid poplar wood chips to produce 76 million gallons/year of gasoline and diesel. The processing steps include: 1.Feed drying and size reduction 2.Fast pyrolysis to a highly oxygenated liquid product 3.Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen 4.Hydrocracking of the heavy portion of the stable hydrocarbon oil 5.Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks 6. Hydrogen production to support the hydrotreater reactors. The “as received” feedstock to the pyrolysis plant will be “reactor ready.” This development will likely further decrease the cost of producing the fuel. An important sensitivity is the possibility of co-locating the plant with an existing refinery. In this case, the plant consists only of the first three steps

  8. Preliminary results in the fast pyrolysis of biomass to lower olefins

    SciTech Connect

    Diebold, J.P.

    1980-08-01

    The pyrolysis of pure cellulose and -80-mesh birch wood flour in a low-residence-time, entrained-flow tubular reactor yielded primarily gaseous products, with virtually no char formation. There were some condensible by-products which were almost entirely water soluble. The gases contained significant amounts of olefinic hydrocarbons such as ethylene. Although the yields of the olefinic hydrocarbons were not as high as previous yields from trash-derived organics, this study demonstrated that cellulose and biomass can be used to produce ethylene and other olefins in better yields than attained in conventional gasifiers. Very little of the char from birch wood pyrolysis had a charcoal appearance in scanning electron microscope photographs; instead, it had a sintered or agglomerated appearance. This implies that the char was formed by a different mechanism than charcoal and involves a liquification step. The attempts to feed lignin powder into the reactor, which resulted in the material sintering, bubbling, and charring at the reactor entrance, suggest that the agglomerated birch char particles may have been agglomerated birch lignin char particles; in fact, the heat of combustion of the char was close to that of lignin on an ash-free basis. A feed system for continuous pyrolysis research should be more reproducible and resistant to mass flow fluctuations than the China Lake pyrolysis steam as it was evolved to make pyrolysis gases for the previous gas purification system check out and demonstration. This study consisted of only a preliminary screening of the pyrolysis of pure cellulose, wood flour, and pure lignin. The pyrolysis of these materials needs to be further characterized. The ability to use relatively large feedstock particles in fast pyrolysis to produce olefins would significantly reduce the cost and process energy requirements of feedstock preparation.

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

    SciTech Connect

    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. 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.

  10. 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.

  11. Report - Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case

    SciTech Connect

    Jones, S. B.; Valkenburg, C.; Walton, C. W.; Elliott, D. C.; Holladay, J. E.; Stevens, D. J.; Kinchin, C.; Czernik, S.

    2009-02-01

    The purpose of this design case study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels.

  12. 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.

  13. 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.

  14. The cyclone: A multifunctional reactor for the fast pyrolysis of biomass

    SciTech Connect

    Lede, J.

    2000-04-01

    This paper reports the experimental results of the fast pyrolysis of wood sawdust performed in two different cyclone reactors. The mass balances are close to 100% and the char fractions always smaller than 3%. The flexibility of the cyclone reactor is such that, according to the operating conditions, it can be used either for the fast gasification or for the gas liquefaction of biomass. Side experiments reveal that a fraction of the gaseous products can be used as the carrier gas (recycling process) without noticeable changes of the gas composition and with vast gasification yields close to 100%. It is shown that the vapor-phase cracking reactions mainly occur inside a very thin and hot boundary layer close to the heated surface of the cyclone. The results of the modeling of these phenomena are used to derive kinetic constants that provide to be in very good agreement with those of the literature. The conclusion is that the cyclone appears as a very efficient multifunctional reactor making it possible to perform in less than a second heating and pyrolysis of the reactants as well as the quenching and separation of the products.

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

    SciTech Connect

    Oasmaa, Anja; van de Beld, Bert; Saari, Pia; Elliott, Douglas C.; Solantausta, Yrjo

    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, standards 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.

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

    DOE PAGES

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

    2016-09-01

    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 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.« less

  17. 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.

  18. 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

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

    SciTech Connect

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

    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 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.

  20. 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.

  1. 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.

  2. Biological mineral range effects on biomass conversion to aromatic hydrocarbons via catalytic fast pyrolysis over HZSM-5

    USDA-ARS?s Scientific Manuscript database

    A set of 20 biomass samples, comprising 10 genotypes of switchgrass, sorghum and miscanthus grown in two different soils with high and low poultry manure input conditions, and having a wide biological range of mineral content, were subjected to catalytic fast pyrolysis (CFP) over HZMS-5 using py-G...

  3. 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

  4. 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

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

    SciTech Connect

    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. 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.

  6. 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.

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

    SciTech Connect

    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.

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

    SciTech Connect

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

    2016-01-01

    Experimental methods for fast pyrolysis of lignocellulosic biomass to produce bio-oils and for the catalytic hydrotreating of bio-oils to produce fuel range hydrocarbons are presented. Hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil was also assessed. This is the first draft of our video publication for Jove. The manuscript is approved previously as PNNL-SA-108525. Please access the video via http://www.jove.com/video/54088?status=a56094k.

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

    SciTech Connect

    Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar; Shetty, Manish; Nimlos, Mark R.; Román-Leshkov, Yuriy

    2016-07-12

    The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO3/TiO2 and MoO3/ZrO2 at 500 °C and H2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO3 mass ratio exposed to the catalytic bed. For biomass to MoO3 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 and 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 MoO3 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 MoO3/ZrO2 and MoO3/TiO2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo5+ and Mo3+), and that catalyst deactivation is likely associated to coking.

  10. 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% MoO3/TiO2 and MoO3/ZrO2 at 500 °C and H2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO3 mass ratio exposed to the catalytic bed. For biomass to MoO3 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 and phenols are observed, with a concomitant decrease ofmore » 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 MoO3 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 MoO3/ZrO2 and MoO3/TiO2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo5+ and Mo3+), and that catalyst deactivation is likely associated to coking.« less

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

    SciTech Connect

    Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar; Shetty, Manish; Nimlos, Mark R.; Román-Leshkov, Yuriy

    2016-01-01

    The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO3/TiO2 and MoO3/ZrO2 at 500 degrees C and H2 pressures =0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO3 mass ratio exposed to the catalytic bed. For biomass to MoO3 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 and 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 MoO3 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. Post-reaction XPS analysis on supported MoO3/ZrO2 and MoO3/TiO2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo5+ and Mo3+), and that catalyst deactivation is likely associated to coking.

  12. 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

  13. Techno-Economic Analysis of Biomass Fast Pyrolysis to Transportation Fuels

    SciTech Connect

    Wright, M. M.; Satrio, J. A.; Brown, R. C.; Daugaard, D. E.; Hsu, D. D.

    2010-11-01

    This study develops techno-economic models for assessment of the conversion of biomass to valuable fuel products via fast pyrolysis and bio-oil upgrading. The upgrading process produces a mixture of naphtha-range (gasoline blend stock) and diesel-range (diesel blend stock) products. This study analyzes the economics of two scenarios: onsite hydrogen production by reforming bio-oil, and hydrogen purchase from an outside source. The study results for an nth plant indicate that petroleum fractions in the naphtha distillation range and in the diesel distillation range are produced from corn stover at a product value of $3.09/gal ($0.82/liter) with onsite hydrogen production or $2.11/gal ($0.56/liter) with hydrogen purchase. These values correspond to a $0.83/gal ($0.21/liter) cost to produce the bio-oil. Based on these nth plant numbers, product value for a pioneer hydrogen-producing plant is about $6.55/gal ($1.73/liter) and for a pioneer hydrogen-purchasing plant is about $3.41/gal ($0.92/liter). Sensitivity analysis identifies fuel yield as a key variable for the hydrogen-production scenario. Biomass cost is important for both scenarios. Changing feedstock cost from $50-$100 per short ton changes the price of fuel in the hydrogen production scenario from $2.57-$3.62/gal ($0.68-$0.96/liter).

  14. Catalytic Hydroprocessing of Biomass Fast Pyrolysis Bio-oil to Produce Hydrocarbon Products

    SciTech Connect

    Elliott, Douglas C.; Hart, Todd R.; Neuenschwander, Gary G.; Rotness, Leslie J.; Zacher, Alan H.

    2009-10-01

    Catalytic hydroprocessing has been applied to biomass fast pyrolysis liquid product (bio-oil) in a bench-scale continuous-flow fixed-bed reactor system. The intent of the research was to develop process technology to convert the bio-oil into a petroleum refinery feedstock to supplement fossil energy resources and to displace imported feedstock. The project was a cooperative research and development agreement among UOP LLC, the National Renewable Energy Laboratory and the Pacific Northwest National Laboratory (PNNL). This paper is focused on the process experimentation and product analysis undertaken at PNNL. The paper describes the experimental methods used and relates the results of the product analyses. A range of catalyst formulations were tested over a range of operating parameters including temperature, pressure, and flow-rate with bio-oil derived from several different biomass feedstocks. Effects of liquid hourly space velocity and catalyst bed temperature were assessed. Details of the process results were presented including mass and elemental balances. Detailed analysis of the products were provided including elemental composition, chemical functional type determined by mass spectrometry, and product descriptors such as density, viscosity and Total Acid Number (TAN). In summation, the paper provides an understanding of the efficacy of hydroprocessing as applied to bio-oil.

  15. Enhancement of biomass conversion in catalytic fast pyrolysis by microwave-assisted formic acid pretreatment.

    PubMed

    Feng, Yu; Li, Guangyu; Li, Xiangyu; Zhu, Ning; Xiao, Bo; Li, Jian; Wang, Yujue

    2016-08-01

    This study investigated microwave-assisted formic acid (MW-FA) pretreatment as a possible way to improve aromatic production from catalytic fast pyrolysis (CFP) of lignocellulosic biomass. Results showed that short duration of MW-FA pretreatment (5-10min) could effectively disrupt the recalcitrant structure of beech wood and selectively remove its hemicellulose and lignin components. This increased the accessibility of cellulose component of biomass to subsequent thermal conversion in CFP. Consequently, the MW-FA pretreated beech wood produced 14.0-28.3% higher yields (26.4-29.8C%) for valuable aromatic products in CFP than the untreated control (23.2C%). In addition, the yields of undesired solid residue (char/coke) decreased from 33.1C% for the untreated control to 28.6-29.8C% for the MW-FA pretreated samples. These results demonstrate that MW-FA pretreatment can provide an effective way to improve the product distribution from CFP of lignocellulose.

  16. 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

  17. Chapter 8: Biomass Pyrolysis Oils

    SciTech Connect

    McCormick, Robert L.; Baldwin, Robert M.; Arbogast, Stephen; Bellman, Don; Paynter, Dave; Wykowski, Jim

    2016-09-06

    Fast pyrolysis is heating on the order of 1000 degrees C/s in the absence of oxygen to 40-600 degrees C, which causes decomposition of the biomass. Liquid product yield from biomass can be as much as 80% of starting dry weight and contains up to 75% of the biomass energy content. Other products are gases, primarily carbon monoxide, carbon dioxide, and methane, as well as solid char and ash. Residence time in the reactor is only 0.5-2 s so that relatively small, low-capital-cost reactors can be used. The low capital cost combined with greenhouse gas emission reductions relative to petroleum fuels of 50-95% makes pyrolysis an attractive process. The pyrolysis liquids have been investigated as a refinery feedstock and as stand-alone fuels. Utilization of raw pyrolysis oil has proven challenging. The organic fraction is highly corrosive because of its high organic acid content. High water content lowers the net heating value and can increase corrosivity. It can be poorly soluble in petroleum or petroleum products and can readily absorb water. Distillation residues can be as high as 50%, viscosity can be high, oils can exhibit poor stability in storage, and they can contain suspended solids. The ignition quality of raw pyrolysis oils is poor, with cetane number estimates ranging from 0 to 35, but more likely to be in the lower end of that range. While the use of raw pyrolysis oils in certain specific applications with specialized combustion equipment may be possible, raw oils must be significantly upgraded for use in on-highway spark-ignition (SI) and compression-ignition (CI) engines. Upgrading approaches most often involve catalytic hydrodeoxygenation, one of a class of reactions known as hydrotreating or hydroprocessing. This chapter discusses the properties of raw and upgraded pyrolysis oils, as well as the potential for integrating biomass pyrolysis with a petroleum refinery to significantly reduce the hydroprocessing cost.

  18. 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.

  19. Entrained-Flow, Fast Ablative Pyrolysis of Biomass - Annual Report, 1 December 1984 - 31 December 1985

    SciTech Connect

    Diebold, J. P.; Scahill, J. W.; Evans, R. J.

    1986-07-01

    The ablative, fast pyrolysis system was relocated to SERI's new, permanent Field Test Laboratory. Pyrolysis system modifications were made to increase the energy available to the vortex reactor and to enhance the collection efficiency of primary pyrolysis vapors. Mathematical modeling of the vapor cracker has resulted in the ability to accurately predict experimental results with respect to the thermal cracking of the primary vapors, the generation of noncondensible gases, and the gas composition. The computer algorithm of this model can be readily used to perform experimental simulation and/or reactor scale-up due to its fundamental nature. Preliminary screening tests with pure ZSM-5 zeolite catalyst, supplied by Mobil Research and Development Corporation, have shown promise for the conversion of primary pyrolysis oil vapors to aromatic hydrocarbons; i.e., gasoline.

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

    DOE PAGES

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

    2017-01-12

    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 is seen. The ternary systemmore » (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

  1. 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.

  2. 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

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

    SciTech Connect

    Xiong, Qingang; Zhang, Jingchao; Wiggins, Gavin; Daw, C. Stuart; Xu, Fei

    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 the 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.

  4. Biomass-to-hydrogen via fast pyrolysis and catalytic steam reforming

    SciTech Connect

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

    1996-10-01

    Pyrolysis of lignocellulosic biomass and reforming the pyroligneous oils is being studied as a strategy for producing hydrogen. Novel technologies for the rapid pyrolysis of biomass have been developed in the past decade. They provide compact and efficient systems to transform biomass into vapors that are condensed to oils, with yields as high as 75-80 wt.% of the anhydrous biomass. This {open_quotes}bio-oil{close_quotes} is a mixture of aldehydes, alcohols, acids, oligomers from the constitutive carbohydrates and lignin, and some water derived from the dehydration reactions. Hydrogen can be produced by reforming the bio-oil or its fractions with steam. A process of this nature has the potential to be cost competitive with conventional means of producing hydrogen. The reforming facility can be designed to handle alternate feedstocks, such as natural gas and naphtha, if necessary. Thermodynamic modeling of the major constituents of the bio-oil has shown that reforming is possible within a wide range of temperatures and steam-to-carbon ratios. Existing catalytic data on the reforming of oxygenates have been studied to guide catalyst selection. Tests performed on a microreactor interfaced with a molecular beam mass spectrometer showed that, by proper selection of the process variables: temperature, steam-to-carbon ratio, gas hourly space velocity, and contact time, almost total conversion of carbon in the feed to CO and CO{sub 2} could be obtained. These tests also provided possible reaction mechanisms where thermal cracking competes with catalytic processes. Bench-scale, fixed bed reactor tests demonstrated high hydrogen yields from model compounds and carbohydrate-derived pyrolysis oil fractions. Reforming bio-oil or its fractions required proper dispersion of the liquid to avoid vapor-phase carbonization of the feed in the inlet to the reactor. A special spraying nozzle injector was designed and successfully tested with an aqueous fraction of bio-oil.

  5. 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.

  6. 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

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

    SciTech Connect

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

    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 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.

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

    SciTech Connect

    Engtrakul, Chaiwat; Hu, Michael Z.; Bischoff, Brian L.; Jang, Gyoung G.

    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 result 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.

  9. 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.

  10. Analysis of Oxygenated Compounds in Hydrotreated Biomass Fast Pyrolysis Oil Distillate Fractions

    SciTech Connect

    Christensen, Earl D.; Chupka, Gina; Luecke, Jon; Smurthwaite, Tricia D.; Alleman, Teresa L.; Iisa, Kristiina; Franz, James A.; Elliott, Douglas C.; McCormick, Robert L.

    2011-10-06

    Three hydrotreated bio-oils with different oxygen contents (8.2, 4.9, and 0.4 w/w) were distilled to produce Light, Naphtha, Jet, Diesel, and Gasoil boiling range fractions that were characterized for oxygen containing species by a variety of analytical methods. The bio-oils were originally generated from lignocellulosic biomass in an entrained-flow fast pyrolysis reactor. Analyses included elemental composition, carbon type distribution by {sup 13}C NMR, acid number, GC-MS, volatile organic acids by LC, and carbonyl compounds by DNPH derivatization and LC. Acid number titrations employed an improved titrant-electrode combination with faster response that allowed detection of multiple endpoints in many samples and for acid values attributable to carboxylic acids and to phenols to be distinguished. Results of these analyses showed that the highest oxygen content bio-oil fractions contained oxygen as carboxylic acids, carbonyls, aryl ethers, phenols, and alcohols. Carboxylic acids and carbonyl compounds detected in this sample were concentrated in the Light, Naphtha, and Jet fractions (<260 C boiling point). Carboxylic acid content of all of the high oxygen content fractions was likely too high for these materials to be considered as fuel blendstocks although potential for blending with crude oil or refinery intermediate streams may exist for the Diesel and Gasoil fractions. The 4.9 % oxygen sample contained almost exclusively phenolic compounds found to be present throughout the boiling range of this sample, but imparting measurable acidity primarily in the Light, Naphtha and Jet fractions. Additional study is required to understand what levels of the weakly acidic phenols could be tolerated in a refinery feedstock. The Diesel and Gasoil fractions from this upgraded oil had low acidity but still contained 3 to 4 wt% oxygen present as phenols that could not be specifically identified. These materials appear to have excellent potential as refinery feedstocks and some

  11. Fast co-pyrolysis of biomass and lignite in a micro fluidized bed reactor analyzer.

    PubMed

    Mao, Yebing; Dong, Lei; Dong, Yuping; Liu, Wenping; Chang, Jiafu; Yang, Shuai; Lv, Zhaochuan; Fan, Pengfei

    2015-04-01

    The co-pyrolysis characteristic of biomass and lignite were investigated in a Micro Fluidized Bed Reaction Analyzer under isothermal condition. The synergetic effect was evaluated by comparing the experimental gas yields and distributions with the calculated values, and iso-conversional method was used to calculate the kinetic parameters of formation of each gas component. The results showed that synergetic effect was manifested in co-pyrolysis. For the range of conversion investigated, the activation energies for H2, CH4, CO and CO2 were 72.90 kJ/mol, 43.90 kJ/mol, 18.51 kJ/mol and 13.44 kJ/mol, respectively; the reactions for CH4 and CO2 conformed to 2 order chemical reaction model, and for H2 and CO conformed to 1.5 order chemical reaction model; the pre-exponential factors for CH4, CO2, H2 and CO were 249.0 S(-1), 5.290 S(-1), 237.4 S(-1) and 2.693 S(-1), respectively. The discrepancy of the kinetic parameters implied that there were different pathways for forming the different gas.

  12. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Fast Pyrolysis and Hydrotreating Bio-Oil Pathway

    SciTech Connect

    Jones, Susanne B.; Meyer, Pimphan A.; Snowden-Swan, Lesley J.; Padmaperuma, Asanga B.; Tan, Eric; Dutta, Abhijit; Jacobson, Jacob; Cafferty, Kara

    2013-11-01

    This report describes a proposed thermochemical process for converting biomass into liquid transportation fuels via fast pyrolysis followed by hydroprocessing of the condensed pyrolysis oil. As such, the analysis does not reflect the current state of commercially-available technology but includes advancements that are likely, and targeted to be achieved by 2017. The purpose of this study is to quantify the economic impact of individual conversion targets to allow a focused effort towards achieving cost reductions.

  13. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Fast Pyrolysis and Hydrotreating Bio-oil Pathway

    SciTech Connect

    Jones, S.; Meyer, P.; Snowden-Swan, L.; Padmaperuma, A.; Tan, E.; Dutta, A.; Jacobson, J.; Cafferty, K.

    2013-11-01

    This report describes a proposed thermochemical process for converting biomass into liquid transportation fuels via fast pyrolysis followed by hydroprocessing of the condensed pyrolysis oil. As such, the analysis does not reflect the current state of commercially-available technology but includes advancements that are likely, and targeted to be achieved by 2017. The purpose of this study is to quantify the economic impact of individual conversion targets to allow a focused effort towards achieving cost reductions.

  14. 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.

  15. 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.

  16. 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

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

    SciTech Connect

    Xiong, Qingang; Ramirez, Emilio; Pannala, Sreekanth; Daw, C. Stuart; Xu, Fei

    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 the 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.

  18. Structure-property characteristics of pyrolytic lignins derived from fast pyrolysis of a lignin rich biomass extract

    USDA-ARS?s Scientific Manuscript database

    In this study, various fractions of pyrolytic lignin were isolated from the fast pyrolysis oil of Etek lignin, a residue of acidic processing of wood. Based on the solubility differences in selected solvents, the water insolubles of the pyrolysis oil were separated into various fractions (methanol-i...

  19. 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...

  20. Experimental investigation into fast pyrolysis of biomass using an entrained flow reactor

    NASA Astrophysics Data System (ADS)

    Bohn, M.; Benham, C.

    1981-02-01

    Pyrolysis experiments were performed with steam as a carrier gas and two different feedstocks - wheat straw and powdered material derived from municipal solid waste (ECO-II TM). Reactor wall temperature was varied from 7000 to 1400 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 are due to the presence of plastics in the feedstock.

  1. 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.

  2. Ablative fast pyrolysis of biomass in the entrained-flow cyclonic reactor at SERI

    NASA Astrophysics Data System (ADS)

    Diebold, J.; Scahill, J.

    1982-06-01

    Progress with the entrained flow cyclonic reactor at SERI is detailed. Feedstocks successfully used include: wood flour and fairly large sawdust. It is shown that relatively complete vaporization of the biomass is realized and that the yields of tar or gas can be varied over quite a range with trends following first order kinetic concepts.

  3. Ablative fast pyrolysis of biomass in the entrained-flow cyclonic reactor at SERI

    SciTech Connect

    Diebold, J.; Scahill, J.

    1982-06-01

    Progress with the entrained flow cyclonic reactor at SERI is detailed. Feedstocks successfully used include wood flour and fairly large sawdust. Preliminary results show that relatively complete vaporization of the biomass is realized and that the yields of tar or gas can be varied over quite a range with trends following first order kinetic concepts.

  4. Combustion, pyrolysis, gasification, and liquefaction of biomass

    SciTech Connect

    Reed, T.B.

    1980-09-01

    All the products now obtained from oil can be provided by thermal conversion of the solid fuels biomass and coal. As a feedstock, biomass has many advantages over coal and has the potential to supply up to 20% of US energy by the year 2000 and significant amounts of energy for other countries. However, it is imperative that in producing biomass for energy we practice careful land use. Combustion is the simplest method of producing heat from biomass, using either the traditional fixed-bed combustion on a grate or the fluidized-bed and suspended combustion techniques now being developed. Pyrolysis of biomass is a particularly attractive process if all three products - gas, wood tars, and charcoal - can be used. Gasification of biomass with air is perhaps the most flexible and best-developed process for conversion of biomass to fuel today, yielding a low energy gas that can be burned in existing gas/oil boilers or in engines. Oxygen gasification yields a gas with higher energy content that can be used in pipelines or to fire turbines. In addition, this gas can be used for producing methanol, ammonia, or gasoline by indirect liquefaction. Fast pyrolysis of biomass produces a gas rich in ethylene that can be used to make alcohols or gasoline. Finally, treatment of biomass with high pressure hydrogen can yield liquid fuels through direct liquefaction.

  5. Production of p-xylene from biomass by catalytic fast pyrolysis using ZSM-5 catalysts with reduced pore openings.

    PubMed

    Cheng, Yu-Ting; Wang, Zhuopeng; Gilbert, Christopher J; Fan, Wei; Huber, George W

    2012-10-29

    Pores for thought: Chemical liquid deposition of silica onto ZSM-5 catalysts led to smaller pore openings that resulted in >90% selectivity for p-xylene over the other xylenes in the catalytic fast pyrolysis of furan and 2-methylfuran (see scheme). The p-xylene selectivity increased from 51% with gallium spray-dried ZSM-5 to 72% with a pore-mouth-modified catalyst in the pyrolysis of pine wood. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Experimental investigation into fast pyrolysis of biomass using an entrained-flow reactor

    SciTech Connect

    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 are 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.

  7. 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.

  8. 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.

  9. 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.

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

    SciTech Connect

    2016-10-11

    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).

  11. 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"

    SciTech Connect

    Kevin L. Kenney; Kara G. Cafferty; Jacob J. Jacobson; Ian J. Bonner; Garold L. Gresham; J. Richard Hess; William A. Smith; David N. Thompson; Vicki S. Thompson; Jaya Shankar Tumuluru; Neal Yancey

    2014-01-01

    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 the 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.

  12. 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

    SciTech Connect

    Dutta, Abhijit; Sahir, Asad; Tan, Eric; Humbird, David; Snowden-Swan, Lesley J.; Meyer, Pimphan; Ross, Jeff; Sexton, Danielle; Yap, Raymond; Lukas, John Lukas

    2015-03-01

    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 assumptions 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.

  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. Microwave-assisted pyrolysis of biomass for liquid biofuels production.

    PubMed

    Yin, Chungen

    2012-09-01

    Production of 2nd-generation biofuels from biomass residues and waste feedstock is gaining great concerns worldwide. Pyrolysis, a thermochemical conversion process involving rapid heating of feedstock under oxygen-absent condition to moderate temperature and rapid quenching of intermediate products, is an attractive way for bio-oil production. Various efforts have been made to improve pyrolysis process towards higher yield and quality of liquid biofuels and better energy efficiency. Microwave-assisted pyrolysis is one of the promising attempts, mainly due to efficient heating of feedstock by "microwave dielectric heating" effects. This paper presents a state-of-the-art review of microwave-assisted pyrolysis of biomass. First, conventional fast pyrolysis and microwave dielectric heating is briefly introduced. Then microwave-assisted pyrolysis process is thoroughly discussed stepwise from biomass pretreatment to bio-oil collection. The existing efforts are summarized in a table, providing a handy overview of the activities (e.g., feedstock and pretreatment, reactor/pyrolysis conditions) and findings (e.g., pyrolysis products) of various investigations.

  15. 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

  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.

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

    SciTech Connect

    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). Among 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.

  18. Microwave induced pyrolysis of oil palm biomass.

    PubMed

    Salema, Arshad Adam; Ani, Farid Nasir

    2011-02-01

    The purpose of this paper was to carry out microwave induced pyrolysis of oil palm biomass (shell and fibers) with the help of char as microwave absorber (MA). Rapid heating and yield of microwave pyrolysis products such as bio-oil, char, and gas was found to depend on the ratio of biomass to microwave absorber. Temperature profiles revealed the heating characteristics of the biomass materials which can rapidly heat-up to high temperature within seconds in presence of MA. Some characterization of pyrolysis products was also presented. The advantage of this technique includes substantial reduction in consumption of energy, time and cost in order to produce bio-oil from biomass materials. Large biomass particle size can be used directly in microwave heating, thus saving grinding as well as moisture removal cost. A synergistic effect was found in using MA with oil palm biomass.

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

    SciTech Connect

    Dutta, Abhijit; Schaidle, Joshua A.; Humbird, David; Baddour, Frederick G.; Sahir, Asad

    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 report 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. Since this

  20. 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

  1. 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.

  2. 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

    SciTech Connect

    Dutta, Abhijit; Sahir, A. H.; Tan, Eric; Humbird, David; Snowden-Swan, Lesley J.; Meyer, Pimphan A.; Ross, Jeff; Sexton, Danielle; Yap, Raymond; Lukas, John

    2015-03-01

    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 assumptions 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.

  3. Fast Pyrolysis of Agricultural Wastes in a Fluidized Bed Reactor

    NASA Astrophysics Data System (ADS)

    Wang, X. H.; Chen, H. P.; Yang, H. P.; Dai, X. M.; Zhang, S. H.

    Solid biomass can be converted into liquid fuel through fast pyrolysis, which is convenient to be stored and transported with potential to be used as a fossil oil substitute. In China, agricultural wastes are the main biomass materials, whose pyrolysis process has not been researched adequately compared to forestry wastes. As the representative agricultural wastes in China, peanut shell and maize stalk were involved in this paper and pine wood sawdust was considered for comparing the different pyrolysis behaviors of agricultural wastes and forestry wastes. Fast pyrolysis experiments were carried out in a bench-scale fluidized-bed reactor. The bio-oil yieldsof peanut shell and maize stalk were obviously lower than that ofpine sawdust. Compared with pine sawdust, the char yields of peanut shell and maize stalk were higher but the heating value of uncondensable gaswas lower. This means that the bio-oil cost will be higher for agricultural wastes if taking the conventional pyrolysis technique. And the characteristic and component analysis resultsof bio-oil revealed that the quality of bio-oil from agricultural wastes, especially maize stalk, was worse than that from pine wood. Therefore, it is important to take some methods to improve the quality of bio-oilfrom agricultural wastes, which should promote the exploitation of Chinese biomass resources through fast pyrolysis in afluidized bed reactor.

  4. Modification of bio-char derived from fast pyrolysis of biomass and its application in removal of tetracycline from aqueous solution.

    PubMed

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

    2012-10-01

    In this work, bio-char, a mass productive by-product of biomass fast pyrolysis, was adopted as an adsorbent to remove tetracycline (TC) from aqueous solution. To enhance the adsorption capacity, a simple modification of bio-char with acid and alkali was carried out. Bio-char samples were characterized by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption isotherm. The results show that the alkali treated bio-char possesses larger surface area than those of raw and acid treated bio-chars, and accordingly exhibits a more excellent adsorption performance (58.8 mg/g) than the other two bio-chars and other adsorbents reported previously. The graphite-like structure of bio-char facilitates the formation of π-π interactions between ring structure in tetracycline molecule and graphite-like sheets. The surface area showed significant effects on TC adsorption as well as O-containing functional groups, whereas the initial pH of solution has small effects on TC adsorption under the experimental conditions.

  5. In-Situ Catalytic Fast Pyrolysis Technology Pathway

    SciTech Connect

    Biddy, M.; Dutta, A.; Jones, S.; Meyer, A.

    2013-03-01

    This technology pathway case investigates converting woody biomass using in-situ catalytic fast pyrolysis followed by upgrading to gasoline-, diesel-, and jet-range hydrocarbon blendstocks. Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.

  6. Ex-Situ Catalytic Fast Pyrolysis Technology Pathway

    SciTech Connect

    Biddy, M.; Dutta, A.; Jones, S.; Meyer, A.

    2013-03-01

    This technology pathway case investigates converting woody biomass using ex-situ catalytic fast pyrolysis followed by upgrading to gasoline-, diesel-, and jet-range hydrocarbon blendstocks. Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.

  7. Perspective on Catalytic Hydrodeoxygenation of Biomass Pyrolysis Oils: Essential Roles of Fe-Based Catalysts

    SciTech Connect

    Hong, Yongchun; Hensley, Alyssa; McEwen, Jean-Sabin; Wang, Yong

    2016-06-27

    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 exhibit 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.

  8. Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: 2012 State of Technology and Projections to 2017

    SciTech Connect

    Jones, Susanne B.; Snowden-Swan, Lesley J.

    2013-08-27

    This report summarizes the economic impact of the work performed at PNNL during FY12 to improve fast pyrolysis oil upgrading via hydrotreating. A comparison is made between the projected economic outcome and the actual results based on experimental data. Sustainability metrics are also included.

  9. Biofuel from fast pyrolysis and catalytic hydrodeoxygenation.

    SciTech Connect

    Elliott, Douglas C.

    2015-09-04

    This review addresses recent developments in biomass fast pyrolysis bio-oil upgrading by catalytic hydrotreating. The research in the field has expanded dramatically in the past few years with numerous new research groups entering the field while existing efforts from others expand. The issues revolve around the catalyst formulation and operating conditions. Much work in batch reactor tests with precious metal catalysts needs further validation to verify long-term operability in continuous flow systems. The effect of the low level of sulfur in bio-oil needs more study to be better understood. Utilization of the upgraded bio-oil for feedstock to finished fuels is still in an early stage of understanding.

  10. Stabilization of Fast Pyrolysis Oil: Post Processing Final Report

    SciTech Connect

    Elliott, Douglas C.; Lee, Suh-Jane; Hart, Todd R.

    2012-03-01

    UOP LLC, a Honeywell Company, assembled a comprehensive team for a two-year project to demonstrate innovative methods for the stabilization of pyrolysis oil in accordance with DOE Funding Opportunity Announcement (FOA) DE-PS36-08GO98018, Biomass Fast Pyrolysis Oil (Bio-oil) Stabilization. In collaboration with NREL, PNNL, the USDA Agricultural Research Service (ARS), Pall Fuels and Chemicals, and Ensyn Corporation, UOP developed solutions to the key technical challenges outlined in the FOA. The UOP team proposed a multi-track technical approach for pyrolysis oil stabilization. Conceptually, methods for pyrolysis oil stabilization can be employed during one or both of two stages: (1) during the pyrolysis process (In Process); or (2) after condensation of the resulting vapor (Post-Process). Stabilization methods fall into two distinct classes: those that modify the chemical composition of the pyrolysis oil, making it less reactive; and those that remove destabilizing components from the pyrolysis oil. During the project, the team investigated methods from both classes that were suitable for application in each stage of the pyrolysis process. The post processing stabilization effort performed at PNNL is described in this report. The effort reported here was performed under a CRADA between PNNL and UOP, which was effective on March 13, 2009, for 2 years and was subsequently modified March 8, 2011, to extend the term to December 31, 2011.

  11. 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...

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

    SciTech Connect

    Mukarakate, C.; Robichaud, D.; Donohoe, B.; Jarvis, M.; Mino, K.; Bahng, M. K.; Nimlos, M.

    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. 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.

  13. Hydrocarbon Liquid Production from Biomass via Hot-Vapor-Filtered Fast Pyrolysis and Catalytic Hydroprocessing of the Bio-oil

    SciTech Connect

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

    2014-08-14

    Hot-vapor filtered bio-oils were produced from two different biomass feedstocks, oak and switchgrass, and the oils were evaluated in hydroprocessing tests for production of liquid hydrocarbon products. Hot-vapor filtering reduced bio-oil yields and increased gas yields. The yields of fuel carbon as bio-oil were reduced by ten percentage points by hot-vapor filtering for both feedstocks. The unfiltered bio-oils were evaluated alongside the filtered bio-oils using a fixed bed catalytic hydrotreating test. These tests showed good processing results using a two-stage catalytic hydroprocessing strategy. Equal-sized catalyst beds, a sulfided Ru on carbon catalyst bed operated at 220°C and a sulfided CoMo on alumina catalyst bed operated at 400°C were used with the entire reactor at 100 atm operating pressure. The products from the four tests were similar. The light oil phase product was fully hydrotreated so that nitrogen and sulfur were below the level of detection, while the residual oxygen ranged from 0.3 to 2.0%. The density of the products varied from 0.80 g/ml up to 0.86 g/ml over the period of the test with a correlated change of the hydrogen to carbon atomic ratio from 1.79 down to 1.57, suggesting some loss of catalyst activity through the test. These tests provided the data needed to assess the suite of liquid fuel products from the process and the activity of the catalyst in relationship to the existing catalyst lifetime barrier for the technology.

  14. Biomass Feedstocks for Renewable Fuel Production: A review of the impacts of feedstock and pretreatment on the yield and product distribution of fast pyrolysis bio-oils and vapors

    SciTech Connect

    Daniel Carpenter; Stefan Czernik; Whitney Jablonski; Tyler L. Westover

    2014-02-01

    Renewable transportation fuels from biomass have the potential to substantially reduce greenhouse gas emissions and diversify global fuel supplies. Thermal conversion by fast pyrolysis converts up to 75% of the starting plant material (and its energy content) to a bio-oil intermediate suitable for upgrading to motor fuel. Woody biomass, by far the most widely-used and researched material, is generally preferred in thermochemical processes due to its low ash content and high quality bio-oil produced. However, the availability and cost of biomass resources, e.g. forest residues, agricultural residues, or dedicated energy crops, vary greatly by region and will be key determinates in the overall economic feasibility of a pyrolysis-to-fuel process. Formulation or blending of various feedstocks, combined with thermal and/or chemical pretreatment, could facilitate a consistent, high-volume, lower-cost biomass supply to an emerging biofuels industry. However, the impact of biomass type and pretreatment conditions on bio-oil yield and quality, and the potential process implications, are not well understood. This literature review summarizes the current state of knowledge regarding the effect of feedstock and pretreatments on the yield, product distribution, and upgradability of bio-oil.

  15. 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.

  16. Environmental control technology for biomass flash pyrolysis

    SciTech Connect

    Harkness, J.B.L.; Doctor, R.D.; Seward, W.H.

    1980-01-01

    The rapid commercialization of biomass gasification and pyrolysis technologies will raise questions concerning the environmental impacts of these systems and the associated costs for appropriate control technologies. This study concentrates on characterizing the effluent emissions and control technologies for a dual fluid-bed pyrolysis unit run by Arizona State University, Tempe, Arizona. The ASU system produces a raw product gas that is passed through a catalytic liquefaction system to produce a fuel comparable to No. 2 fuel oil. Argonne National Laboratory is conducting a program that will survey several biomass systems to standardize the sampling techniques, prioritize standard analyses and develop a data base so that environmental issues later may be addressed before they limit or impede the commercialization of biomass gasification and pyrolysis technologies. Emissions will be related to both the current and anticipated emissions standards to generate material balances and set design parameters for effluent treatment systems. This will permit an estimate to be made of the capital and operating costs associated with these technologies.

  17. 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

  18. 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.

  19. 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.

  20. 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.

  1. Fast Pyrolysis Conversion Tests of Forest Concepts' Crumbles™. Final Report

    SciTech Connect

    Santosa, Daniel M.; Zacher, Alan H.; Eakin, David E.

    2012-04-02

    The report describes the work done by PNNL on assessing Forest Concept's engineered feedstock using the bench-scale continuous fast pyrolysis system to produce liquid bio-oil, char and gas. Specifically, bio-oil from the following process were evaluated for its yield and quality to determine impact of varying feed size parameters. Furthermore, the report also describes the handling process of the biomass and the challenges of operating the system with above average particle size.

  2. Hydrotreating of fast pyrolysis oils from protein-rich pennycress seed presscake

    USDA-ARS?s Scientific Manuscript database

    The fast pyrolysis oils produced from proteinaceous biomass, such as pennycress presscake differ significantly from those produced from biomass with mostly lignocellulosic composition. Those from proteinaceous biomass tend to be deoxygenated, contain more nitrogen, be less acidic and be more stable...

  3. Fast Pyrolysis of Wood for Biofuels: Spatiotemporally Resolved Diffuse Reflectance In situ Spectroscopy of Particles.

    PubMed

    Paulsen, Alex D; Hough, Blake R; Williams, C Luke; Teixeira, Andrew R; Schwartz, Daniel T; Pfaendtner, Jim; Dauenhauer, Paul J

    2014-02-20

    Fast pyrolysis of woody biomass is a promising process capable of producing renewable transportation fuels to replace gasoline, diesel, and chemicals currently derived from nonrenewable sources. However, biomass pyrolysis is not yet economically viable and requires significant optimization before it can contribute to the existing oil-based transportation system. One method of optimization uses detailed kinetic models for predicting the products of biomass fast pyrolysis, which serve as the basis for the design of pyrolysis reactors capable of producing the highest value products. The goal of this work is to improve upon current pyrolysis models, usually derived from experiments with low heating rates and temperatures, by developing models that account for both transport and pyrolysis decomposition kinetics at high heating rates and high temperatures (>400 °C). A new experimental technique is proposed herein: spatiotemporally resolved diffuse reflectance in situ spectroscopy of particles (STR-DRiSP), which is capable of measuring biomass composition during fast pyrolysis with high spatial (10 μm) and temporal (1 ms) resolution. Compositional data were compared with a comprehensive 2D single-particle model, which incorporated a multistep, semiglobal reaction mechanism, prescribed particle shrinkage, and thermophysical properties that varied with temperature, composition, and orientation. The STR-DRiSP technique can be used to determine the transport-limited kinetic parameters of biomass decomposition for a wide variety of biomass feedstocks.

  4. Regulation for Optimal Liquid Products during Biomass Pyrolysis: A Review

    NASA Astrophysics Data System (ADS)

    Wang, F.; Hu, L. J.; Zheng, Y. W.; Huang, Y. B.; Yang, X. Q.; Liu, C.; Kang, J.; Zheng, Z. F.

    2016-08-01

    The liquid product obtained from biomass pyrolysis is very valuable that it could be used for extraction of chemicals as well as for liquid fuel. The desire goal is to obtain the most bio-oil with desired higher heating value (HHV), high physicochemical stability. The yields and chemical composition of products from biomass pyrolysis are closely related to the feedstock, pyrolysis parameters and catalysts. Current researches mainly concentrated on the co-pyrolysis of different biomass and introduce of novel catalysts as well as the combined effect of catalysts and pyrolysis parameters. This review starts with the chemical composition of biomass and the fundamental parameters and focuses on the influence of catalysts on bio-oil. What is more, the pyrolysis facilities at commercial scales were also involved. The classic researches and the current literature about the yield and composition of products (mainly liquid products) are summarized.

  5. 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.

  6. Dissolved phosphorus speciation of flash carbonization, slow pyrolysis, and fast pyrolysis biochars

    USDA-ARS?s Scientific Manuscript database

    Pyrolysis of waste biomass is a promising technology to produce sterile and renewable organic phosphorus fertilizers. Systematic studies are necessary to understand how different pyrolysis platforms influence the chemical speciation of dissolved (bioavailable) phosphorus. This study employed solut...

  7. 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...

  8. Evaluation of Catalysts from Different Origin for Vapor Phase Upgrading in Biomass Pyrolysis

    SciTech Connect

    Zhang, X.; Mukarakate, C.; Zheng, Z.; Nimlos, M.

    2012-01-01

    Liquid fuels and chemicals from biomass resources arouse much interests in research and development. Fast pyrolysis of biomass has the potential to effectively change solid biomass materials into liquid products. However, bio-oil from traditional pyrolysis processes is difficult to apply in industry, because of its complicated composition, high oxygen content, low stability, etc. Upgrading or refining of the bio-oil should be performed for industrial application of biomass pyrolysis. Often, the process would be done in a separate reactor downstream of the pyrolysis process. In this paper, a laboratory scale micro test facility was constructed, wherein the pyrolysis of pine and catalytic upgrading of the resulting vapors were closely coupled in one reactor. The composition of vapor effluent was monitored with a molecular beam mass spectrometer (MBMS) for the online evaluation of the catalyst performance. Catalysts from different origin were tested and compared for the effectiveness of pyrolysis vapor upgrading, namely commercial zeolites, Ni based steam reforming catalyst, CaO, MgO, and several laboratory-made catalysts. The reaction temperature for catalytic upgrading varied between 400 and 600 centigrade, and the gaseous residence time ranged from 0.1 second to above 2 second, to simulate the conditions in industrial application. It is revealed that some catalysts are active in transform most of primary biomass pyrolysis vapors into hydrocarbons, resulting in nonoxygenated products, which is beneficial for downstream utilization. Others are not as effective, results in minor improvement compared with blank test results.

  9. 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.

  10. 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...

  11. 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

  12. 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

  13. 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.

  14. INTEGRATED PYROLYSIS COMBINED CYCLE BIOMASS POWER SYSTEM CONCEPT DEFINITION

    SciTech Connect

    Eric Sandvig; Gary Walling; Robert C. Brown; Ryan Pletka; Desmond Radlein; Warren Johnson

    2003-03-01

    Advanced power systems based on integrated gasification/combined cycles (IGCC) are often presented as a solution to the present shortcomings of biomass as fuel. Although IGCC has been technically demonstrated at full scale, it has not been adopted for commercial power generation. Part of the reason for this situation is the continuing low price for coal. However, another significant barrier to IGCC is the high level of integration of this technology: the gas output from the gasifier must be perfectly matched to the energy demand of the gas turbine cycle. We are developing an alternative to IGCC for biomass power: the integrated (fast) pyrolysis/ combined cycle (IPCC). In this system solid biomass is converted into liquid rather than gaseous fuel. This liquid fuel, called bio-oil, is a mixture of oxygenated organic compounds and water that serves as fuel for a gas turbine topping cycle. Waste heat from the gas turbine provides thermal energy to the steam turbine bottoming cycle. Advantages of the biomass-fueled IPCC system include: combined cycle efficiency exceeding 37 percent efficiency for a system as small as 7.6 MW{sub e}; absence of high pressure thermal reactors; decoupling of fuel processing and power generation; and opportunities for recovering value-added products from the bio-oil. This report provides a technical overview of the system including pyrolyzer design, fuel clean-up strategies, pyrolysate condenser design, opportunities for recovering pyrolysis byproducts, gas turbine cycle design, and Rankine steam cycle. The report also reviews the potential biomass fuel supply in Iowa, provide and economic analysis, and present a summery of benefits from the proposed system.

  15. Calcium-catalyzed pyrolysis of lignocellulosic biomass components.

    PubMed

    Case, Paige A; Truong, Chi; Wheeler, M Clayton; DeSisto, William J

    2015-09-01

    The present study examines the effect of calcium pretreatment on pyrolysis of individual lignocellulosic compounds. Previous work has demonstrated that the incorporation of calcium compounds with the feedstock prior to pyrolysis has a significant effect on the oxygen content and stability of the resulting oil. The aim of this work was to further explore the chemistry of calcium-catalyzed pyrolysis. Bench-scale pyrolysis of biomass constituents, including lignin, cellulose and xylan is performed and compared to the oils produced from pyrolysis of the same components after calcium pretreatment. The resulting oils were analyzed by quantitative GC-MS and SEC. These analyses, together with data collected from previous work provide evidence which was used to develop proposed reaction pathways for pyrolysis of calcium-pretreatment biomass. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. 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...

  17. 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.

  18. 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.

  19. [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.

  20. Impact of thermal pretreatment on the fast pyrolysis conversion of Southern Pine

    SciTech Connect

    Tyler L. Westover; Manunya Phanphanich; Micael L. Clark; Sharna R. Rowe; Steven E. Egan; Christopher T Wright; Richard D. Boardman; Alan H. Zacher

    2013-01-01

    Background: Thermal pretreatment of biomass ranges from simple (nondestructive) drying to more severe treatments that cause devolatization, depolymerization and carbonization. These pretreatments have demonstrated promise for transforming raw biomass into feedstock material that has improved milling, handling, storage and conversion properties. In this work, southern pine material was pretreated at 120, 180, 230 and 270 degrees C, and then subjected to pyrolysis tests in a continuous-feed bubbling-fluid bed pyrolysis system. Results: High pretreatment temperatures were associated with lower specific grinding energies, higher grinding rates and lower hydrogen and oxygen contents. Higher pretreatment temperatures were also correlated with increased char production, decreased total acid number and slight decrease in the oxygen content of the pyrolysis liquid fraction. Conclusion: Thermal pretreatment has both beneficial and detrimental impacts on fast pyrolysis conversion of pine material to bio-oil, and the effect of thermal pretreatment on upgrading of pyrolysis bio-oil requires further attention.

  1. Combustion Properties of Biomass Flash Pyrolysis Oils: Final Project Report

    SciTech Connect

    C. R. Shaddix; D. R. Hardesty

    1999-04-01

    Thermochemical pyrolysis of solid biomass feedstocks, with subsequent condensation of the pyrolysis vapors, has been investigated in the U.S. and internationally as a means of producing a liquid fuel for power production from biomass. This process produces a fuel with significantly different physical and chemical properties from traditional petroleum-based fuel oils. In addition to storage and handling difficulties with pyrolysis oils, concern exists over the ability to use this fuel effectively in different combustors. The report endeavors to place the results and conclusions from Sandia's research into the context of international efforts to utilize pyrolysis oils. As a special supplement to this report, Dr. Steven Gust, of Finland's Neste Oy, has provided a brief assessment of pyrolysis oil combustion research efforts and commercialization prospects in Europe.

  2. 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

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

    SciTech Connect

    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 simulate 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.

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

    SciTech Connect

    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 simulate 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.

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

    SciTech Connect

    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 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.

  6. 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.

  7. Mass balance and exergy analysis of a fast pyrolysis system

    USDA-ARS?s Scientific Manuscript database

    Mass balance closure and exergetic efficiency is evaluated for a bench scale fast pyrolysis system. The USDA Agricultural Research Service (ARS) has developed this system for processing energy crops and agricultural residues for bio-oil (pyrolysis oil or pyrolysis liquids) production. Mass balance c...

  8. 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

  9. In-Situ Catalytic Fast Pyrolysis Technology Pathway

    SciTech Connect

    Biddy, Mary J.; Dutta, Abhijit; Jones, Susanne B.; Meyer, Pimphan A.

    2013-03-31

    In support of the Bioenergy Technologies Office, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) are undertaking studies of biomass conversion technologies to hydrocarbon fuels to identify barriers and target research toward reducing conversion costs. Process designs and preliminary economic estimates for each of these pathway cases were developed using rigorous modeling tools (Aspen Plus and Chemcad). These analyses incorporated the best information available at the time of development, including data from recent pilot and bench-scale demonstrations, collaborative industrial and academic partners, and published literature and patents. This pathway case investigates converting woody biomass using in-situ catalytic fast pyrolysis followed by upgrading to gasoline, diesel, and jet range blendstocks. Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.

  10. Ex-Situ Catalytic Fast Pyrolysis Technology Pathway

    SciTech Connect

    Biddy, Mary J.; Dutta, Abhijit; Jones, Susanne B.; Meyer, Pimphan A.

    2013-03-31

    In support of the Bioenergy Technologies Office, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) are undertaking studies of biomass conversion technologies to hydrocarbon fuels to identify barriers and target research toward reducing conversion costs. Process designs and preliminary economic estimates for each of these pathway cases were developed using rigorous modeling tools (Aspen Plus and Chemcad). These analyses incorporated the best information available at the time of development, including data from recent pilot and bench-scale demonstrations, collaborative industrial and academic partners, and published literature and patents. This pathway case investigates converting woody biomass using ex-situ catalytic fast pyrolysis followed by upgrading to gasoline , diesel and jet range blendstocks . Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.

  11. Thermochemical behavior of tris(2-butoxyethyl) phosphate (TBEP) during co-pyrolysis with biomass.

    PubMed

    Qian, Ting-Ting; Li, De-Chang; Jiang, Hong

    2014-09-16

    Co-pyrolysis of plastic waste and wood biomass to recover valuable chemicals is a cost-effective waste-recycling technology. However, widely used organophosphate ester additives in plastic, such as tris(2-butoxyethyl) phosphate (TBEP), can form diverse phosphorus (P)-containing species. These P-containing compounds can pose new environmental challenges when the biochar is reused. In this study, a mixture of TBEP and lignin was used to simulate the feedstock of plastic waste and wood biomass, and the thermochemical behavior of TBEP in slow pyrolysis (20 K min(-1)) and fast pyrolysis at 400-600 °C was investigated. The results show that low temperature in fast pyrolysis favors the enrichment of P in char. Up to 76.6% of initial P in the feedstock is retained in the char resulting from 400 °C, while only 51% is retained in the char from 600 °C. Slow pyrolysis favors the formation of stable P species regardless of the temperature; only 7% of the P retained in the char is extractable from char from slow pyrolysis, while 20-40% of P can be extracted from char resulting from fast pyrolysis. The addition of CaCl2 and MgCl2 can significantly increase the fraction of P retained in the char by the formation of Ca, Mg-P compounds. Online TG-FTIR-MS analysis suggests that TBEP undergoes decomposition through different temperature-dependent pathways. The P-containing radicals react with the aromatic rings produced by the pyrolysis of lignin to form Ar-P species, which is an important factor influencing the distribution and stabilization of P in char.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

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

    SciTech Connect

    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 to 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.

  17. Additives initiate selective production of chemicals from biomass pyrolysis.

    PubMed

    Leng, Shuai; Wang, Xinde; Wang, Lei; Qiu, Huizhe; Zhuang, Guilin; Zhong, Xing; Wang, Jianguo; Ma, Fengyun; Liu, Jingmei; Wang, Qiang

    2014-03-01

    To improve chemicals selectivity under low temperature, a new method that involves the injection of additives into biomass pyrolysis is introduced. This method allows biomass pyrolysis to achieve high selectivity to chemicals under low temperature (300°C), while nothing was obtained in typical pyrolysis under 300°C. However, by using the new method, the first liquid drop emerged at the interval between 140°C and 240°C. Adding methanol to mushroom scrap pyrolysis obtained high selectivity to acetic acid (98.33%), while adding ethyl acetate gained selectivity to methanol (65.77%) in bagasse pyrolysis and to acetone (72.51%) in corncob pyrolysis. Apart from basic chemicals, one high value-added chemical (2,3-dihydrobenzofuran) was also detected, which obtained the highest selectivity (10.33%) in corncob pyrolysis through the addition of ethyl acetate. Comparison of HZSM-5 and CaCO3 catalysis showed that benzene emerged in the liquid because of the larger degree of cracking and hydrodeoxygenation over HZSM-5.

  18. Liquid-phase processing of fast pyrolysis bio-oil using platinum/HZSM-5 catalyst

    NASA Astrophysics Data System (ADS)

    Santos, Bjorn Sanchez

    Recent developments in converting biomass to bio-chemicals and liquid fuels provide a promising sight to an emerging biofuels industry. Biomass can be converted to energy via thermochemical and biochemical pathways. Thermal degradation processes include liquefaction, gasification, and pyrolysis. Among these biomass technologies, pyrolysis (i.e. a thermochemical conversion process of any organic material in the absence of oxygen) has gained more attention because of its simplicity in design, construction and operation. This research study focuses on comparative assessment of two types of pyrolysis processes and catalytic upgrading of bio-oil for production of transportation fuel intermediates. Slow and fast pyrolysis processes were compared for their respective product yields and properties. Slow pyrolysis bio-oil displayed fossil fuel-like properties, although low yields limit the process making it uneconomically feasible. Fast pyrolysis, on the other hand, show high yields but produces relatively less quality bio-oil. Catalytic transformation of the high-boiling fraction (HBF) of the crude bio-oil from fast pyrolysis was therefore evaluated by performing liquid-phase reactions at moderate temperatures using Pt/HZSM-5 catalyst. High yields of upgraded bio-oils along with improved heating values and reduced oxygen contents were obtained at a reaction temperature of 200°C and ethanol/HBF ratio of 3:1. Better quality, however, was observed at 240 °C even though reaction temperature has no significant effect on coke deposition. The addition of ethanol in the feed has greatly attenuated coke deposition in the catalyst. Major reactions observed are esterification, catalytic cracking, and reforming. Overall mass and energy balances in the conversion of energy sorghum biomass to produce a liquid fuel intermediate obtained sixteen percent (16 wt.%) of the biomass ending up as liquid fuel intermediate, while containing 26% of its initial energy.

  19. 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.

  20. Total Acid Value Titration of Hydrotreated Biomass Fast Pyrolysis Oil: Determination of Carboxylic Acids and Phenolics with Multiple End-Point Detection

    SciTech Connect

    Christensen, E.; Alleman, T. L.; McCormick, R. L.

    2013-01-01

    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 due 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.

  1. Fast Pyrolysis Process Development Unit for Validating Bench Scale Data

    SciTech Connect

    Brown, Robert C.; Jones, Samuel T.

    2010-03-31

    The purpose of this project was to prepare and operate a fast pyrolysis process development unit (PDU) that can validate experimental data generated at the bench scale. In order to do this, a biomass preparation system, a modular fast pyrolysis fluidized bed reactor, modular gas clean-up systems, and modular bio-oil recovery systems were designed and constructed. Instrumentation for centralized data collection and process control were integrated. The bio-oil analysis laboratory was upgraded with the addition of analytical equipment needed to measure C, H, O, N, S, P, K, and Cl. To provide a consistent material for processing through the fluidized bed fast pyrolysis reactor, the existing biomass preparation capabilities of the ISU facility needed to be upgraded. A stationary grinder was installed to reduce biomass from bale form to 5-10 cm lengths. A 25 kg/hr rotary kiln drier was installed. It has the ability to lower moisture content to the desired level of less than 20% wt. An existing forage chopper was upgraded with new screens. It is used to reduce biomass to the desired particle size of 2-25 mm fiber length. To complete the material handling between these pieces of equipment, a bucket elevator and two belt conveyors must be installed. The bucket elevator has been installed. The conveyors are being procured using other funding sources. Fast pyrolysis bio-oil, char and non-condensable gases were produced from an 8 kg/hr fluidized bed reactor. The bio-oil was collected in a fractionating bio-oil collection system that produced multiple fractions of bio-oil. This bio-oil was fractionated through two separate, but equally important, mechanisms within the collection system. The aerosols and vapors were selectively collected by utilizing laminar flow conditions to prevent aerosol collection and electrostatic precipitators to collect the aerosols. The vapors were successfully collected through a selective condensation process. The combination of these two mechanisms

  2. Federal Air Pollutant Emission Regulations and Preliminary Estimates of Potential-to-Emit from Biorefineries, Pathway #2: Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Fast Pyrolysis and Hydrotreating Bio-oil Pathway

    SciTech Connect

    Bhatt, Arpit; Zhang, Yimin; Heath, Garvin; Thomas, Mae; Renzaglia, Jason

    2017-01-01

    Biorefineries are subject to environmental laws, including complex air quality regulations that aim to protect and improve the quality of the air. These regulations govern the amount of certain types of air pollutants that can be emitted from different types of emission sources. To determine which federal air emission regulations potentially apply to the fast pyrolysis biorefinery, we first identified the types of regulated air pollutants emitted to the ambient environment by the biorefinery or from specific equipment. Once the regulated air pollutants are identified, we review the applicability criteria of each federal air regulation to determine whether the fast pyrolysis biorefinery or specific equipment is subject to it. We then estimate the potential-to-emit of pollutants likely to be emitted from the fast pyrolysis biorefinery to understand the air permitting requirements.

  3. 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...

  4. State-of-the-Art of Fast Pyrolysis in IEA Bioenergy Member Countries

    SciTech Connect

    Meier, Dietrich; van de Beld, Bert; Bridgwater, Anthony V.; Elliott, Douglas C.; Oasmaa, Anja; Preto, Fernando

    2013-04-01

    Fast pyrolysis of biomass is becoming increasingly important in some member countries of the International Energy Agency(IEA). Six countries have joined the IEA Task 34 of the Bioenergy Activity: Canada, Finland, Germany, Netherlands, UK, and USA. The National Task Leaders give an overview of the current activities in their countries both on research, pilot and demonstration level.

  5. Pyrolysis characteristics and kinetics of aquatic biomass using thermogravimetric analyzer.

    PubMed

    Wu, Kejing; Liu, Ji; Wu, Yulong; Chen, Yu; Li, Qinghai; Xiao, Xin; Yang, Mingde

    2014-07-01

    The differences in pyrolysis process of three species of aquatic biomass (microalgae, macroalgae and duckweed) were investigated by thermogravimetric analysis (TGA). Three stages were observed during the pyrolysis process and the main decomposition stage could be divided further into three zones. The pyrolysis characteristics of various biomasses were different at each zone, which could be attributed to the differences in their components. A stepwise procedure based on iso-conversional and master-plots methods was used for the kinetic and mechanism analysis of the main decomposition stage. The calculation results based on the kinetic model was in good agreement with the experimental data of weight loss, and each biomass had an increasing activation energy of 118.35-156.13 kJ/mol, 171.85-186.46 kJ/mol and 258.51-268.71 kJ/mol in zone 1, 2 and 3, respectively. This study compares the pyrolysis behavior of various aquatic biomasses and provides basis for further applications of the biomass thermochemical conversion. Copyright © 2014. Published by Elsevier Ltd.

  6. Experimental investigation of pyrolysis process of woody biomass mixture

    NASA Astrophysics Data System (ADS)

    Kosanić, Tijana R.; Ćeranić, Mirjana B.; Đurić, Slavko N.; Grković, Vojin R.; Milotić, Milan M.; Brankov, Saša D.

    2014-06-01

    This paper describes an experimental investigation of pyrolysis of woody biomass mixture. The mixture consists of oak, beech, fir, cherry, walnut and linden wood chips with equal mass fractions. During the experiment, the sample mass inside the reactor was 10 g with a particle diameter of 5-10 mm. The sample in the reactor was heated in the temperature range of 24-650°C. Average sample heating rates in the reactor were 21, 30 and 54 °C/min. The sample mass before, during and after pyrolysis was determined using a digital scale. Experimental results of the sample mass change indicate that the highest yield of pyrolytic gas was achieved at the temperature slightly above 650°C and ranged from 77 to 85%, while char yield ranged from 15 to 23%. Heating rate has significant influence on the pyrolytic gas and char yields. It was determined that higher pyrolysis temperatures and heating rates induce higher yields of pyrolytic gas, while the char mass reduces. Condensation of pyrolytic gas at the end of the pyrolysis process at 650°C produced 2.4-2.72 g of liquid phase. The results obtained represent a starting basis for determining material and heat balance of pyrolysis process as well as woody biomass pyrolysis equipment.

  7. Catalytic microwave pyrolysis of biomass for renewable phenols and fuels

    NASA Astrophysics Data System (ADS)

    Bu, Quan

    Bio-oil is an unstable intermediate and needs to be upgraded before its use. This study focused on improving the selectivity of bio-oilby catalytic pyrolysis of biomass using activated carbon (AC) catalysts. Firstly, the effects of process conditions on product quality and product yield were investigated by catalytic microwave pyrolysis of biomass using AC as a catalyst. The optimized reaction condition for bio-oil and volatile was determined. Chemical composition analysis by GC/MS showed that phenols rich bio-oils were obtained. Furthermore, the effects of different carbon sources based AC catalysts on products yield and chemical composition selectivity of obtained bio-oils were investigated during microwave pyrolysis of Douglas fir pellet. The catalysts recycling test of the selected catalysts indicated that the AC catalysts can be used for 3-4 times with high concentration of phenolic compounds. The individual surface polar/acidic oxygen functional groups analysis suggested the changes of functional groups in ACs explained the reaction mechanism of this process. In addition, the potential for production of renewable phenols and fuels by catalytic pyrolysis of biomass using lignin as a model compound was explored. The main chemical compounds of the obtained bio-oils were phenols, guaiacols, hydrocarbons and esters. The thermal decomposition behaviors of lignin and kinetics study were investigated by TGA. The change of functional groups of AC catalyst indicated the bio-oil reduction was related to the reaction mechanism of this process. Finally, the effects of Fe-modified AC catalyst on bio-oil upgrading and kintic study of biomass pyrolysis were investigated. The catalytic pyrolysis of biomass using the Fe-modified AC catalyst may promote the occurrence of the fragmentation of cellulose, rather than repolymerization as in the non-catalytic pyrolysis which leads to partial of guaiacols derived from furans. Results showed that the main chemical compounds of bio

  8. 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.

  9. Presence of metals in biomass residues after pyrolysis

    NASA Astrophysics Data System (ADS)

    Guehenneux, G.; Varin, S.; Baussand, P.

    2003-05-01

    In contribution to research into renewable energy, pyrolysis tests are run to develop the process of pyrolysis of biomass allowing the production of Hydrogen. Various families of combustibles (oleaginous, lignocellulosics, and seeds) have been tested at different temperatures. The pyrolysis of biomass is hampered by technical problems such as the blockage of the furnace by tars. The residues are collected and treated in a solution of chloric and nitric acid, so that the mineral part is extracted and then analysed by ICP. The first results indicate the presence ofmetals: Ni, Mg, Zn, Mn, Fe... Various proposais for the use of these residues so as to avoid pollution due to their accumulation have been put forward. These ashes can be recombined with fuels, acting as catalysts to reduce the formation of tar and increase the production of hydrogen.

  10. 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.

  11. 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.

  12. Microwave-assisted catalytic pyrolysis of lignocellulosic biomass for production of phenolic-rich bio-oil.

    PubMed

    Mamaeva, Alisa; Tahmasebi, Arash; Tian, Lu; Yu, Jianglong

    2016-07-01

    Catalytic microwave pyrolysis of peanut shell (PT) and pine sawdust (PS) using activated carbon (AC) and lignite char (LC) for production of phenolic-rich bio-oil and nanotubes was investigated in this study. The effects of process parameters such as pyrolysis temperature and biomass/catalyst ratio on the yields and composition of pyrolysis products were investigated. Fast heating rates were achieved under microwave irradiation conditions. Gas chromatography-mass spectrometry (GC-MS) analysis of bio-oil showed that activated carbon significantly enhanced the selectivity of phenolic compounds in bio-oil. The highest phenolics content in the bio-oil (61.19 %(area)) was achieved at 300°C. The selectivity of phenolics in bio-oil was higher for PT sample compared to that of PS. The formation of nanotubes in PT biomass particles was observed for the first time in biomass microwave pyrolysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    SciTech Connect

    Mukarakate, Calvin; Mittal, Ashutosh; Ciesielski, Peter N.; Budhi, Sridhar; Thompson, Logan; Iisa, Kristiina; Nimlos, Mark R.; Donohoe, Bryon S.

    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 fast 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.

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

    SciTech Connect

    Mukarakate, Calvin; Mittal, Ashutosh; Ciesielski, Peter N.; Budhi, Sridhar; Thompson, Logan; Iisa, Kristiina; Nimlos, Mark R.; Donohoe, Bryon S.

    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 fast 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.

  15. Kinetic modeling of solid yields formation in the fast pyrolysis of mahogany wood

    NASA Astrophysics Data System (ADS)

    Wijayanti, W.; Sasongko, M. N.

    2016-03-01

    There have been many research of biomass pyrolysis not only in heat transfer point of view but also in chemical reaction point of view. In the present study, the rate of reaction (kinetic rate) formation of solid yield was calculated by varying the pyrolysis temperature that gives a chance of 250 °C, 350 °C, 450 °C, 500 °C, 600 °C, 700 °C, until 800°C with heating rate around 700 °C/hour. The heating rate used was the fast pyrolysis in which the heating rate for heating furnaces takes place quickly. Pyrolysis was accomplished by direct pyrolysis process in which each process was conducted at the certain pyrolysis temperature variation that took over 3 hours. Biomass used was mahogany wood, while the inert gas used to hold in order to avoid combustion was nitrogen gas. The decreasing of solid yields formation obtained was used to calculate the kinetic rate of the pyrolysis process. It was calculated by using the similar Arrhenius equation that considering the temperature changes during the process and the decreasing mass of solid yield formation occurred. The kinetic rate results showed the decomposition of biomass occurs tended in two stages, namely a stage of water evaporation and degradation of biomass solid yield coal followed by a stage of constant formation. The decomposition is expressed by the magnitude of the rate of reaction at 25˚C-517˚C temperature range with a reaction rate constant k1 = 2151.67 exp (-2141/Tp). While at pyrolysis temperatures above 517˚C, the reaction rate constant is expressed with k2 = 32.20 exp (-127.8 / Tp).

  16. 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.

  17. Mass spectrometric studies of fast pyrolysis of cellulose.

    PubMed

    Degenstein, John C; Hurt, Matt; Murria, Priya; Easton, McKay; Choudhari, Harshavardhan; Yang, Linan; Riedeman, James; Carlsen, Mark S; Nash, John J; Agrawal, Rakesh; Delgass, W Nicholas; Ribeiro, Fabio H; Kenttämaa, Hilkka I

    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 and 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.

  18. Mass spectrometric studies of fast pyrolysis of cellulose

    SciTech Connect

    Degenstein, John; Hurt, Matt; Murria, Priya; Easton, McKay; Choudhari, Harshavardhan; Yang, Linan; Riedeman, James; Carlsen, Mark; Nash, John; Agrawal, Rakesh; Delgass, W.; Ribeiro, Fabio; Kenttämaa, Hilkka

    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 and 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.

  19. Kinetics study on biomass pyrolysis for fuel gas production.

    PubMed

    Chen, Guan-Yi; Fang, Meng-Xiang; Andries, J; Luo, Zhong-Yang; Spliethoff, H; Cen, Ke-Fa

    2003-01-01

    Kinetic knowledge is of great importance in achieving good control of the pyrolysis and gasification process and optimising system design. An overall kinetic pyrolysis scheme is therefore addressed here. The kinetic modelling incorporates the following basic steps: the degradation of the virgin biomass materials into primary products (tar, gas and semi-char), the decomposition of primary tar into secondary products and the continuous interaction between primary gas and char. The last step is disregarded completely by models in the literature. Analysis and comparison of predicted results from different kinetic schemes and experimental data on our fixed bed pyrolyser yielded very positive evidence to support our kinetic scheme.

  20. Miscanthus as a feedstock for fast-pyrolysis: does agronomic treatment affect quality?

    PubMed

    Hodgson, E M; Fahmi, R; Yates, N; Barraclough, T; Shield, I; Allison, G; Bridgwater, A V; Donnison, I S

    2010-08-01

    The objectives of the experiment were to assess the impact of nitrogen (N) and potassium (K) fertiliser application on the cell wall composition and fast-pyrolysis conversion quality of the commercially cultivated hybrid Miscanthus x giganteus. Five different fertiliser treatments were applied to mature Miscanthus plants which were sampled at five intervals over a growing season. The different fertiliser treatments produced significant variation in concentrations of cell wall components and ash within the biomass and affected the composition and quality of the resulting fast-pyrolysis liquids. The results indicated that application of high rates of N fertiliser had a negative effect on feedstock quality for this conversion pathway: reducing the proportion of cell wall components and increasing accumulation of ash in the harvested biomass. No exclusive effect of potassium fertiliser was observed. The low-N fertiliser treatment produced high quality, low ash-high lignin biomass most suitable as a feedstock for thermo-chemical conversion.

  1. Fast pyrolysis char - Assessment of alternative uses within the bioliq® concept.

    PubMed

    Funke, A; Niebel, A; Richter, D; Abbas, M M; Müller, A-K; Radloff, S; Paneru, M; Maier, J; Dahmen, N; Sauer, J

    2016-01-01

    Experiments with a process development unit for fast pyrolysis of biomass residues of 10kgh(-1) have been performed to quantify the impact of two different product recovery options. Wheat straw, miscanthus and scrap wood have been used as feedstock. A separate recovery of char increases the organic oil yield as compared to a combined recovery of char and organic condensate (OC). Furthermore, it allows for an alternative use of the byproduct char which represents an important product fraction for the high ash biomass residues under consideration. The char produced shows little advantage over its biomass precursor when considered as energy carrier due to its high ash content. Significant value can be added by demineralizing and activating the char. The potential to increase the economic feasibility of fast pyrolysis is shown by an assessment of the bioliq® process chain. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Influence of pyrolysis temperature on physicochemical properties of biochar obtained from the fast pyrolysis of pitch pine (Pinus rigida).

    PubMed

    Kim, Kwang Ho; Kim, Jae-Young; Cho, Tae-Su; Choi, Joon Weon

    2012-08-01

    The aim of this study was to investigate the influence of pyrolysis temperature on the physicochemical properties and structure of biochar. Biochar was produced by fast pyrolysis of pitch pine (Pinus rigida) using a fluidized bed reactor at different pyrolysis temperatures (300, 400 and 500 °C). The produced biochars were characterized by elemental analysis, Brunauer-Emmett-Teller (BET) surface area, particle size distributions, field-emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FTIR) spectroscopy, solid-state (13)C nuclear magnetic resonance (NMR) and X-ray diffraction (XRD). The yield of biochar decreased sharply from 60.7% to 14.4%, based on the oven-dried biomass weight, when the pyrolysis temperature rose from 300 °C to 500 °C. In addition, biochars were further carbonized with an increase in pyrolysis temperature and the char's remaining carbons were rearranged in stable form. The experimental results suggested that the biochar obtained at 400 and 500 °C was composed of a highly ordered aromatic carbon structure.

  3. 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

  4. Numerical Modelling of a Fast Pyrolysis Process in a Bubbling Fluidized Bed Reactor

    NASA Astrophysics Data System (ADS)

    Jalalifar, S.; Ghiji, M.; Abbassi, R.; Garaniya, V.; Hawboldt, K.

    2017-07-01

    In this study, the Eulerian-Granular approach is applied to simulate a fast pyrolysis bubbling fluidized bed reactor. Fast pyrolysis converts biomass to bio-products through thermochemical conversion in absence of oxygen. The aim of this study is to employ a numerical framework for simulation of the fast pyrolysis process and extend this to more complex reactor geometries. The framework first needs to be validated and this was accomplished by modelling a lab-scale pyrolysis fluidized bed reactor in 2-D and comparing with published data. A multi-phase CFD model has been employed to obtain clearer insights into the physical phenomena associated with flow dynamics and heat transfer, and by extension the impact on reaction rates. Biomass thermally decomposes to solid, condensable and non-condensable and therefore a multi-fluid model is used. A simplified reaction model is sued where the many components are grouped into a solid reacting phase, condensable/non-condensable phase, and non-reacting solid phase (the heat carrier). The biomass decomposition is simplified to four reaction mechanisms based on the thermal decomposition of cellulose. A time-splitting method is used for coupling of multi-fluid model and reaction rates. A good agreement is witnessed in the products yield between the CFD simulation and the experiment.

  5. 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.

  6. 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.

  7. Radiant flash pyrolysis of biomass using a xenon flashtube

    SciTech Connect

    Hopkins, M.W.; Antal, M.J. Jr.

    1984-06-01

    Biomass materials, including lignin, redwood, corn cob, Calotropis Procera, Leucaena wood, Kraft paper, newsprint, cow manure, D-glucose, and D-cellobiose, were pyrolyzed in vacuum by the visible radiant flux emitted from a Xenon flashtube. The flux density exceeded 8 kW/cm/sup 2/ during the 1 ms flash. Sirup yields were low (avg 25%), while the gas yield was high (avg 32%). The gaseous products were composed primarily of CO and CO/sub 2/. The high relative yields of CO establish the existence of a high temperature fragmentation pathway active during the flash pyrolysis of all biomass materials. 39 references, 2 figures, 5 tables.

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

    SciTech Connect

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

    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-5 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.

  9. 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

  10. 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.

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

    DOEpatents

    Baird, Lance Awender; Brandvold, Timothy A.

    2015-11-24

    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 through 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.

  12. 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

  13. Influence of Partial Combustion on Rapid Pyrolysis of Wood Biomass

    NASA Astrophysics Data System (ADS)

    Yasuda, Hajime; Yamada, Osamu; Kaiho, Mamoru; Shinagawa, Takuya; Matsui, Satoshi; Iwasaki, Toshihiko; Shimada, Sohei

    A batch reactor was made and used in this work. In an actual rapid pyrolyzer/gasifier, each biomass is thrown into high temperature zone in the reactor. In order to simulate the reaction occurred in a fluidized bed rapid pyrolyzer/gasifier, the reactor was designed to inject samples into reaction zone directly and to control the reaction time optionally. Rapid pyrolysis of wood biomasses, such as Konara, bagasse, and EFB (Empty Fruit Bunch), was carried out at 1073K in nitrogen with the reaction time range of 2-20s. Difference in product distribution with varying reaction time was observed apparently among Konara, bagasse, and EFB. The difference in the reactivity among sorts of biomass should be considered even when their elemental composition and/or components ratio are similar. Rapid pyrolysis of wood biomass (Japanese cedar) with small amount of oxygen as gasification agent was also carried out. The amount of product gas was decreased through 1s to 2s and the decreasing rate was higher with increase in the amount of oxygen.

  14. Summary of Fast Pyrolysis and Upgrading GHG Analyses

    SciTech Connect

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

    2012-12-07

    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.

  15. 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.

  16. 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.

  17. 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...

  18. Thermal decomposition and gasification of biomass pyrolysis gases using a hot bed of waste derived pyrolysis char.

    PubMed

    Al-Rahbi, Amal S; Onwudili, Jude A; Williams, Paul T

    2016-03-01

    Chars produced from the pyrolysis of different waste materials have been investigated in terms of their use as a catalyst for the catalytic cracking of biomass pyrolysis gases during the two-stage pyrolysis-gasification of biomass. The chars were produced from the pyrolysis of waste tyres, refused derived fuel and biomass in the form of date stones. The results showed that the hydrocarbon tar yields decreased significantly with all the char materials used in comparison to the non-char catalytic experiments. For example, at a cracking temperature of 800°C, the total product hydrocarbon tar yield decreased by 70% with tyre char, 50% with RDF char and 9% with biomass date stones char compared to that without char. There was a consequent increase in total gas yield. Analysis of the tar composition showed that the content of phenolic compounds decreased and polycyclic aromatic hydrocarbons increased in the product tar at higher char temperatures.

  19. 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

  20. Phenols from pyrolysis and co-pyrolysis of tobacco biomass components.

    PubMed

    Kibet, Joshua K; Khachatryan, Lavrent; Dellinger, Barry

    2015-11-01

    Phenol and its derivatives (phenol, o-, m-, p-cresols, catechol, hydroquinone, methoxy substituted phenols, etc. referred to as phenolic compounds or phenols) are well-known toxicants that exist in the environment and affect both human and natural ecosystems. This study explores quantitatively the yields of phenolic compounds from the thermal degradation (pyrolysis and oxidative pyrolysis) of common tobacco biomass components (lignin, tyrosine, ethyl cellulose, sodium alginate, and laminarin) as well as some mixtures (lignin/tyrosine, ethyl cellulose/tyrosine and sodium alginate/tyrosine) considered important in high temperature cooking, tobacco smoking, and forest fires. Special attention has been given to binary mixtures including those containing tyrosine-pyrolysis of binary mixtures of tyrosine with lignin and ethyl cellulose results in significant reductions in the yields of majority phenols relative to those from the thermal degradation of tyrosine. These results imply that the significant reductions of phenol yields in mixtures are not only dependent upon the mass fractions of the components but also the synergetic inhibition effect of biomass components on the thermal degradation of tyrosine. A mechanistic description of this phenomenon is suggested. The results may also be implied in tobacco industry that the cigarette paper (as ethyl cellulose derivative) may play a critical role in reducing the concentration of phenolic compounds released during tobacco burning.

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

    SciTech Connect

    Klinger, Jordan; Bar-Ziv, Ezra; Shonnard, David; Westover, Tyler; Emerson, Rachel

    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, and verified with independent experimental data collected with a microwave-assisted pyrolysis system. These trends include production of permanent gas (CO, CO2), 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.

  2. 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, CO2), 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

  3. Life Cycle Assessment of Gasoline and Diesel Produced via Fast Pyrolysis and Hydroprocessing

    SciTech Connect

    Hsu, D. D.

    2011-03-01

    In this work, a life cycle assessment (LCA) estimating greenhouse gas (GHG) emissions and net energy value (NEV) of the production of gasoline and diesel from forest residues via fast pyrolysis and hydroprocessing, from production of the feedstock to end use of the fuel in a vehicle, is performed. The fast pyrolysis and hydrotreating and hydrocracking processes are based on a Pacific Northwest National Laboratory (PNNL) design report. The LCA results show GHG emissions of 0.142 kg CO2-equiv. per km traveled and NEV of 1.00 MJ per km traveled for a process using grid electricity. Monte Carlo uncertainty analysis shows a range of results, with all values better than those of conventional gasoline in 2005. Results for GHG emissions and NEV of gasoline and diesel from pyrolysis are also reported on a per MJ fuel basis for comparison with ethanol produced via gasification. Although pyrolysis-derived gasoline and diesel have lower GHG emissions and higher NEV than conventional gasoline does in 2005, they underperform ethanol produced via gasification from the same feedstock. GHG emissions for pyrolysis could be lowered further if electricity and hydrogen are produced from biomass instead of from fossil sources.

  4. 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.

  5. 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

  6. 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

  7. Production of sugar and sugar derivatives by pyrolysis of biomass

    SciTech Connect

    Shafizadeh, F.

    1983-01-01

    Thermochemical conversion of biomass to sugar and sugar derivatives is hindered by the inhomogeneity of the substrate and the low specificity of the pyrolytic reactions. Recent analysis and investigation of these reactions have shown that they could be controlled and catalyzed to minimize the side reactions and increase the yield of individual compounds. These compounds include levoglucosan which could be obtained in high yields within the temperature range of 350-400/sup 0/C when the substrate has undergone previous acid treatment or a trace amount of acid is present. This phenomenon has been used for production of sugars from softwood and hardwood based on prehydrolysis and subsequent pyrolysis to a tar that could be posthydrolyzed to sugars. Acid-catalyzed pyrolysis of cellulosic materials, particularly waste paper, gives a pyrolyzate containing mainly levoglucosenone which has proved to be a highly reactive compound for production of a variety of carbohydrate derivatives. Pyrolysis of carbohydrates also provides several other furan and pyran derivatives that could be used as synthetic intermediates. 28 references, 22 figures, 11 tables.

  8. Comparison for the compositions of fast and slow pyrolysis oils by NMR characterization.

    PubMed

    Ben, Haoxi; Ragauskas, Arthur J

    2013-11-01

    The pyrolysis of softwood (SW) kraft lignin and pine wood in different pyrolysis systems were examined at 400, 500 and 600 °C. NMR including quantitative (13)C and Heteronuclear Single-Quantum Correlation (HSQC)-NMR, and Gel Permeation Chromatography (GPC) were used to characterize various pyrolysis oils. The content of methoxyl groups decreased by 76% for pine wood and 70% for lignin when using fast pyrolysis system. The carbonyl groups also decreased by 76% and nearly completely eliminated in 600 °C pine wood fast pyrolysis oil. Compared to the slow pyrolysis process, fast pyrolysis process was found to improve the cleavage of methoxyl groups, aliphatic CC bonds and carbonyl groups and produce more polyaromatic hydrocarbons (PAH) from lignin and aliphatic CO bonds from carbohydrates. Another remarkable difference between fast and slow pyrolysis oils was the molecular weight of fast pyrolysis oils increased by 85-112% for pine wood and 104-112% for lignin.

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. 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 (Ea) 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.

  14. 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.

  15. 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

  16. 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.

  17. 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

  18. MBMS of biomass pyrolysis vapors and catalytic upgrading

    SciTech Connect

    French, R.J.; Rejai, B.

    1995-03-01

    Studies of the production of transportation fuels from woody plants and other biomass sources at NREL have included the catalytic upgrading of vapors produced by the pyrolysis of wood and other materials. Molecular beam mass spectrometry is uniquely suited to the screening of this chemistry because of its ability to fingerprint the complete slate of pyrolysis or catalysis products in real time. It can also follow transient behavior at the rate of several spectra per second, which is useful in modeling the behavior of a riser-cracker or similar industrial system. Laboratory work was done on a dual-bed vertical reactor in which the sample (3-80 mg of solid sample) is pyrolyzed in the lower section of the reactor and then passed over 0.2-1.0 g of various catalysts. It is then diluted and introduced into the molecular beam. This system can be used to compare various catalysts and feedstocks. In other experiments, a pilot-scale (15kg/hr) pyrolysis plant with catalytic riser cracker was monitored with the NREL transportable MBMS. Continuous sampling was done via an atmospheric pressure, heated line. Nitrogen dilution was used to suppress condensation and water clusters. Results will be shown comparing products from wood, sunflower seeds, and mixtures of paper and plastics. Over MFI zeolite catalyst, a product slate similar to the methanol-to-gasoline process is observed--a mixture of alkane, alkene and aromatic compounds--with additional CO and CO{sub 2}. Higher yields of alkenes are produced by the oily and plastic-containing samples. The pilot plant gives spectra similar to the laboratory data. The TMBMS correctly identified improved operating conditions.

  19. Spontaneous Aerosol Ejection: Origin of Inorganic Particles in Biomass Pyrolysis.

    PubMed

    Teixeira, Andrew R; Gantt, Rachel; Joseph, Kristeen E; Maduskar, Saurabh; Paulsen, Alex D; Krumm, Christoph; Zhu, Cheng; Dauenhauer, Paul J

    2016-06-08

    At high thermal flux and temperatures of approximately 500 °C, lignocellulosic biomass transforms to a reactive liquid intermediate before evaporating to condensable bio-oil for downstream upgrading to renewable fuels and chemicals. However, the existence of a fraction of nonvolatile compounds in condensed bio-oil diminishes the product quality and, in the case of inorganic materials, catalyzes undesirable aging reactions within bio-oil. In this study, ablative pyrolysis of crystalline cellulose was evaluated, with and without doped calcium, for the generation of inorganic-transporting aerosols by reactive boiling ejection from liquid intermediate cellulose. Aerosols were characterized by laser diffraction light scattering, inductively coupled plasma spectroscopy, and high-speed photography. Pyrolysis product fractionation revealed that approximately 3 % of the initial feed (both organic and inorganic) was transported to the gas phase as aerosols. Large bubble-to-aerosol size ratios and visualization of significant late-time ejections in the pyrolyzing cellulose suggest the formation of film bubbles in addition to the previously discovered jet formation mechanism. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. 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.

  1. Desulphurization of lignites by slow, fast, and flash pyrolysis and high intensity dry magnetic separation

    SciTech Connect

    Koca, H.; Kockar, O.M.; Koca, S.

    2007-07-01

    Slow, fast and flash pyrolysis followed by high intensity dry magnetic (HIDM) separation experiments were conducted to obtain improved solid fuels. Pyrolysis experiments were performed in three different apparatus, and important parameters of processes, temperature, particle size, residence time and heating rate were studied to determine the optimum conditions. Desulphurization of lignites by flash pyrolysis is more successful than slow and fast pyrolysis. At optimum conditions of pyrolysis, up to 58.15, 60.24, and 62.31% sulphur reductions were obtained in slow, fast and flash pyrolysis, respectively. Char, obtained from the pyrolysis experiments, was further cleaned by a Permroll HIDM separator. Sulphur reduction enhanced up to 82.68, 84.40, and 86.55% in the char of slow, fast and flash pyrolysis, respectively.

  2. 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

  3. A granular-biomass high temperature pyrolysis model based on the Darcy flow

    NASA Astrophysics Data System (ADS)

    Guan, Jian; Qi, Guoli; Dong, Peng

    2015-03-01

    We established a model for the chemical reaction kinetics of biomass pyrolysis via the high-temperature thermal cracking of liquid products. We divided the condensable volatiles into two groups, based on the characteristics of the liquid prdoducts., tar and biomass oil. The effects of temperature, residence time, particle size, velocity, pressure, and other parameters on biomass pyrolysis and high-temperature tar cracking were investigated numerically, and the results were compared with experimental data. The simulation results showed a large endothermic pyrolysis reaction effect on temperature and the reaction process. The pyrolysis reaction zone had a constant temperature period in several layers near the center of large biomass particles. A purely physical heating process was observed before and after this period, according to the temperature index curve.

  4. 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...

  5. 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.

  6. Microwave induced fast pyrolysis of scrap rubber tires

    NASA Astrophysics Data System (ADS)

    Ani, Farid Nasir; Mat Nor, Nor Syarizan

    2012-06-01

    Pyrolysis is the thermal degradation of carbonaceous solid by heat in the absence of oxygen. The feedstocks, such as biomass or solid wastes are heated to a temperature between 400 and 600°C, without introducing oxygen to support the reaction. The reaction produces three products: gas, pyro-fuel oil and char. This paper presents the techniques of producing pyro-oil from waste tires, as well as investigation of the fuel properties suitable for diesel engine applications. In this study, microwave heating technique is employed to pyrolyse the used rubber tires into pyro-oil. Thermal treatment of as received used rubber tires is carried out in a modified domestic microwave heated fixed bed technology. It has been found that, rubber tires, previously used by various researchers, are poor microwave absorbers. Studies have shown that an appropriate microwave-absorbing material, such as biomass char or activated carbon, could be added to enhance the pyrolysis process; thus producing the pyro-oil. The characteristics of pyro-oil, as well as the effect of microwave absorber on its yield, are briefly described in this paper. The temperature profiles during the microwave heating process are also illustratively emphasized. The study provides a means of converting scrap tires into pyro-oil and pyrolytic carbon black production. The proposed microwave thermal conversion process therefore has the potentials of substantially saving time and energy.

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

    SciTech Connect

    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 suspended 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.

  8. 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.

  9. 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.

  10. Co-pyrolysis of coal/biomass and coal/sewage sludge mixtures

    SciTech Connect

    Storm, C.; Ruediger, H.; Spliethoff, H.; Hein, K.R.G.

    1999-01-01

    Biomass and sewage sludge are attracting increasing interest in power plant technology as a source of carbon-dioxide-neutral fuels. A new way to reduce the consumption of fossil fuels could be the co-combustion or co-gasification of coal and biomass or coal and sewage sludge. In both cases, pyrolysis is the first step in the technical process. In order to obtain detailed information about the pyrolysis of coal/biomass and coal/sewage sludge mixtures as well as unblended fuels, the Institut fuer Verfahrenstechnik and Dampfkesselwesen (IVD) at the University of Stuttgart has carried out investigations using an electrically heated entrained flow reactor. The test runs provided information about fuel conversion efficiency, pyrolysis gas and tar yield, and composition of pyrolysis gas and tar. Besides gas and tar analysis investigations regarding the path of trace elements, like heavy metals, alkali, chlorine and nitrogen components, during the pyrolysis process varying different parameters have been carried out. The fuel nitrogen distribution between pyrolysis gas, tar, and char has been analyzed, as well as the ash composition, and, thus, the release of mineral components during pyrolysis.

  11. 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.

  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. 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.

  14. 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.

  15. Co-pyrolysis of Chinese lignite and biomass in a vacuum reactor.

    PubMed

    Yang, Xiao; Yuan, Chengyong; Xu, Jiao; Zhang, Weijiang

    2014-12-01

    A vacuum fixed bed reactor was applied to pyrolyze lignite, biomass (rice husk) and their blend with high temperature (900 °C) and low heating rate (10 °C/min). Pyrolytic products were kept in the vacuum reactor during the whole pyrolysis process, guaranteeing a long contact time (more than 2 h) for their interactions. Remarkable synergetic effects were observed. Addition of biomass obviously influenced the tar and char yields, gas volume yield, gas composition, char structure and tar composition during co-pyrolysis. It was highly possible that char gasification, gaseous phase interactions, and secondary tar cracking were facilitated when lignite and biomass were co-pyrolyzed.

  16. Enhancing biochar yield by co-pyrolysis of bio-oil with biomass: impacts of potassium hydroxide addition and air pretreatment prior to co-pyrolysis.

    PubMed

    Veksha, Andrei; Zaman, Waheed; Layzell, David B; Hill, Josephine M

    2014-11-01

    The influence of KOH addition and air pretreatment on co-pyrolysis (600 °C) of a mixture of bio-oil and biomass (aspen wood) was investigated with the goal of increasing biochar yield. The bio-oil was produced as a byproduct of the pyrolysis of biomass and recycled in subsequent runs. Co-pyrolysis of the biomass with the recycled bio-oil resulted in a 16% mass increase in produced biochar. The yields were further increased by either air pretreatment or KOH addition prior to co-pyrolysis. Air pretreatment at 220 °C for 3 h resulted in the highest mass increase (32%) compared to the base case of pyrolysis of biomass only. No synergistic benefit was observed by combining KOH addition with air pretreatment. In fact, KOH catalyzed reactions that increased the bed temperature resulting in carbon loss via formation of CO and CO2.

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

    SciTech Connect

    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 from 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.

  18. 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.

  19. 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.

  20. 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.

  1. Comparative study of pyrolysis of algal biomass from natural lake blooms with lignocellulosic biomass.

    PubMed

    Maddi, Balakrishna; Viamajala, Sridhar; Varanasi, Sasidhar

    2011-12-01

    Pyrolysis experiments were performed with algal and lignocellulosic feedstocks under similar reactor conditions 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 protein degradation). Algal bio-char also had a significantly higher N-content. Overall, our results suggest that it is feasible to convert algal cultures deficient in lipids, such as nuisance algae obtained from natural blooms, into liquid fuels by thermochemical methods. As such, pyrolysis technologies being developed for lignocellulosic biomass may be directly applicable to algal feedstocks as well.

  2. Co-pyrolysis of low rank coals and biomass: Product distributions

    SciTech Connect

    Soncini, Ryan M.; Means, Nicholas C.; Weiland, Nathan T.

    2013-10-01

    Pyrolysis and gasification of combined low rank coal and biomass feeds are the subject of much study in an effort to mitigate the production of green house gases from integrated gasification combined cycle (IGCC) systems. While co-feeding has the potential to reduce the net carbon footprint of commercial gasification operations, the effects of co-feeding on kinetics and product distributions requires study to ensure the success of this strategy. Southern yellow pine was pyrolyzed in a semi-batch type drop tube reactor with either Powder River Basin sub-bituminous coal or Mississippi lignite at several temperatures and feed ratios. Product gas composition of expected primary constituents (CO, CO{sub 2}, CH{sub 4}, H{sub 2}, H{sub 2}O, and C{sub 2}H{sub 4}) was determined by in-situ mass spectrometry while minor gaseous constituents were determined using a GC-MS. Product distributions are fit to linear functions of temperature, and quadratic functions of biomass fraction, for use in computational co-pyrolysis simulations. The results are shown to yield significant nonlinearities, particularly at higher temperatures and for lower ranked coals. The co-pyrolysis product distributions evolve more tar, and less char, CH{sub 4}, and C{sub 2}H{sub 4}, than an additive pyrolysis process would suggest. For lignite co-pyrolysis, CO and H{sub 2} production are also reduced. The data suggests that evolution of hydrogen from rapid pyrolysis of biomass prevents the crosslinking of fragmented aromatic structures during coal pyrolysis to produce tar, rather than secondary char and light gases. Finally, it is shown that, for the two coal types tested, co-pyrolysis synergies are more significant as coal rank decreases, likely because the initial structure in these coals contains larger pores and smaller clusters of aromatic structures which are more readily retained as tar in rapid co-pyrolysis.

  3. 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 CxHy 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.

  4. The origin of molecular mobility during biomass pyrolysis as revealed by in situ (1)H NMR spectroscopy.

    PubMed

    Dufour, Anthony; Castro-Diaz, Miguel; Brosse, Nicolas; Bouroukba, Mohamed; Snape, Colin

    2012-07-01

    The thermochemical conversion of lignocellulosic biomass feedstocks offers an important potential route for the production of biofuels and value-added green chemicals. Pyrolysis is the first phenomenon involved in all biomass thermochemical processes and it controls to a major extent the product composition. The composition of pyrolysis products can be affected markedly by the extent of softening that occurs. In spite of extensive work on biomass pyrolysis, the development of fluidity during the pyrolysis of biomass has not been quantified. This paper provides the first experimental investigation of proton mobility during biomass pyrolysis by in situ (1)H NMR spectroscopy. The origin of mobility is discussed for cellulose, lignin and xylan. The effect of minerals on cellulose mobility is also investigated. Interactions between polymers in the native biomass network are revealed by in situ (1)H NMR analysis. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. 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.

  6. 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.

  7. High yield bio-oil production from fast pyrolysis by metabolic controlling of Chlorella protothecoides.

    PubMed

    Miao, Xiaoling; Wu, Qingyu

    2004-05-13

    The use of renewable energy sources is becoming increasingly necessary to mitigate global warming. Recently much research has been focused on identifying suitable biomass species, which can provide high-energy outputs, to replace conventional fossil fuels. This paper reports an approach for increasing the yield of bio-oil production from fast pyrolysis after manipulating the metabolic pathway in microalgae through heterotrophic growth. The yield of bio-oil (57.9%) produced from heterotrophic Chlorella protothecoides cells was 3.4 times higher than from autotrophic cells by fast pyrolysis. The bio-oil was characterized by a much lower oxygen content, with a higher heating value (41 MJ kg(-1)), a lower density (0.92 kg l(-1)), and lower viscosity (0.02 Pas) compared to those of bio-oil from autotrophic cells and wood. These properties are comparable to fossil oil. The research could contribute to the creation of a system to produce energy from microalgae, and also could have great commercial potential for liquid fuel production.

  8. Life cycle greenhouse gas emissions analysis of catalysts for hydrotreating of fast pyrolysis bio-oil

    SciTech Connect

    Snowden-Swan, Lesley J.; Spies, Kurt A.; Lee, Guo-Shuh J.; Zhu, Yuanyuan

    2016-03-01

    Bio-oil from fast pyrolysis of biomass requires multi-stage catalytic hydroprocessing to produce hydrocarbon drop-in fuels. The current proposed process design involves fixed beds of ruthenium-based catalyst and conventional petroleum hydrotreating catalyst. Similar to petroleum processing, the catalyst is spent as a result of coking and other deactivation mechanisms, and must be changed out periodically. Biofuel life cycle greenhouse gas (GHG) assessments typically ignore the impact of catalyst consumed during fuel conversion as a result of limited lifetime, representing a data gap in the analyses. To help fill this data gap, life cycle GHGs were estimated for two representative examples of fast pyrolysis bio-oil hydrotreating catalyst, NiMo/Al2O3 and Ru/C, and integrated into the conversion-stage GHG analysis. Life cycle GHGs for the NiMo/Al2O3 and Ru/C catalysts are estimated at 5.5 and 81 kg CO2-e/kg catalyst, respectively. Contribution of catalyst consumption to total conversion-stage GHGs is 0.5% for NiMo/Al2O3 and 5% for Ru/C. This analysis does not consider secondary sourcing of metals for catalyst manufacture and therefore these are likely to be conservative estimates compared to applications where a spent catalyst recycler can be used.

  9. Pyrolysis Research at the National Renewable Energy Laboratory

    SciTech Connect

    Iisa, Kristiina; Ciesielski, Peter N.; Nimlos, Mark R.

    2014-01-01

    The overwhelming majority of biomass pyrolysis research at NREL is supported by the US Department of Energy's Office of the Biomass Program and is focused on the production of 'drop-in' transportation fuels. This includes studies of fast pyrolysis and vapor phase upgrading of pyrolysis vapors to produce hydrocarbon fuel blendstocks or refinery feedstocks.

  10. Sustainability assessment of water hyacinth fast pyrolysis in the Upper Paraguay River basin, Brazil.

    PubMed

    Buller, Luz Selene; Ortega, Enrique; Bergier, Ivan; Mesa-Pérez, Juan Miguel; Salis, Suzana Maria; Luengo, Carlos Alberto

    2015-11-01

    Fast pyrolysis of naturally produced water hyacinth was assessed through Emergy accounting approach. Two analyses were carried out to evaluate the influence of additional services and externalities on Emergy indicators for a pyrolysis plant unit able to process 1000 kg of dry biomass per hour. The initial approach was a traditional Emergy assessment in which financial fluxes and externalities were not considered. The second approach included taxes and fees of the Brazilian government, interests related to financing operations and assumes a reserve financial fund of 5% of the total investment as externalities cost. For the first evaluation, the renewability of 86% indicates that local and renewable resources mainly support the process and the Emergy Yield Ratio of 3.2 shows that the system has a potential contribution to the regional economy due to the local resources use. The inclusion of financial fluxes and externalities in the second evaluation reduces both renewability and Emergy Yield Ratio, whereas it increases the Emergy Investment Ratio which means a higher dependence on external resources. The second analysis allows portraying significant forces of the industrial and financial systems and the evaluation of the externalities' impact on the general system Emergy behavior. A comparison of the renewability of water hyacinth fast pyrolysis with other biofuels like soybean biodiesel and sugarcane ethanol indicates that the former is less dependent on fossil fuel resources, machinery and fertilizers. To complement the sustainability assessment provided by the Emergy method, a regular financial analysis for the second defined system was done. It shows that the system is financially attractive even with the accounting of additional costs. The results obtained in this study could be used as the maximum and minimum thresholds to subsidize regulatory policies for new economic activities in tropical wetlands involving natural resources exploitation and bio

  11. Hirshfeld charge analysis and model compound studies of biomass pyrolysis

    SciTech Connect

    Cutler, A.H.

    1985-01-01

    The method of partitioning molecular electron densities into atomic changes proposed by F.L. Hirshfeld has been compared to other methods and to empirical expectations. It is found to bear similarities to other theoretical methods. Previous theoretical treatments of kinetics in laminar flow reactors are discussed. It is found that the effects of diffusion on calculated kinetics are surprisingly small. The errors in the measured activation energy of a first order reaction due to experimental uncertainty are derived and discussed. High temperature pyrolysis of t-butyl alcohol (973-1113 K) and acetaldehyde (1033-1153 K) in steam at various reactant concentrations were carried out, giving activation parameters and product distributions in agreement with previous work. Acetaldehyde pyrolysis product distributions agree with previous work. It is concluded that the reactor has no effect on the kinetics or mechanisms of radical chain reactions. The kinetics and mechanism of 1,3-dioxolane pyrolysis were determined in atmospheric pressure steam between 963 K and 1093 K with reactant concentrations of 6.82 x 10/sup -7/ to 1.36 x 10/sup -4/ mol/l using a laminar flow reactor. The reaction was found to be first order. Some mechanistic aspects of levoglucosan pyrolysis are discussed in light of these results in dioxolane and recently published results on glycerol pyrolysis.

  12. 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...

  13. Weibull mixture model for isoconversional kinetic analysis of biomass oxidative pyrolysis

    NASA Astrophysics Data System (ADS)

    Cai, J. M.; Chen, S. Y.

    2010-03-01

    In this work, the possibility of applying the weighted sum of three cumulative Weibull distribution functions for the fitting of the kinetic conversion data of biomass oxidative pyrolysis has been investigated. The kinetic conversion data of the thermal decomposition of olive oil solid waste in oxygen atmosphere for different heating rates have been analyzed. The results have shown that the experimental data can be perfectly reproduced by the general fitting function. Therefore, it is possible to obtain the corresponding conversion rate values of biomass oxidative pyrolysis by differentiating directly the fitted kinetic conversion data. Additionally, the logistic mixture model has been applied to the same experimental data. It can be found that the newly proposed function can provide a better fit of the data than the logistic mixture model. Based on the fitting of Weibull mixture model, the kinetic triples (E, A and f(α)) of oxidative pyrolysis of olive solid waste were obtained by means of Friedman's differential isoconversional method.

  14. Effect of Potassium on the Mechanisms of Biomass Pyrolysis Studied using Complementary Analytical Techniques.

    PubMed

    Le Brech, Yann; Ghislain, Thierry; Leclerc, Sébastien; Bouroukba, Mohammed; Delmotte, Luc; Brosse, Nicolas; Snape, Colin; Chaimbault, Patrick; Dufour, Anthony

    2016-04-21

    Complementary analytical methods have been used to study the effect of potassium on the pyrolysis mechanisms of cellulose and lignocellulosic biomasses. Thermogravimetry, calorimetry, high-temperature (1) H NMR spectroscopy (in situ and real-time analysis of the fluid phase formed during pyrolysis), and water extraction of quenched char followed by size-exclusion chromatography coupled with mass spectrometry have been combined. Potassium impregnated in cellulose suppresses the formation of anhydrosugars, reduces the formation of mobile protons, and gives rise to a mainly exothermic signal. The evolution of mobile protons formed from K-impregnated cellulose has a very similar pattern to the evolution of the mass loss rate. This methodology has been also applied to analyze miscanthus, demineralized miscanthus, miscanthus re-impregnated with potassium after demineralization, raw oak, and Douglas fir. Hydrogen mobility and transfer are of high importance in the mechanisms of biomass pyrolysis.

  15. 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.

  16. Sustainability: The capacity of smokeless biomass pyrolysis for energy production, global carbon capture and sequestration

    USDA-ARS?s Scientific Manuscript database

    Application of modern smokeless biomass pyrolysis for biochar and biofuel production is potentially a revolutionary approach for global carbon capture and sequestration at gigatons of carbon (GtC) scales. A conversion of about 7% of the annual terrestrial gross photosynthetic product (120 GtC y-1) i...

  17. 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.

  18. Fast microwave-assisted pyrolysis of microalgae using microwave absorbent and HZSM-5 catalyst.

    PubMed

    Borges, Fernanda Cabral; Xie, Qinglong; Min, Min; Muniz, Luis Antônio Rezende; Farenzena, Marcelo; Trierweiler, Jorge Otávio; Chen, Paul; Ruan, Roger

    2014-08-01

    Fast microwave-assisted pyrolysis (fMAP) in the presence of a microwave absorbent (SiC) and catalyst (HZSM-5) was tested on a Chlorella sp. strain and on a Nannochloropsis strain. The liquid products were characterized, and the effects of temperature and catalyst:biomass ratio were analyzed. For Chlorella sp., a temperature of 550 °C, with no catalyst were the optimal conditions, resulting in a maximum bio-oil yield of 57 wt.%. For Nannochloropsis, a temperature of 500 °C, with 0.5 of catalyst ratio were shown to be the optimal condition, resulting in a maximum bio-oil yield of 59 wt.%. These results show that the use of microwave absorbents in fMAP increased bio-oil yields and quality, and it is a promising technology to improve the commercial application and economic outlook of microwave pyrolysis technology. Additionally, the use of a different catalyst needs to be considered to improve the bio-oil characteristics. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Supply Chain Sustainability Analysis of Fast Pyrolysis and Hydrotreating Bio-Oil to Produce Hydrocarbon Fuel

    SciTech Connect

    Adom, Felix K.; Cai, Hao; Dunn, Jennifer B.; Hartley, Damon; Searcy, Erin; Tan, Eric; Jones, Sue; Snowden-Swan, Lesley

    2016-03-31

    This report describes the supply chain sustainability analysis (SCSA) of renewable gasoline and diesel produced via fast pyrolysis of a blended woody feedstock. The metrics considered in this analysis include supply chain greenhouse gas (GHG) emissions and water consumption.

  20. 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.

  1. Syngas production by two-stage method of biomass catalytic pyrolysis and gasification.

    PubMed

    Xie, Qinglong; Kong, Sifang; Liu, Yangsheng; Zeng, Hui

    2012-04-01

    A two-stage technology integrated with biomass catalytic pyrolysis and gasification processes was utilized to produce syngas (H(2)+CO). In the presence of different nickel based catalysts, effects of pyrolysis temperature and gasification temperature on gas production were investigated. Experimental results showed that more syngas and char of high quality could be obtained at a temperature of 750°C in the stage of pyrolysis, and in the stage of gasification, pyrolysis char (produced at 750°C) reacted with steam and the maximum yield of syngas was obtained at 850°C. Syngas yield in this study was greatly increased compared with previous studies, up to 3.29Nm(3)/kg biomass. The pyrolysis process could be well explained by Arrhenius kinetic first-order rate equation. XRD analyses suggested that formation of Mg(0.4)Ni(0.6)O and increase of Ni(0) crystallite size were two main reasons for the deactivation of nickel based catalysts at higher temperature.

  2. 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

    2017-09-06

    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.

  3. 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.

  4. Direct Numerical Simulation of biomass pyrolysis and combustion with gas phase reactions

    NASA Astrophysics Data System (ADS)

    Awasthi, A.; Kuerten, J. G. M.; Geurts, B. J.

    2016-09-01

    We present Direct Numerical Simulation of biomass pyrolysis and combustion in a turbulent channel flow. The model includes simplified models for biomass pyrolysis and char combustion along with a model for particle tracking. The gas phase is modelled as a mixture of reacting gas species. The gas-particle interactions for mass, momentum, and energy exchange are included by two-way coupling terms. The effect of two-way coupling on the conversion time of biomass particles is found noticeable for particle volume fractions > 10-5. We also observe that at constant volume fraction the effect of two-way coupling increases as the particle size is reduced, due to the higher total heat exchange area in case of smaller particles. The inclusion of gas phase homogeneous reactions in the DNS model decreases the biomass pyrolysis time due to higher gas temperatures. In contrast, including gas phase reactions increases the combustion time of biomass due to the lower concentration of oxygen at the particle surface.

  5. 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.

  6. Experimental evaluation of a solar fired flash pyrolysis of biomass reactor

    SciTech Connect

    Antal, M.J. Jr.; Edwards, W.E.; Steenblik, R.A.; Brown, C.T.; Knight, J.A.; Elston, L.W.; Hurst, D.R.

    1981-01-01

    A Princeton-Georgia Institute of Technology flash pyrolysis of biomass test program was conducted at the DOE Advanced Components Test Facility (CTF) at Georgia Tech in August 1980. The 400 kWth solar thermal facility was used to provide a source of highly concentrated radiant energy for the flash pyrolysis of four types of biomass in a steam counterflow quartz reactor. The biomass materials were microcrystalline cellulose, hardwood sawdust, ground corn cob, and Kraft lignin. The experiments at Princeton and Georgia Tech suggest the use of concentrated radiant energy as a selective means for the production of either a hydrocarbon rich synthesis gas or sugar related syrups from biomass by flash pyrolysis. Experiments at Princeton have indicated that sugar related syrups are selectively produced when the biomass particles are rapidly heated by radiation in a cool gaseous environment. The gas temperatures in the reactor during the test program at Georgia Tech were relatively high, which selectively turned the chemistry toward the production of hydrocarbon rich synthesis gases.

  7. Mild hydrothermal conditioning prior to torrefaction and slow pyrolysis of low-value biomass.

    PubMed

    Van Poucke, R; Nachenius, R W; Agbo, K E; Hensgen, F; Bühle, L; Wachendorf, M; Ok, Y S; Tack, F M G; Prins, W; Ronsse, F; Meers, E

    2016-10-01

    The aim of this research was to establish whether hydrothermal conditioning and subsequent thermochemical processing via batch torrefaction or slow pyrolysis may improve the fuel quality of grass residues. A comparison in terms of fuel quality was made of the direct thermochemical processing of the feedstock versus hydrothermal conditioning as a pretreatment prior to thermochemical processing. Hydrothermal conditioning reduced ash content, and particularly nitrogen, potassium and chlorine contents in the biomass. The removal of volatile organic matter associated with thermochemical processes can increase the HHV to levels of volatile bituminous coal. However, slow pyrolysis only increased the HHV of biomass provided a low ash content (<6%) feedstock was used. In conclusion, hydrothermal conditioning can have a highly positive influence on the efficiency of thermochemical processes for upgrading low-value (high-ash) biomass to a higher quality fuel. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Release characteristics of alkali and alkaline earth metallic species during biomass pyrolysis and steam gasification process.

    PubMed

    Long, Jiang; Song, Hu; Jun, Xiang; Sheng, Su; Lun-Shi, Sun; Kai, Xu; Yao, Yao

    2012-07-01

    Investigating the release characteristics of alkali and alkaline earth metallic species (AAEMs) is of potential interest because of AAEM's possible useful service as catalysts in biomass thermal conversion. In this study, three kinds of typical Chinese biomass were selected to pyrolyse and their chars were subsequently steam gasified in a designed quartz fixed-bed reactor to investigate the release characteristics of alkali and alkaline earth metallic species (AAEMs). The results indicate that 53-76% of alkali metal and 27-40% of alkaline earth metal release in pyrolysis process, as well as 12-34% of alkali metal and 12-16% of alkaline earth metal evaporate in char gasification process, and temperature is not the only factor to impact AAEMs emission. The releasing characteristics of AAEMs during pyrolysis and char gasification process of three kinds of biomass were discussed in this paper. Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. Raw material recycling of biomass with the VEBA OEL pyrolysis and gasification processes

    SciTech Connect

    Redepenning, K.H.

    1994-12-31

    From the early days of the VEBA OEL refineries originate the upgrading processes for liquid and pasty refinery residues. For treatment of residues or biomass these processes have a special importance because in comparison to combustion they are characterised by low pollutant loads and efficient energy conversion as well as high reliability when handling difficult residues. These processes are: 1. Pyrolysis of particularly heterogenous materials, such as biomass or composting residues. 2. Gasification or inertising of inorganic component, alternatively in conjunction with pyrolysis arranged upstream as a thermal pretreatment. A special feature of these processes with environmental policy relevance is the possibility of the raw material utilisation of the synthesis gases in the chemical or refinery industries. If due to the selection of location, raw material utilisation is not applicable, however, the conversion of the synthesis gases into electricity in a combined cycle unit is possible. What is significant in the process path pyrolysis, gasification and cogeneration is the high electric efficiency achievable. The high efficiency of pyrolysis and gasification is based on the conversion of the residues or biomass into high-energy intermediate products and linking with a co-generation process. In the first step, intermediate products are obtained by means of pyrolysis with condensation of the low-temperature carbonisation vapours which are characterised by their storability and grindability. In the second process step the intermediate pyrolysis products are fed to an entrained flow gasification unit operated at a pressure of approx. 20-23 {times} 10{sup 5} Pa which makes it possible to vitrify the inorganic constituents to form a slag difficult to elute and to obtain synthesis gases particularly low in noxious matter. In the final step the gases present under pressure can be passed on to the gas turbines of a progressive cogeneration gas turbine power station.

  10. Fast pyrolysis of microalgae remnants in a fluidized bed reactor for bio-oil and biochar production.

    PubMed

    Wang, Kaige; Brown, Robert C; Homsy, Sally; Martinez, Liliana; Sidhu, Sukh S

    2013-01-01

    In this study, pyrolysis of microalgal remnants was investigated for recovery of energy and nutrients. Chlorella vulgaris biomass was first solvent-extracted for lipid recovery then the remnants were used as the feedstock for fast pyrolysis experiments using a fluidized bed reactor at 500 °C. Yields of bio-oil, biochar, and gas were 53, 31, and 10 wt.%, respectively. Bio-oil from C. vulgaris remnants was a complex mixture of aromatics and straight-chain hydrocarbons, amides, amines, carboxylic acids, phenols, and other compounds with molecular weights ranging from 70 to 1200 Da. Structure and surface topography of the biochar were analyzed. The high inorganic content (potassium, phosphorous, and nitrogen) of the biochar suggests it may be suitable to provide nutrients for crop production. The bio-oil and biochar represented 57% and 36% of the energy content of the microalgae remnant feedstock, respectively.

  11. Thermochemical conversion of raw and defatted algal biomass via hydrothermal liquefaction and slow pyrolysis.

    PubMed

    Vardon, Derek R; Sharma, Brajendra K; Blazina, Grant V; Rajagopalan, Kishore; Strathmann, Timothy J

    2012-04-01

    Thermochemical conversion is a promising route for recovering energy from algal biomass. Two thermochemical processes, hydrothermal liquefaction (HTL: 300 °C and 10-12 MPa) and slow pyrolysis (heated to 450 °C at a rate of 50 °C/min), were used to produce bio-oils from Scenedesmus (raw and defatted) and Spirulina biomass that were compared against Illinois shale oil. Although both thermochemical conversion routes produced energy dense bio-oil (35-37 MJ/kg) that approached shale oil (41 MJ/kg), bio-oil yields (24-45%) and physico-chemical characteristics were highly influenced by conversion route and feedstock selection. Sharp differences were observed in the mean bio-oil molecular weight (pyrolysis 280-360 Da; HTL 700-1330 Da) and the percentage of low boiling compounds (bp<400 °C) (pyrolysis 62-66%; HTL 45-54%). Analysis of the energy consumption ratio (ECR) also revealed that for wet algal biomass (80% moisture content), HTL is more favorable (ECR 0.44-0.63) than pyrolysis (ECR 0.92-1.24) due to required water volatilization in the latter technique.

  12. 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.

  13. Corrosion Studies Of Raw And Treated Biomass-Derived Pyrolysis Oils

    SciTech Connect

    Keiser, James R; Howell, Michael; Lewis Sr, Samuel Arthur; Connatser, Raynella M

    2012-01-01

    Rapid pyrolysis of biomass generates a liquid with properties that are particularly attractive for production of hydrocarbons that could be substituted for liquid fuels derived from petroleum. However, the high oxygen content of the biomass derived liquids presents a number of problems because of the high water content and the considerable concentration of carboxylic acids. Measurements of total acid number (TAN) of pyrolysis oil (bio-oil) samples show that values in the 90-100 range are fairly common. This level of acidity has been shown to cause corrosion problems that have to be addressed in the selection of structural materials that are used in the production, subsequent processing, storage and transport of the pyrolysis oils. Chemical analyses have been performed and laboratory corrosion studies have been conducted in order to assess the aggressiveness of the raw pyrolysis oil from several sources as well as the corrosion caused by a bio-oil that has been treated to reduce the acid and oxygen content. Components of biomass pyrolyzers have also been fabricated from various candidate alloys, and these components have been exposed for extended periods during operation of the pyrolyzers. This paper will report on results of these analyses and corrosion studies.

  14. Production of green aromatics and olefins by catalytic fast pyrolysis of wood sawdust

    SciTech Connect

    Carlson, Torren R.; Cheng, Yu-Ting; Jae, Jungho; Huber, George W.

    2011-10-26

    Catalytic fast pyrolysis of pine wood sawdust and furan (a model biomass compound) with ZSM-5 based catalysts was studied with three different reactors: a bench scale bubbling fluidized bed reactor, a fixed bed reactor and a semi-batch pyroprobe reactor. The highest aromatic yield from sawdust of 14% carbon in the fluidized bed reactor was obtained at low biomass weight hourly space velocities (less than 0.5 h-1) and high temperature (600 °C). Olefins (primarily ethylene and propylene) were also produced with a carbon yield of 5.4% carbon. The biomass weight hourly space velocity and the reactor temperature can be used to control both aromatic yield and selectivity. At low biomass WHSV the more valuable monocyclic aromatics are produced and the formation of less valuable polycyclic aromatics is inhibited. Lowering the reaction temperature also results in more valuable monocyclic aromatics. The olefins produced during the reaction can be recycled to the reactor to produce additional aromatics. Propylene is more reactive than ethylene. Co-feeding propylene to the reactor results in a higher aromatic yield in both continuous reactors and higher conversion of the intermediate furan in the fixed bed reactor. When olefins are recycled aromatic yields from wood of 20% carbon can be obtained. After ten reaction–regeneration cycles there were metal impurities deposited on the catalyst, however, the acid sites on the zeolite are not affected. Of the three reactors tested the batch pyroprobe reactor yielded the most aromatics, however, the aromatic product is largely naphthalene. The continuous reactors produce less naphthalene and the sum of aromatics plus olefin products is higher than the pyroprobe reactor.

  15. Comparative study on pyrolysis of lignocellulosic and algal biomass using a thermogravimetric and a fixed-bed reactor.

    PubMed

    Yuan, Ting; Tahmasebi, Arash; Yu, Jianglong

    2015-01-01

    Pyrolysis characteristics of four algal and lignocellulosic biomass samples were studied by using a thermogravimetric analyzer (TGA) and a fixed-bed reactor. The effects of pyrolysis temperature and biomass type on the yield and composition of pyrolysis products were investigated. The average activation energy for pyrolysis of biomass samples by FWO and KAS methods in this study were in the range of 211.09-291.19kJ/mol. CO2 was the main gas component in the early stage of pyrolysis, whereas H2 and CH4 concentrations increased with increasing pyrolysis temperature. Bio-oil from Chlorellavulgaris showed higher content of nitrogen containing compounds compared to lignocellulosic biomass. The concentration of aromatic organic compounds such as phenol and its derivatives were increased with increasing pyrolysis temperature up to 700°C. FTIR analysis results showed that with increasing pyrolysis temperature, the concentration of OH, CH, CO, OCH3, and CO functional groups in char decreased sharply. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Effects of biomass type, blend composition, and co-pyrolysis temperature on hybrid coal quality

    NASA Astrophysics Data System (ADS)

    Sasongko, Dwiwahju; Wulandari, Winny; Rubani, Inga Shaffira; Rusydiansyah, Rifqi

    2017-01-01

    An experimental study on co-pyrolysis of coal with biomass wastes to produce hybrid coal was conducted to investigate the effects of important process variables, namely biomass type (rice husk and sawdust), blend composition, and co-pyrolysis temperature on the quality of hybrid coal. The experiments were carried out using a vertical tubular furnace equipped with temperature controller to maintain the co-pyrolysis reactor at a given temperature. Nitrogen gas was introduced into the furnace to create an inert environment preventing the sample from burning. A known mass of solid sample consisting of manually granulated blend of coal and biomass with binder in spherical shape was contained in a basket made of stainless sieve. After a given residence time, the sample was taken from the furnace. The blend sample prior to experiment and the produced hybrid coal were then characterized for its proximate analysis, ultimate analysis and calorific value. Experimental findings suggested that by increasing co-pyrolysis temperature from 200 to 400 °C, the calorific value of hybrid coal will increase by 14.5-17.7% to be 5585-7060 kcal/kg. It was also showed that 30% increase in the biomass content in the fuel blend would produce a hybrid coal that emitting up to 25.9% less in CO2 when used for combustion, although its calorific value decreased down to 8% compared to the biomass blend. It is shown that hybrid coal obtained from this study is comparable in calorific value to bituminous coal, thus suitable for power plant while being more environmentally friendly.

  17. Influence of biomass blending on pyrolysis process using TGA-FTIR technique

    NASA Astrophysics Data System (ADS)

    Bibrzycki, Jakub; Katelbach-Woźniak, Anna; Szlek, Andrzej

    2014-08-01

    Devolatilization is the most important step in the biomass combustion. It is beneficial to use a fuel, which releases volatiles in a wider range of temperature that make easier proper air distribution. The main objective of this paper is influence investigation of biomass mixing on devolatilization process. Thermobalance coupled with FTIR spectrometer has been used for investigation of devolatilization process and analysis of released gases composition. For the experiments inert atmosphere, sample mass of 50 mg and heating rate of 10 K/min have been used. As investigated fuels, the most popular types of biomass such as pine, willow and wheat straw have been used. Results show that by mixing different types of biomasses one can influence maximal rate of pyrolysis (DTGmax), corresponding temperature and composition of released volatiles. Results prove existence of interactions between different sorts of biomass.

  18. 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.

  19. 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...

  20. [Influence of urea formaldehyde resin on pyrolysis of biomass: a modeling study by TG-FTIR].

    PubMed

    Li, Si-jin; Mu, Jun; Zhang, Yu

    2014-06-01

    Pyrolysis is an efficient and recycling way to utilize waste wood-based panels, in which urea-formaldehyde resin (UF) is the main difference between wood-based board and other kinds of biomass. The present paper studied the three main components (cellulose, hemicelluloses, lignin) of poplar wood, in order to effectively and environmentally utilize or dispose of waste wood-based panels with pyrolysis technique, to study the influence of urea formaldehyde resin on pyrolytic characteristic of wood during the process of the pyrolysis of waste wood-based panels, and to in-depth explore the mechanism of the effect of UF on each component of wood. Innovatively, the weight-loss character and gas evolution rule of the model (made from cellulose, xylan and lignin, based on the chemical components stud of poplar wood), the main components as well as the ones mixed with UF were analyzed by TG-FTIR (thermogravimetric analyzer coupled to a Fourier transform infrared spectrometer). Results indicated that UF promoted the generation of water and carboxylic acid substances during the cellulose pyrolysis process. UF combined with lignin, formed some kind of unstable nitrogenous structure which produced a large amount of NH3, which took part in the low-temperature (200-300 degrees C) pyrolysis of lignin, and directly affected the production of pyrolysis products. It can be concluded that during the process of the pyrolysis of waste wood-based panels, lignin was the one that UF mainly impacted among the three main components of wood.

  1. MINIMIZING NET CO2 EMISSIONS BY OXIDATIVE CO-PYROLYSIS OF COAL / BIOMASS BLENDS

    SciTech Connect

    Todd Lang; Robert Hurt

    2001-12-23

    This study presents a set of thermodynamic calculations on the optimal mode of solid fuel utilization considering a wide range of fuel types and processing technologies. The technologies include stand-alone combustion, biomass/coal cofiring, oxidative pyrolysis, and straight carbonization with no energy recovery but with elemental carbon storage. The results show that the thermodynamically optimal way to process solid fuels depends strongly on the specific fuels and technologies available, the local demand for heat or for electricity, and the local baseline energy-production method. Burning renewable fuels reduces anthropogenic CO{sub 2} emissions as widely recognized. In certain cases, however, other processing methods are equally or more effective, including the simple carbonization or oxidative pyrolysis of biomass fuels.

  2. Pyrolysis of oil palm empty fruit bunch biomass pellets using multimode microwave irradiation.

    PubMed

    Salema, Arshad Adam; Ani, Farid Nasir

    2012-12-01

    Oil palm empty fruit bunch pellets were subjected to pyrolysis in a multimode microwave (MW) system (1 kW and 2.45 GHz frequency) with and without the MW absorber, activated carbon. The ratio of biomass to MW absorber not only affected the temperature profiles of the EFB but also pyrolysis products such as bio-oil, char, and gas. The highest bio-oil yield of about 21 wt.% was obtained with 25% MW absorber. The bio-oil consisted of phenolic compounds of about 60-70 area% as detected by GC-MS and confirmed by FT-IR analysis. Ball lightning (plasma arc) occurred due to residual palm oil in the EFB biomass without using an MW absorber. The bio-char can be utilized as potential alternative fuel because of its heating value (25 MJ/kg). Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. 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.

  4. 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.

  5. 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.

  6. Chemicals from Lignin by Catalytic Fast Pyrolysis, from Product Control to Reaction Mechanism.

    PubMed

    Ma, Zhiqiang; Custodis, Victoria; Hemberger, Patrick; Bährle, Christian; Vogel, Frédéric; Jeschk, Gunnar; van Bokhoven, Jeroen A

    2015-01-01

    Conversion of lignin into renewable and value-added chemicals by thermal processes, especially pyrolysis, receives great attention. The products may serve as feedstock for chemicals and fuels and contribute to the development of a sustainable society. However, the application of lignin conversion is limited by the low selectivity from lignin to the desired products. The opportunities for catalysis to selectively convert lignin into useful chemicals by catalytic fast pyrolysis and our efforts to elucidate the mechanism of lignin pyrolysis are discussed. Possible research directions will be identified.

  7. Anselme payen award lecture. Chemistry of pyrolysis and of combustion of biomass

    SciTech Connect

    Richards, G.N.

    1995-12-01

    Thermochemical processing remains one of the most promising approaches to utilization of biomass. Yet much remains to be learned of the chemistry involved, especially for the polysaccharide components. This lecture will survey some recent advances in the understanding of the chemical mechanisms in pyrolysis of polysaccharides, especially for cellulose and hemicelluloses. The effects of trace inorganics in control of pyrolysis mechanisms will be emphasized. The effects of position and of orientation of glycosidic linkages will be considered, as will the impact of the presence of lignin. The chemical factors which influence the combustion of biomass are of importance in building fires and in forest and range fires. The volatile products (emissions) from such fires are of significance in world atmospheric and in local toxicological terms and they are considerably influenced by fuel chemistry. This combustion of biomass, especially in the smolder mode, has many features which are closely related to pyrolysis and this lecture will seek to emphasize the synergism of concepts between these two types of thermochemistry.

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

    SciTech Connect

    Han, J.; Elgowainy, A.; Palou-Rivera, I.; Dunn, J.B.; Wang, M.Q.

    2011-12-01

    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. At 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 fuel

  9. 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.

  10. Pyrolysis kinetics study of three biomass solid wastes for thermochemical conversion into liquid fuels

    NASA Astrophysics Data System (ADS)

    Tuly, S. S.; Parveen, M.; Islam, M. R.; Rahman, M. S.; Haniu, H.

    2017-06-01

    Pyrolysis has been considered as the most efficient way of producing liquid fuel from biomass and its wastes. In this study the thermal degradation characteristics and pyrolysis kinetics of three selected biomass samples of Jute stick (Corchorus capsularis), Japanese cedar wood (Cryptomeria japonica) and Tamarind seed (Tamarindus indica) have been investigated in a nitrogen atmosphere at heating rates of 10°C/min and 60°C/min over a temperature range of 30°C to 800°C. The weight loss region for the three biomass solid wastes has shifted to a higher temperature range and the weight loss rate has increased with increasing heating rate. In this case, the three biomass samples have represented the similar behavior. The initial reaction temperature has decreased with increasing heating rate but the reaction range and reaction rate have increased. The percentage of total weight loss is higher for cedar wood than jute stick and tamarind seed. For the three biomass wastes, the overall rate equation has been modeled properly by one simplified equation and from here it is possible to determine kinetic parameters of unreacted materials based on Arrhenious form. The calculated rate equation compares thoroughly well with the measured TG and DTG data.

  11. 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.

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

    SciTech Connect

    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 from 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.

  13. 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...

  14. Biomass pyrolysis: thermal decomposition mechanisms of furfural and benzaldehyde.

    PubMed

    Vasiliou, AnGayle K; Kim, Jong Hyun; Ormond, Thomas K; Piech, Krzysztof M; Urness, Kimberly N; Scheer, Adam M; Robichaud, David J; Mukarakate, Calvin; Nimlos, Mark R; Daily, John W; Guan, Qi; Carstensen, Hans-Heinrich; Ellison, G Barney

    2013-09-14

    The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 μsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.

  15. Biomass pyrolysis: Thermal decomposition mechanisms of furfural and benzaldehyde

    NASA Astrophysics Data System (ADS)

    Vasiliou, AnGayle K.; Kim, Jong Hyun; Ormond, Thomas K.; Piech, Krzysztof M.; Urness, Kimberly N.; Scheer, Adam M.; Robichaud, David J.; Mukarakate, Calvin; Nimlos, Mark R.; Daily, John W.; Guan, Qi; Carstensen, Hans-Heinrich; Ellison, G. Barney

    2013-09-01

    The thermal decompositions of furfural and benzaldehyde have been studied in a heated microtubular flow reactor. The pyrolysis experiments were carried out by passing a dilute mixture of the aromatic aldehydes (roughly 0.1%-1%) entrained in a stream of buffer gas (either He or Ar) through a pulsed, heated SiC reactor that is 2-3 cm long and 1 mm in diameter. Typical pressures in the reactor are 75-150 Torr with the SiC tube wall temperature in the range of 1200-1800 K. Characteristic residence times in the reactor are 100-200 μsec after which the gas mixture emerges as a skimmed molecular beam at a pressure of approximately 10 μTorr. Products were detected using matrix infrared absorption spectroscopy, 118.2 nm (10.487 eV) photoionization mass spectroscopy and resonance enhanced multiphoton ionization. The initial steps in the thermal decomposition of furfural and benzaldehyde have been identified. Furfural undergoes unimolecular decomposition to furan + CO: C4H3O-CHO (+ M) → CO + C4H4O. Sequential decomposition of furan leads to the production of HC≡CH, CH2CO, CH3C≡CH, CO, HCCCH2, and H atoms. In contrast, benzaldehyde resists decomposition until higher temperatures when it fragments to phenyl radical plus H atoms and CO: C6H5CHO (+ M) → C6H5CO + H → C6H5 + CO + H. The H atoms trigger a chain reaction by attacking C6H5CHO: H + C6H5CHO → [C6H6CHO]* → C6H6 + CO + H. The net result is the decomposition of benzaldehyde to produce benzene and CO.

  16. Obtaining fermentable sugars by dilute acid hydrolysis of hemicellulose and fast pyrolysis of cellulose.

    PubMed

    Jiang, Liqun; Zheng, Anqing; Zhao, Zengli; He, Fang; Li, Haibin; Liu, Weiguo

    2015-04-01

    The objective of this study was to get fermentable sugars by dilute acid hydrolysis of hemicellulose and fast pyrolysis of cellulose from sugarcane bagasse. Hemicellulose could be easily hydrolyzed by dilute acid as sugars. The remained solid residue of acid hydrolysis was utilized to get levoglucosan by fast pyrolysis economically. Levoglucosan yield from crystalline cellulose could be as high as 61.47%. Dilute acid hydrolysis was also a promising pretreatment for levoglucosan production from lignocellulose. The dilute acid pretreated sugarcane bagasse resulted in higher levoglucosan yield (40.50%) in fast pyrolysis by micropyrolyzer, which was more effective than water washed (29.10%) and un-pretreated (12.84%). It was mainly ascribed to the effective removal of alkali and alkaline earth metals and the accumulation of crystalline cellulose. This strategy seems a promising route to achieve inexpensive fermentable sugars from lignocellulose for biorefinery. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Non-isothermal pyrolysis of de-oiled microalgal biomass: Kinetics and evolved gas analysis.

    PubMed

    Maurya, Rahulkumar; Ghosh, Tonmoy; Saravaia, Hitesh; Paliwal, Chetan; Ghosh, Arup; Mishra, Sandhya

    2016-12-01

    Non-isothermal (β=5, 10, 20, 35°C/min) pyrolysis of de-oiled microalgal biomass (DMB) of Chlorella variabilis was investigated by TGA-MS (30-900°C, Argon atmosphere) to understand thermal decomposition and evolved gas analysis (EGA). The results showed that three-stage thermal decomposition and three volatilization zone (100-400°C, 400-550°C and 600-750°C) of organic matters during pyrolysis. The highest rate of weight-loss is 8.91%/min at 302°C for 35°C/min heating-rate. Kinetics of pyrolysis were investigated by iso-conversional (KAS, FWO) and model-fitting (Coats-Redfern) method. For Zone-1and3, similar activation energy (Ea) is found in between KAS (α=0.4), FWO (α=0.4) and Avrami-Erofe'ev (n=4) model. Using the best-fitted kinetic model Avrami-Erofe'ev (n=4), Ea values (R(2)=>0.96) are 171.12 (Zone-1), 404.65 (Zone-2) and 691.42kJ/mol (Zone-3). EGA indicate the abundance of most gases observed consequently between 200-300°C and 400-500°C. The pyrolysis of DMB involved multi-step reaction mechanisms for solid-state reactions having different Ea values. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Tar reduction in pyrolysis vapours from biomass over a hot char bed.

    PubMed

    Gilbert, P; Ryu, C; Sharifi, V; Swithenbank, J

    2009-12-01

    The behaviour of pyrolysis vapours over char was investigated in order to maximise tar conversion for the development of a new fixed bed gasifier. Wood samples were decomposed at a typical pyrolysis temperature (500 degrees C) and the pyrolysis vapours were then passed directly through a tar cracking zone in a tubular reactor. The product yields and properties of the condensable phases and non-condensable gases were studied for different bed lengths of char (0-450 mm), temperatures (500-800 degrees C), particle sizes (10 and 15 mm) and nitrogen purge rates (1.84-14.70 mm/s). The carbon in the condensable phases showed about 66% reduction by a 300 mm long char section at 800 degrees C, compared to that for pyrolysis at 500 degrees C. The amount of heavy condensable phase decreased with increasing temperature from about 18.4 wt% of the biomass input at 500 degrees C to 8.0 wt% at 800 degrees C, forming CO, H(2) and other light molecules. The main mode of tar conversion was found to be in the vapour phase when compared to the results without the presence of char. The composition of the heavy condensable phase was simplified into much fewer secondary and tertiary tar components at 800 degrees C. Additional measures were required to maximise the heterogeneous effect of char for tar reduction.

  19. 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.

  20. Superheated steam pyrolysis of biomass elemental components and Sugi (Japanese cedar) for fuels and chemicals.

    PubMed

    Sagehashi, Masaki; Miyasaka, Noritaka; Shishido, Hiromu; Sakoda, Akiyoshi

    2006-07-01

    To develop a novel noncatalytic biomass refinery process that can be used as a portable process, superheated steam pyrolysis was investigated to produce both carbonized solid fuels and chemicals using a large-scale reactor. Individual biomass components and native biomass (Sugi, Japanese cedar) were pyrolyzed. Between 150 and 400 degrees C, the vaporizing fractions of cellulose, xylan, and kraft lignin were summarized using a numerical model. Cellulose was converted to glycolaldehyde, furfural, 5-hydroxymethyl furfural and levoglucosan, whereas xylan was converted to glycolaldehyde, furfural, and acetic acid. Kraft lignin produced a slight yield of phenol and guaiacol. The total vaporization fraction of Sugi and its vaporizing rate were explained sufficiently using a numerical model based on the weighted average of the vaporizing properties of the individual components. However, the yields of phenol, guaiacol, and acetic acid were underestimated, while the yields of furfurals and levoglucosan were overestimated. Possible synergetic effects among chemicals in the superheated steam pyrolysis of native biomass were also discussed.

  1. Optimization of Biofuel and Biochar Production from the Slow Pyrolysis of Biomass

    NASA Astrophysics Data System (ADS)

    Fang, J.; Gao, B.; Nsf Reu in Water Resources

    2010-12-01

    Slow pyrolysis was performed on biomass samples (i.e., energy cane and air potato) to determine the most energy efficient conditions for producing biofuel and biochar. The potential of air potato as a source of fuel and char was also investigated. Dry biomass samples of 10, 15 and 20 g were heated in a reactor at a final temperatures of 300, 450, or 600 °C, and the minimum amount of time required to complete pyrolysis was recorded. Maximum biochar yield was obtained at 300°C for both energy cane and air potato at all masses, and maximum bio-oil yield was obtained at 450°C for all samples. Pyrolysis required the least amount of time at 450°C. Bio-oil yields for air potato were slightly lower than that of energy cane, while biochar yield was slightly higher. Since air potato showed similar product yields to energy cane, this indicates it has potential to be a good feedstock for biofuel and biochar productions.

  2. 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.

  3. 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.

  4. 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

  5. Effect of Cellulose, Hemi-cellulose and Lignin Compositions in Woody and Grass Biomass on Pyrolysis Process

    NASA Astrophysics Data System (ADS)

    Okumura, Yukihiko; Okada, Takuya; Okazaki, Ken

    This paper reports on the pyrolysis process of various biomass materials in a thermobalance. In particular, the primary yields of total volatiles, tar and non-condensable gases, together with the composition of non-condensable gases, are measured as a function of temperature. The use of a high-intensity infrared heating source, in conjunction with a non-absorbing carrier gas (viz. argon), is reported to reduce the significance of secondary gas-phase pyrolysis reactions. The results indicate that the pyrolysis process of wood and grass biomass (tar and gas evolution process) is greatly affected by the main composition (cellulose, hemicellulose and lignin) and the linear trends with atomic H/C ratio are observed in the tar yield, total volatile yield CO, CO2 and CH4 yields. The volatile yields of wood and grass biomass are predicted based only on the values of ultimate analysis of the biomass.

  6. Catalytic Hydroprocessing of Fast Pyrolysis Bio-oil from Pine Sawdust

    SciTech Connect

    Elliott, Douglas C.; Hart, Todd R.; Neuenschwander, Gary G.; Rotness, Leslie J.; Olarte, Mariefel V.; Zacher, Alan H.; Solantausta, Yrjo

    2012-06-01

    Catalytic hydroprocessing has been applied to the fast pyrolysis liquid product (bio-oil) from softwood biomass in a bench-scale continuous-flow fixed-bed reactor system. The intent of the research was to develop process technology to convert the bio-oil into a petroleum refinery feedstock to supplement fossil energy resources and to displace imported feedstock. This paper is focused on the process experimentation and product analysis. The paper describes the experimental methods used and relates the results of the product analyses. A range of operating parameters including temperature, and flow-rate were tested with bio-oil derived from pine wood as recovered and pyrolyzed in the pilot pyrolyzer of Metso Power in Tampere, Finland. Effects of time on stream and catalyst activity were assessed. Details of the process results were presented included product yields and hydrogen consumption. Detailed analysis of the products were provided including elemental composition and product descriptors such as density, viscosity and Total Acid Number (TAN). In summation, the paper provides an initial understanding of the efficacy of hydroprocessing as applied to the Finnish pine bio-oil.

  7. Techno-economic analysis of monosaccharide production via fast pyrolysis of lignocellulose.

    PubMed

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

    2013-01-01

    The economic feasibility of a facility producing monosaccharides, hydrogen and transportation fuels via fast pyrolysis and upgrading pathway was evaluated by modeling a 2000 dry metric ton biomass/day facility using Aspen Plus®. Equipment sizing and cost were based on Aspen Economic Evaluation® software. The results indicate that monosaccharide production capacity could reach 338 metric tons/day. Co-product yields of hydrogen and gasoline were 23.4 and 141 metric tons/day, respectively. The total installed equipment and total capital costs were estimated to be $210 million and $326 million, respectively. A facility internal rate of return (IRR) of 11.4% based on market prices of $3.33/kg hydrogen, $2.92/gal gasoline and diesel, $0.64/kg monosaccharide was calculated. Sensitivity analysis demonstrates that fixed capital cost, feedstock cost, product yields, and product credits have the greatest impacts on facility IRR. Further research is needed to optimize yield of sugar via the proposed process to improve economic feasibility.

  8. 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

  9. Production of phenols and biofuels by catalytic microwave pyrolysis of lignocellulosic biomass.

    PubMed

    Bu, Quan; Lei, Hanwu; Ren, Shoujie; Wang, Lu; Zhang, Qin; Tang, Juming; Ruan, Roger

    2012-03-01

    Catalytic microwave pyrolysis of biomass using activated carbon (AC) was investigated to determine the effects of pyrolytic conditions on the yields of phenol and phenolics. Bio-oils with high concentrations of phenol (38.9%) and phenolics (66.9%) were obtained. These levels were higher than those obtained by pyrolysis without AC addition and were closely related to the decomposition of lignin. A high concentration of esters (42.2% in the upgraded bio-oil) was obtained in the presence of Zn powder as catalyst and formic acid/ethanol as reaction medium. Most of the esters identified by GC-MS were long chain fatty acid esters. The high content of phenols and esters obtained in this study can be used as partial replacement of petroleum fuels after separation of oxygenates or as feedstock for organic syntheses in the chemical industry after purification.

  10. Effects of inherent alkali and alkaline earth metallic species on biomass pyrolysis at different temperatures.

    PubMed

    Hu, Song; Jiang, Long; Wang, Yi; Su, Sheng; Sun, Lushi; Xu, Boyang; He, Limo; Xiang, Jun

    2015-09-01

    This work aimed to investigate effects of inherent alkali and alkaline earth metallic species (AAEMs) on biomass pyrolysis at different temperatures. The yield of CO, H2 and C2H4 was increased and that of CO2 was suppressed with increasing temperature. Increasing temperature could also promote depolymerization and aromatization reactions of active tars, forming heavier polycyclic aromatic hydrocarbons, leading to decrease of tar yields and species diversity. Diverse performance of inherent AAEMs at different temperatures significantly affected the distribution of pyrolysis products. The presence of inherent AAEMs promoted water-gas shift reaction, and enhanced the yield of H2 and CO2. Additionally, inherent AAEMs not only promoted breakage and decarboxylation/decarbonylation reaction of thermally labile hetero atoms of the tar but also enhanced thermal decomposing of heavier aromatics. Inherent AAEMs could also significantly enhance the decomposition of levoglucosan, and alkaline earth metals showed greater effect than alkali metals. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Catalytic pyrolysis of wood biomass in an auger reactor using calcium-based catalysts.

    PubMed

    Veses, A; Aznar, M; Martínez, I; Martínez, J D; López, J M; Navarro, M V; Callén, M S; Murillo, R; García, T

    2014-06-01

    Wood catalytic pyrolysis using calcium-based materials was studied in an auger reactor at 450°C. Two different catalysts, CaO and CaO·MgO were evaluated and upgraded bio-oils were obtained in both cases. Whilst acidity and oxygen content remarkable decrease, both pH and calorific value increase with respect to the non-catalytic test. Upgrading process was linked to the fact that calcium-based materials could not only fix the CO2-like compounds but also promoted the dehydration reactions. In addition, process simulation demonstrated that the addition of these catalysts, especially CaO, could favour the energetic integration since a lowest circulation of heat carrier between combustor and auger reactor should be needed. An energy self-sustained system was obtained where thermal energy required for biomass drying and for pyrolysis reaction was supplied by non-condensable gas and char combustion, respectively.

  12. 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 NH3 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 H2 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

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

    SciTech Connect

    Yung, Matthew M.; Starace, Anne K.; Mukarakate, Calvin; Crow, Allison M.; Leshnov, Marissa A.; Magrini, Kimberly A.

    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 on 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 NH3 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 H2 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.

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

    SciTech Connect

    Yung, Matthew M.; Starace, Anne K.; Mukarakate, Calvin; Crow, Allison M.; Leshnov, Marissa A.; Magrini, Kimberly A.

    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 on 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 NH3 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 H2 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.

  15. 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.

  16. 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.

  17. 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.

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

    SciTech Connect

    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 longer 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.

  19. 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.

  20. Release of fuel-bound nitrogen in biomass during high temperature pyrolysis and gasification

    SciTech Connect

    Zhou, J.; Masutani, S.M.; Ishimura, D.M.; Turn, S.Q.; Kinoshita, C.M.

    1997-12-31

    Pyrolysis and gasification of two biomass feedstocks with significantly different fuel-bound nitrogen (FBN) content were investigated to determine the effect of operating conditions on the partitioning of FBN among gas species. Experiments were performed in a bench-scale, indirectly-heated, fluidized bed reactor. Data were obtained over a range of temperatures and equivalence ratios representative of commercial biomass gasification processes. An assay of all major nitrogenous components of the gasification products was performed for the first time, providing a clear accounting of the evolution of FBN. Results indicate that: (1) NH{sub 3} is the dominant nitrogenous gas species produced during pyrolysis of biomass; (2) the majority of FBN is converted to NH{sub 3} or N{sub 2} during gasification; relative levels of NH{sub 3} and N{sub 2} are determined by thermochemical reactions which are affected strongly by temperature; (3) N{sub 2} appears to be produced from NH{sub 3} in the gas phase.

  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. Influence of inorganic compounds on char formation and quality of fast pyrolysis oils

    SciTech Connect

    Agbleyor, F.A.; Besler, S.; Montane, D.

    1995-12-01

    Inorganic compounds, especially potassium, calcium, sodium, silicon, phosphorus, and chlorine, are the main constituents of ash in biomass feedstocks. The concentrations of ash in biomass feedstocks range from less than 1% in softwoods to 15% in herbaceous biomass and agricultural residues. During biomass pyrolysis, these inorganics, especially potassium and calcium, catalyze both decomposition and char formation reactions. Decomposition reactions may either result in levoglucosan-rich or hydroxyacetaldehyde-rich pyrolysis products depending on the concentration of the ash in the feedstocks. The catalytic effect of the ash levels off at high organic ion concentrations. Chars formed during these reactions invariably end up in the pyrolysis oils (biofuel oils). A high proportion of the alkali metals in the ash are sequestered in the chars. The presence of high concentrations of alkali metals in the biofuel oils make them unsuitable for combustion in boilers, diesel engines, and in turbine operations. The highest concentration of alkali metals are found in herbaceous feedstocks and agricultural residue biofuel oils. Leaching studies conducted on the chars suspended in the oils showed no leaching of the alkali metals from the chars into the oils. Our data suggest that hot gas filtration of the oils can effectively reduce the alkali metals contents of the biofuel oils to acceptable levels to be used as turbine, diesel engine, and boiler fuels.

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

    SciTech Connect

    Elliott, Douglas C.; Wang, Huamin; Rover, Majorie; Whitmer, Lysle; Smith, Ryan; Brown, Robert C.

    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 hydrotreating 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.

  4. 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

  5. Fast microwave-assisted catalytic pyrolysis of sewage sludge for bio-oil production.

    PubMed

    Xie, Qinglong; Peng, Peng; Liu, Shiyu; Min, Min; Cheng, Yanling; Wan, Yiqin; Li, Yun; Lin, Xiangyang; Liu, Yuhuan; Chen, Paul; Ruan, Roger

    2014-11-01

    In this study, fast microwave-assisted catalytic pyrolysis of sewage sludge was investigated for bio-oil production, with HZSM-5 as the catalyst. Pyrolysis temperature and catalyst to feed ratio were examined for their effects on bio-oil yield and composition. Experimental results showed that microwave is an effective heating method for sewage sludge pyrolysis. Temperature has great influence on the pyrolysis process. The maximum bio-oil yield and the lowest proportions of oxygen- and nitrogen-containing compounds in the bio-oil were obtained at 550°C. The oil yield decreased when catalyst was used, but the proportions of oxygen- and nitrogen-containing compounds were significantly reduced when the catalyst to feed ratio increased from 1:1 to 2:1. Essential mineral elements were concentrated in the bio-char after pyrolysis, which could be used as a soil amendment in place of fertilizer. Results of XRD analyses demonstrated that HZSM-5 catalyst exhibited good stability during the microwave-assisted pyrolysis of sewage sludge. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Guidelines for Transportation, Handling, and Use of Fast Pyrolysis Bio-Oil. Part 1. Flammability and Toxicity

    SciTech Connect

    Oasmaa, Anja; Kalli, Anssi; Lindfors, Christian; Elliott, Douglas C.; Springer, David L.; Peacocke, Cordner; Chiaramonti, David

    2012-05-04

    An alternative sustainable fuel, biomass-derived fast pyrolysis oil or 'bio-oil', is coming into the market. Fast pyrolysis pilot and demonstration plants for fuel applications producing tonnes of bio-oil are in operation, and commercial plants are under design. There will be increasingly larger amounts of bio-oil transportation on water and by land, leading to a need for specifications and supporting documentation. Bio-oil is different from conventional liquid fuels, and therefore must overcome both technical and marketing hurdles for its acceptability in the fuels market. A comprehensive Material Safety Data Sheet (MSDS) is required, backed with independent testing and certification. In order to standardise bio-oil quality specifications are needed. The first bio-oil burner fuel standard in ASTM (D7544) was approved in 2009. CEN standardisation has been initiated in Europe. In the EU a new chemical regulation system, REACH (Registration, Evaluation and Authorisation of Chemicals) is being applied. Registration under REACH has to be made if bio-oil is produced or imported to the EU. In the USA and Canada, bio-oil has to be filed under TOSCA (US Toxic Substances Control Act). In this paper the state of the art on standardisation is discussed, and new data for the transportation guidelines is presented. The focus is on flammability and toxicity.

  7. Prediction of product distribution in fine biomass pyrolysis in fluidized beds based on proximate analysis.

    PubMed

    Kim, Sung Won

    2015-01-01

    A predictive model was satisfactorily developed to describe the general trends of product distribution in fluidized beds of lignocellulosic biomass pyrolysis. The model was made of mass balance based on proximate analysis and an empirical relationship with operating parameters including fluidization hydrodynamics. The empirical relationships between product yields and fluidization conditions in fluidized bed pyrolyzers were derived from the data of this study and literature. The gas and char yields showed strong functions of temperature and vapor residence time in the pyrolyzer. The yields showed a good correlation with fluidization variables related with hydrodynamics and bed mixing. The predicted product yields based on the model well accorded well with the experimental data.

  8. 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 ...

  9. Quantitative 13C NMR characterization of fast pyrolysis oils

    SciTech Connect

    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.

  10. Characterization of various fast pyrolysis bio-oils by NMR spectroscopy

    USDA-ARS?s Scientific Manuscript database

    NMR spectroscopy, including 1H, 13 C and DEPT spectra were used to characterize fast pyrolysis oil from numerous energy crops and other agricultural feedstocks. The bio-oils studied were produced from swithchgrass, alfalfa stems, corn stover, guayule (whole plant and latex extracted bagasse) and ch...

  11. 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....

  12. 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...

  13. Activated Carbon Derived from Fast Pyrolysis Liquids Production of Agricultural Residues and Energy Crops

    USDA-ARS?s Scientific Manuscript database

    Fast pyrolysis is a thermochemical method that can be used for processing energy crops such as switchgrass, alfalfa, soybean straw, corn stover as well as agricultural residuals (broiler litter) for bio-oil production. Researchers with the Agriculture Research Service (ARS) of the USDA developed a 2...

  14. Mass balance, energy and exergy analysis of bio-oil production by fast pyrolysis

    USDA-ARS?s Scientific Manuscript database

    Mass, energy and exergy balances are analyzed for bio-oil production in a bench scale fast pyrolysis system developed by the USDA’s Agricultural Research Service (ARS) for the processing of commodity crops to fuel intermediates. Because mass balance closure is difficult to achieve due, in part, to ...

  15. 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.

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

    PubMed

    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

  17. 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

  18. 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

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

    SciTech Connect

    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 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. 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. Leaching behaviour and ecotoxicity evaluation of chars from the pyrolysis of forestry biomass and polymeric materials.

    PubMed

    Bernardo, M; Mendes, S; Lapa, N; Gonçalves, M; Mendes, B; Pinto, F; Lopes, H

    2014-09-01

    The main objective of this study was to assess the environmental risk of chars derived from the pyrolysis of mixtures of pine, plastics, and scrap tires, by studying their leaching potential and ecotoxicity. Relationships between chemical composition and ecotoxicity were established to identify contaminants responsible for toxicity. Since metallic contaminants were the focus of the present study, an EDTA washing step was applied to the chars to selectively remove metals that can be responsible for the observed toxicity. The results indicated that the introduction of biomass to the pyrolysis feedstock enhanced the acidity of chars and promote the mobilisation of inorganic compounds. Chars resulting from the pyrolysis of blends of pine and plastics did not produce ecotoxic eluates. A relationship between zinc concentrations in eluates and their ecotoxicity was found for chars obtained from mixtures with tires. A significant reduction in ecotoxicity was found when the chars were treated with EDTA, which was due to a significant reduction in zinc in chars after EDTA washing.

  1. Volatilisation of alkali and alkaline earth metallic species during the pyrolysis of biomass: differences between sugar cane bagasse and cane trash.

    PubMed

    Keown, Daniel M; Favas, George; Hayashi, Jun-ichiro; Li, Chun-Zhu

    2005-09-01

    Sugar cane bagasse and cane trash were pyrolysed in a novel quartz fluidised-bed/fixed-bed reactor. Quantification of the Na, K, Mg and Ca in chars revealed that pyrolysis temperature, heating rate, valence and biomass type were important factors influencing the volatilisation of these alkali and alkaline earth metallic (AAEM) species. Pyrolysis at a slow heating rate (approximately 10 K min(-1)) led to minimal (often <20%) volatilisation of AAEM species from these biomass samples. Fast heating rates (>1000 K s(-1)), encouraging volatile-char interactions with the current reactor configuration, resulted in the volatilisation of around 80% of Na, K, Mg and Ca from bagasse during pyrolysis at 900 degrees C. Similar behaviour was observed for monovalent Na and K with cane trash, but the volatilisation of Mg and Ca from cane trash was always restricted. The difference in Cl content between bagasse and cane trash was not sufficient to fully explain the difference in the volatilisation of Mg and Ca.

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

    SciTech Connect

    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. Thermochemical conversion technology options include both gasification and pyrolysis to enable the developing lignocellulosic biorefineries and maximize biomass resource utilization for production of biofuels.

  3. 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.

  4. Experimental study of cyclone pyrolysis - Suspended combustion air gasification of biomass.

    PubMed

    Zhao, Yijun; Feng, Dongdong; Zhang, Zhibo; Sun, Shaozeng; Zhou, Xinwei; Luan, Jiyi; Wu, Jiangquan

    2017-11-01

    Based on the original biomass cyclone gasifier, the cyclone pyrolysis-suspension combustion gasification technology was constituted with a bottom wind ring to build the biochar suspension combustion zone. This technology decouples the biomass pyrolysis, gasification (reduction reaction) and combustion (oxidation reaction) within the same device. With the feed amount and total air fixed, the effect of air rate arrangement on temperature distribution of the gasifier, syngas components and gasification parameters was studied. With the secondary air rate (0.20) and bottom air rate (0.50), the gasification efficiency was best, with gas heating value of 5.15MJ/Nm(3), carbon conversion rate of 71.50%, gasification efficiency of 50.80% and syngas yield of 1.29Nm(3)/kg. The device with biochar for the tar catalytic cracking was installed at the gasifier outlet, effectively reducing the tar content in syngas, with a minimum value of 1.02g/Nm(3). Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. GC-MS determination of polycyclic aromatic hydrocarbons evolved from pyrolysis of biomass.

    PubMed

    Fabbri, Daniele; Adamiano, Alessio; Torri, Cristian

    2010-05-01

    A method for the determination of polycyclic aromatic hydrocarbons (PAHs) in liquid pyrolysate of biomass (bio-oil) was developed with attention to greenness along with accuracy. Bio-oil obtained from preparative pyrolysis at 500 degrees C of poplar wood as representative biomass matrix was dissolved into acetonitrile (ACN). An aliquot of the ACN solution (0.1 mg bio-oil) was added with water (20% v/v) and spiked with perdeuterated standards, then PAHs were extracted with n-hexane and separated from phenolic interferents by silica gel solid-phase extraction (SPE). All 16 priority PAHs were detected at concentrations between 7.7 microg g(-1) (naphthalene) and 0.1 microg g(-1) (benz[a]anthracene) with RSD in the 6-23% range. Recovery of perdeuterated acenaphthene, phenanthrene and chrysene was 84, 93 and 90%, respectively. Results obtained from the analysis of bio-oil were used to evaluate the performance of analytical pyrolysis conducted with a heated platinum filament in off-line configuration. Two sampling procedures were compared: (1) sorption onto silica gel followed by elution with n-hexane (Py-SPE), (2) dynamic solid-phase micro-extraction followed by fibre cleanup with aqueous ammonia (Py-SPME). Emission levels of priority PAHs could be determined by Py-SPE with RSD in the 13-45% range, while Py-SPME was unsatisfactory for quantitation. Emission levels determined by Py-SPE fell in the 6.4-0.1 microg g(-1) range slightly higher than those calculated from bio-oil analysis. Both Py methods were adequate for screening purposes to assess the effect of catalysts on PAH formation. In particular, they agreed to show that the content of PAHs expected in bio-oil increased dramatically when pyrolysis was conducted over HZSM-5 zeolite.

  6. 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

  7. Novel energy crops for Mediterranean contaminated lands: Valorization of Dittrichia viscosa and Silybum marianum biomass by pyrolysis.

    PubMed

    Domínguez, María T; Madejón, Paula; Madejón, Engracia; Diaz, Manuel J

    2017-11-01

    Establishing energy crops could be a cost-efficient alternative towards the valorization of the plant biomass produced in contaminated lands, where they would not compete with food production for land use. Dittrichia viscosa and Silybum marianum are two native Mediterranean species recently identified as potential energy crops for degraded lands. Here, we present the first characterization of the decomposition of the biomass of these species during thermo-chemical conversion (pyrolysis). Using a greenhouse study we evaluated whether the quality of D. viscosa and S. marianum biomass for energy production through pyrolysis could be substantially influenced by the presence of high concentrations of soluble trace element concentrations in the growing substrate. For each species, biomass produced in two different soil types (with contrasted trace element concentrations and pH) had similar elemental composition. Behavior during thermal decomposition, activation energies and concentrations of pyrolysis gases were also similar between both types of soils. Average activation energy values were 295 and 300 kJ mol(-1) (for a conversion value of α = 0.5) for S. marianum and D. viscosa, respectively. Results suggest that there were no major effects of soil growing conditions on the properties of the biomass as raw material for pyrolysis, and confirm the interest of these species as energy crops for Mediterranean contaminated lands. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. 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.

  9. Combined pretreatment with torrefaction and washing using torrefaction liquid products to yield upgraded biomass and pyrolysis products.

    PubMed

    Chen, Dengyu; Mei, Jiaming; Li, Haiping; Li, Yiming; Lu, Mengting; Ma, Tingting; Ma, Zhongqing

    2017-03-01

    This study presented an approach to upgrade biomass and pyrolysis products using a process based on torrefaction liquid washing combined with torrefaction pretreatment. The torrefaction of cotton stalk was first conducted at 250°C for 30min and then the resulting torrefaction liquid products were collected and reused to wash cottonstalk. The pyrolysis of the original and pretreated cotton stalk was performed at 500°C for 15min in a fixed-bed reactor. The results indicated that the combined pretreatment obviously reduced the metallic species in cotton stalk, decreased the water and acids contents while promoted phenols in bio-oil, declined the ash content in biochar, as well as improved the heating value of non-condensable gas. Overall, the combined pretreatment did not only allow to reuse the liquid products issued from torrefaction pretreatment but also improved the quality of biomass and the pyrolysis products, making it a novel promising pretreatment method.

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

    SciTech Connect

    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 important 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 significant

  11. 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...

  12. 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.

  13. 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.

  14. 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

  15. Toxic potentiality of bio-oils, from biomass pyrolysis, in cultured cells and Caenorhabditis elegans.

    PubMed

    Chatterjee, Nivedita; Eom, Hyun-Jeong; Jung, Su-Hwa; Kim, Joo-Sik; Choi, Jinhee

    2014-12-01

    Bio-oils, which are multicomponent mixtures, were produced from two different biomass (rice straw (rice oil) and sawdust of oak tree (oak oil)) by using the slow pyrolysis process, and chemical compositional screening with GC-MS detected several hazardous compounds in both bio-oil samples. The two bio-oils vary in their chemical compositional nature and concentrations. To know the actual hazard potentialities of these bio-oils, toxicological assessments were carried out in a comparative approach by using in vitro (Jurkat T and HepG2 cell) as well as in vivo (Caenorhabditis elegans) systems. A dose-dependent increase in cytotoxicity, cell death (apoptosis), and genotoxicity were observed in cultured cell systems. Similarly, the in vivo system, C. elegans also displayed a dose-dependent decrease in survival. It was found that in comparison with rice oil, oak oil displayed higher toxicity to all models systems, and the susceptibility order of the model systems were Jurkat T > HepG2 > C. elegans. Pursuing the study further toward the underlying mechanism by exploiting the C. elegans mutants screening assay, the bio-oils seem to mediate toxicity through oxidative stress and impairment of immunity. Taken together, bio-oils compositions mainly depend on the feedstock used and the pyrolysis conditions which in turn modulate their toxic potentiality.

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

    DOE PAGES

    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

  17. KINETIC STUDY OF COAL AND BIOMASS CO-PYROLYSIS USING THERMOGRAVIMETRY

    SciTech Connect

    Wang, Ping; Hedges, Sheila; Chaudharib, Kiran; Turtonb, Richard

    2013-10-29

    The objectives of this study are to investigate thermal behavior of coal and biomass blends in inert gas environment at low heating rates and to develop a simplified kinetic model using model fitting techniques based on TGA experimental data. Differences in thermal behavior and reactivity in co-pyrolysis of Powder River Basin (PRB) sub-bituminous coal and pelletized southern yellow pine wood sawdust blends at low heating rates are observed. Coal/wood blends have higher reactivity compared to coal alone in the lower temperature due to the high volatile matter content of wood. As heating rates increase, weight loss rates increase. The experiment data obtained from TGA has a better fit with proposed two step first order reactions model compared single first order reaction model.

  18. 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.

  19. 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.

  20. Self-heating co-pyrolysis of excessive activated sludge with waste biomass: energy balance and sludge reduction.

    PubMed

    Ding, Hong-Sheng; Jiang, Hong

    2013-04-01

    In this work, co-pyrolysis of sludge with sawdust or rice husk was investigated. The results showed that the co-pyrolysis technology could be used to dispose of the excessive activated sludge without external energy input. The results also demonstrated that no obvious synergistic effect occurred except for heat transfer in the co-pyrolysis if the co-feeding biomass and sludge had similar thermogravimetric characteristics. The experimental results combined with calculation showed that adding sawdust accounting for 49.6% of the total feedstock or rice husk accounting for 74.7% could produce bio-oil to keep the energy balance of the co-pyrolysis system and self-heat it. The sludge from solar drying bed can be further reduced by 38.6% and 35.1% by weight when co-pyrolyzed with rice husk and sawdust, respectively. This study indicates that sludge reduction without external heat supply through co-pyrolysis of sludge with waste biomass is practically feasible.

  1. Determination of cadmium in water samples by fast pyrolysis-chemical vapor generation atomic fluorescence spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Jingya; Fang, Jinliang; Duan, Xuchuan

    2016-08-01

    A pyrolysis-vapor generation procedure to determine cadmium by atomic fluorescence spectrometry has been established. Under fast pyrolysis, cadmium ion can be reduced to volatile cadmium species by sodium formate. The presence of thiourea enhanced the efficiency of cadmium vapor generation and eliminated the interference of copper. The possible mechanism of vapor generation of cadmium was discussed. The optimization of the parameters for pyrolysis-chemical vapor generation, including pyrolysis temperature, amount of sodium formate, concentration of hydrochloric acid, and carrier argon flow rate were carried out. Under the optimized conditions, the absolute and concentration detection limits were 0.38 ng and 2.2 ng ml- 1, respectively, assuming that 0.17 ml of sample was injected. The generation efficiency of was 28-37%. The method was successfully applied to determine trace amounts of cadmium in two certified reference materials of Environmental Water (GSB07-1185-2000 and GSBZ 50009-88). The results were in good agreement with the certified reference values.

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

    PubMed

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

    2017-09-15

    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. Published by Elsevier Ltd.

  3. 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.

  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. 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.

  6. Analysis and comparison of biomass pyrolysis/gasification condensates: an interim report

    SciTech Connect

    Elliott, D.C.

    1985-09-01

    This report provides results of chemical and physical analysis of condensates from eleven biomass gasification and pyrolysis systems. The analyses were performed in order to provide more detailed data concerning these condensates for the different process research groups and to allow a determination of the differences in properties of the condensates as a function of reactor environment. 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, aqueous phases and, in some cases, both phases depending on the output of the particular reactor system. 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). The analytical data demonstrate 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 as a result of formation of polycyclic aromatic hydrocarbons in high concentrations. 55 refs., 13 figs., 6 tabs.

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

    SciTech Connect

    Oyama, Ted; Agblevor, Foster; Battaglia, Francine; Klein, Michael

    2013-01-18

    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. The 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.

  8. 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.

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

    SciTech Connect

    Klemetsrud, Bethany; Ukaew, Suchada; Thompson, Vicki S.; Thompson, David N.; Klinger, Jordan; Li, Lucia; Eatherton, Dominic; Puengprasert, Parin; Shonnard, David

    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&D 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 from 58

  10. 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

  11. 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.

  12. Pressurized fast-pyrolysis characteristics of typical Chinese coals with different ranks

    SciTech Connect

    Chunyu Li; Jiantao Zhao; Yitian Fang; Yang Wang

    2009-09-15

    The pressurized fast pyrolysis of three typical Chinese coals with different coal ranks (Huolinhe lignite, Shenmu bituminous coal, and Jincheng anthracite) was conducted on a self-made pressurized fixed-bed reactor. The physicochemical characteristics of the chars were studied via scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR). In addition, thermogravimetric analysis (TGA) at ambient pressure has been used to study the influence of the residence time, the pyrolysis temperature, and pressure on the gasification reactivity of residual chars. The results show that the change in char yield and reactivity with pressure, at a residence time of 1 min, is different from that at longer residence time. This is related to the changing impacts of the rapid primary release of volatiles and the slower secondary cracking reactions of the evolved tars and the graphitization of the char structure. Furthermore, as the coal rank, pyrolysis pressure, temperature, and residence time increase, the surface structure of the char becomes much denser, the degree of graphitization is enhanced, and the number of the functional groups is reduced, which lead to the decrease in the gasification reactivity of the coal char. 23 refs., 1 figs., 2 tabs.

  13. 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.

  14. 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

    2017-02-23

    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.

  15. Modeling of biomass to hydrogen via the supercritical water pyrolysis process

    SciTech Connect

    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 reasonable 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.

  16. 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.

  17. 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.

  18. 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).

  19. 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.

  20. 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.

  1. Comprehensive two dimensional gas chromatography with fast-quadrupole mass spectrometry detector analysis of polar compounds extracted from the bio-oil from the pyrolysis of sawdust.

    PubMed

    Schneider, Jaderson K; da Cunha, Michele E; dos Santos, Anaí L; Maciel, Gabriela P S; Brasil, Márcia C; Pinho, Andrea R; Mendes, Fábio L; Jacques, Rosângela A; Caramão, Elina B

    2014-08-22

    In this paper it is studied the most polar fractions of bio-oil produced by fast pyrolysis of Lignocel BK40-90 (sawdust from forest timber). The biomass was submitted to the pyrolysis in an existing FCC pilot plant that was adapted for this procedure. The equipment consists of a fluidized bed reactor with nitrogen injection. The unit operates with continuous biomass feeding and continuous solids circulation. The produced bio-oil was submitted to an aqueous alkaline extraction, isolating the acidic compounds that were analyzed by one-dimensional gas chromatography and comprehensive two-dimensional gas chromatography with quadrupole mass spectrometry detection (qMS). One hundred and thirty compounds (mainly phenols and ketones) were tentatively identified in the extract, some of them by the use of retention indexes. The main differences between chromatographic techniques were the substantial increasing in the peak capacity of GC×GC and the resolution of some co-elutions that occurred in GC/qMS. It is also possible to conclude that this extract is rich in important raw materials for the chemical industry and can be used for this end.

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

    SciTech Connect

    Meyer, Pimphan A.; Snowden-Swan, Lesley J.; Rappé, Kenneth G.; Jones, Susanne B.; Westover, Tyler L.; Cafferty, Kara G.

    2016-11-17

    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 yield 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.

  3. 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.

  4. Comparative analysis of pinewood, peanut shell, and bamboo biomass derived biochars produced via hydrothermal conversion and pyrolysis.

    PubMed

    Huff, Matthew D; Kumar, Sandeep; Lee, James W

    2014-12-15

    Biochars were produced from pinewood, peanut shell, and bamboo biomass through hydrothermal conversion (HTC) at 300 °C and comparatively by slow pyrolysis over a temperature range of 300, 400, and 500 °C. These biochars were characterized by FT-IR, cation exchange capacity (CEC) assay, methylene blue adsorption, as well as proximate and elemental analysis. The experimental results demonstrated higher retained oxygen content in biochars produced at lower pyrolysis temperatures and through HTC, which also correlated to the higher CEC of respective biochars. Furthermore, all types of biochar studied herein were capable of adsorption of methylene blue from solution and the adsorption did not appear to strongly correlate with CEC, indicating that the methylene blue adsorption appears to be dependent more upon the non-electrostatic molecular interactions such as the likely dispersive π-π interactions between the graphene-like sheets of the biochar with the aromatic ring structure of the dye, than the electrostatic CEC. A direct comparison of hydrothermal and pyrolysis converted biochars reveals that biochars produced through HTC have much higher CEC than the biochars produced by slow pyrolysis. Analysis by FT-IR reveals a higher retention of oxygen functional groups in HTC biochars; additionally, there is an apparent trend of increasing aromaticity of the pyrolysis biochars when produced at higher temperatures. The CEC value of the HTC biochar appears correlated with its oxygen functional group content as indicated by the FT-IR measurements and its O:C ratio. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. 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.

  6. 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.

  7. 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

  8. Effect of hot vapor filtration on the characterization of bio-oil from rice husks with fast pyrolysis in a fluidized-bed reactor.

    PubMed

    Chen, Tianju; Wu, Ceng; Liu, Ronghou; Fei, Wenting; Liu, Shiyu

    2011-05-01

    To produce high quality bio-oil from biomass using fast pyrolysis, rice husks were pyrolyzed in a 1-5 kg/h bench-scale fluidized-bed reactor. The effect of hot vapor filtration (HVF) was investigated to filter the solid particles and bio-char. The results showed that the total bio-oil yield decreased from 41.7% to 39.5% by weight and the bio-oil had a higher water content, higher pH, and lower alkali metal content when using HVF. One hundred and twelve different chemical compounds were detected by gas chromatography-mass spectrometry (GC-MS). The molecular weight of the chemical compounds from the condenser and the EP when the cyclone was coupled with HVF in the separation system decreased compared with those from the condenser and EP when only cyclone was used.

  9. Design, fabrication, operation and Aspen simulation of oil shale pyrolysis and biomass gasification process using a moving bed downdraft reactor

    NASA Astrophysics Data System (ADS)

    Golpour, Hassan

    Energy is the major facilitator of the modern life. Every developed and developing economy requires access to advanced sources of energy to support its growth and prosperity. Declining worldwide crude oil reserves and increasing energy needs has focused attention on developing existing unconventional fossil fuels like oil shale and renewable resources such as biomass. Sustainable, renewable and reliable resources of domestically produced biomass comparing to wind and solar energy is a sensible motivation to establish a small-scale power plant using biomass as feed to supply electricity demand and heat for rural development. The work in Paper I focuses on the possibility of water pollution from spent oil shale which should be studied before any significant commercial production is attempted. In Paper II, the proposed Aspen models for oil shale pyrolysis is to identify the key process parameters for the reactor and optimize the rate of production of syncrude from oil shale. The work in Paper III focuses on (1) Design and operation of a vertical downdraft reactor, (2) Establishing an optimum operating methodology and parameters to maximize syngas production through process testing. Finally in Paper IV, a proposed Aspen model for biomass gasification simulates a real biomass gasification system discussed in Paper III.

  10. 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.

  11. 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.

  12. Thermal behaviour and kinetics of alga Polysiphonia elongata biomass during pyrolysis.

    PubMed

    Ceylan, Selim; Topcu, Yıldıray; Ceylan, Zeynep

    2014-11-01

    The pyrolysis characteristics and kinetics of Polysiphonia elongata were investigated using a thermogravimetric analyzer. The main decomposition of samples occurred between 225 °C and 485 °C at heating rates of 5-40 °C/min; owing to release of 78-82% of total volatiles. The heating rate effected pyrolysis characteristics such as maximum devolatilization rate and decomposition temperature. However, total volatile matter yield was not significantly affected by heating rate. The activation energy of pyrolysis reaction was calculated by model free Friedman and Kissenger-Akahira-Sunose methods and mean values were 116.23 kJ/mol and 126.48 kJ/mol, respectively. A variance in the activation energy with the proceeding conversions was observed for the models applied, which shows that the pyrolysis process was composed of multi-step kinetics. The Coats-Redfern method was used to determine pre-exponential factor and reaction order. The obtained parameters were used in simulation of pyrolysis process and results were in a good agreement with experimental data. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Biocrude oils from the fast pyrolysis of poultry litter and hardwood

    SciTech Connect

    Agblevor, F.A.; Beis, S.; Kim, S.S.; Tarrant, R.; Mante, N.O.

    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. 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.

  14. 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.

  15. Pyrolysis of biomass and refuse-derived fuel performance in laboratory scale batch reactor

    NASA Astrophysics Data System (ADS)

    Kluska, Jacek; Klein, Marek; Kazimierski, Paweł; Kardaś, Dariusz

    2014-03-01

    The results of pyrolysis of pine chips and refuse derived fuel fractions are presented. The experiments were carried out in a pilot pyrolysis reactor. The feedstock was analyzed by an elemental analyzer and the X-ray fluorescence spectrometer to determine the elemental composition. To find out optimum conditions for pyrolysis and mass loss as a function of temperature the thermogravimetric analysis was applied. Gases from the thermogravimetric analysis were directed to the infrared spectrometer using gas-flow cuvette to online analysis of gas composition. Chemical composition of the produced gas was measured using gas chromatography with a thermal conductivity detector and a flame ionization detector. The product analysis also took into account the mass balance of individual products.

  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. 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...

  18. 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.

  19. 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

  20. New applications of X-ray tomography in pyrolysis of biomass: Biochar imaging

    SciTech Connect

    Jones, Keith; Ramakrishnan, Girish; Uchimiya, Minori; Orlov, Alexander

    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 to 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.

  1. Production of aromatic hydrocarbons via catalytic pyrolysis of biomass over fe-modified HZSM-5 zeolites

    USDA-ARS?s Scientific Manuscript database

    Iron modified HZSM-5 catalysts were prepared by partial ion exchange of NH4ZSM-5 with Fe (II) at three different loadings (1.4, 2.8 and 4.2 wt%), and their effectiveness for producing aromatic hydrocarbons from cellulose, cellobiose, lignin and switchgrass by catalytic pyrolysis were screened using ...

  2. 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...

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

    SciTech Connect

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

    2008-07-01

    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 yield 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.

  4. 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

  5. Pilot-Scale Biorefinery: Sustainable Transport Fuels from Biomass and Algal Residues via Integrated Pyrolysis, Catalytic Hydroconversion and Co-processing with Vacuum Gas Oil

    SciTech Connect

    Elliott, Douglas; Olarte, M. V.; Hart, T. R.

    2016-07-21

    Beginning in 2010, UOP, along with the Department of Energy and other project partners, designed a pathway for an integrated biorefinery to process solid biomass into transportation fuel blendstocks. The integrated biorefinery (IBR) would convert second generation feedstocks into pyrolysis oil which would then be upgraded into fuel blendstocks without the limitations of traditional biofuels.

  6. Field-to-Fuel Performance Testing of Lignocellulosic Feedstocks: An Integrated Study of the Fast Pyrolysis/Hydrotreating Pathway

    SciTech Connect

    Howe, Daniel T.; Westover, Tyler; Carpenter, Daniel; Santosa, Daniel M.; Emerson, Rachel; Deutch, Steve; Starace, Anne; Kutnyakov, Igor V.; Lukins, Craig D.

    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 high 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).

  7. 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.

  8. Production of low-oxygen bio-oil via ex situ catalytic fast pyrolysis and hydrotreating

    DOE PAGES

    Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; ...

    2017-06-29

    Catalytic fast pyrolysis (CFP) bio-oils with different organic oxygen contents (4-18 wt%) were prepared in a bench-scale dual fluidized bed reactor system by ex situ CFP of southern pine over HZSM-5, and the oils were subsequently hydrotreated over a sulfided CoMo catalyst at 170 bar. The goal was to determine the impact of the CFP oil oxygen content on hydrotreating requirements. The CFP oils with higher oxygen contents included a variety of oxygenates (phenols, methoxyphenols, carbonyls, anhydrosugars) whereas oxygenates in the 4 wt% oxygen oil were almost exclusively phenols. Phenols were the most recalcitrant oxygenates during hydrotreating as well, andmore » the hydrotreated oils consisted mainly of aromatic and partially saturated ring hydrocarbons. The temperature required to produce oil with <1% oxygen was approximately 350 °C for the CFP oil with the lowest oxygen content whereas temperatures around 400 °C were required for the other CFP oils. The carbon efficiency during hydrotreating slightly decreased as the CFP oil oxygen content increased but remained above 90% in all cases, and the carbon efficiency for the integrated process was dominated by the efficiency of the CFP process. In conclusion, a preliminary technoeconomic evaluation suggested that with the current zeolite-based CFP catalysts, it is economically beneficial to preserve carbon during CFP, at the expense of higher oxygen contents in the CFP oil.« less

  9. Steam reforming of bio-oil from rice husks fast pyrolysis for hydrogen production.

    PubMed

    Chen, Tianju; Wu, Ceng; Liu, Ronghou

    2011-10-01

    Steam reforming of two kinds of bio-oil from rice husks fast pyrolysis was conducted for hydrogen production at three temperatures (650, 750 and 850 °C) with Ni-based catalyst in a fixed-bed reactor. The gas composition and organic compounds in liquid condensate were detected by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS), respectively. In addition, the carbon deposition was also investigated. The results showed that the mole fraction range of hydrogen was within 55.8-61.3% at all temperatures and more hydrogen was produced at the higher temperature. The highest H₂ efficiency of bio-oil steam reforming was 45.33% when extra water was added. The bio-oil with lower content of chemical compounds has a higher H₂ efficiency, but its hydrogen volume was less. Analysis of the liquid condensate showed that most of the organic compounds were circularity compounds. The carbon deposition can decrease the bio-oil conversion, and it was easier to form at the temperature of 750 °C.

  10. Quality Control in Fast Pyrolysis Bio-Oil Production and Use

    SciTech Connect

    Oasmaa, Anja; Elliott, Douglas C.; Muller, Stefan

    2009-10-01

    This paper will focus on norms and standards for fast pyrolysis bio-oils. It will include the present status and address what still has to be done on bio-oil specifications and relevant test methods. The paper will address industrial needs in commercialization of the fuel oil use of bio-oil, including the registration application to the REACH program and its consequences within the European Union, as well as development of a standard within ASTM. The paper will discuss the most important properties of bio-oil and the variation in these properties among various bio-oils. It will address the issue of quality follow-up in bio-oil production, including the properties to be followed and the laboratory and on-line monitoring methods. The paper will provide a state of the art of fuel oil specifications, test methods, and testing procedures as they are applied to bio-oil. It will review the effort in support of the implementation of an ASTM standard including the methods validation work.

  11. Accumulation of inorganic impurities on HZSM-5 during catalytic fast pyrolysis of switchgrass

    USDA-ARS?s Scientific Manuscript database

    The fate of inorganic species present in switchgrass during fluidized bed catalytic pyrolysis over HZSM-5 catalysts was studied with emphasis on their accumulation on the catalyst. Five catalytic pyrolysis experiments were performed in two series, reusing the catalyst after each sample. Catalysts w...

  12. 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...

  13. 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...

  14. 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.

  15. Pyrolysis-GC-MS analysis of the formation and degradation stages of charred residues from lignocellulosic biomass.

    PubMed

    González-Vila, F J; Tinoco, P; Almendros, G; Martin, F

    2001-03-01

    The structural transformations undergone by lignocellulosic biomass (freeze-dried rye grass, Lolium rigidum) subjected to progressive isothermal heating (burning at 350 degrees C under oxidizing conditions for 30, 45, 60, 75, and 90 s) have been monitored by Curie-point pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). The pyrograms suggest that even charred residues after severe heating (carbon loss ca. 50%) still contain substantial concentrations of some resistant plant structural components. Several trends were observed when monitoring the relative concentrations of the different groups of pyrolysis compounds released during successive charring stages: (i) the tetrapyrrole moiety of chlorophylls is rapidly destroyed as indicated by the decreasing yields of pyrroles and pyrrolines, whereas the phytol backbone is comparatively more resistant, leading to phytadienes after dehydration and reduction; (ii) the increasing yields of imidazoles from progressively heated samples (maximum at 45 s stage) suggest accumulation of newly formed nitrogen-containing compounds that may survive natural fires; (iii) the lignin backbone shows a relative resistance, the yields of aromatic products pointing to progressive demethoxylation; and, (iv) a selective accumulation of recalcitrant alkyl material occurred, which is interpreted as the result of thermal condensation of hydrocarbons and fatty acids into macromolecular materials in the charred residue. In terms of the intensity of the isothermal heating, the yields of the different classes of alkyl compounds follow the order phytadienes < fatty acids < alkanes < wax esters < sterols.

  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. 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.

  18. Characterizations of Bio-char from Fast Pyrolysis of Meranti Wood Sawdust

    NASA Astrophysics Data System (ADS)

    Mazlan, M. A. F.; Uemura, Y.; Osman, N. B.; Yusup, S.

    2015-06-01

    In this research, Meranti wood sawdust (MWS) was pyrolyzed in a fixed bed drop- type pyrolyzer under an inert condition. The first part of the study is to determine the influence of pyrolysis temperature (450, 500 and 550 °C) on the yield of pyrolysis products. Pyrolysis of the waste MWS material generated the highest amount of bio-char with approximately 38 wt.% at pyrolysis temperature of 450 °C. Next, the char product (from pyrolysis at 450 °C) was analyzed to compare its characteristics with the raw MWS feedstock. The major component of the char is carbon element, significantly contributed to its high calorific value. TGA profile shows the MWS char could withstand high temperature of up to 400 °C. Under extensive heating, particle size of the bio-char from SEM images decreased due to breakage and shrinkage processes.

  19. Intermediate pyrolysis of biomass energy pellets for producing sustainable liquid, gaseous and solid fuels.

    PubMed

    Yang, Y; Brammer, J G; Mahmood, A S N; Hornung, A

    2014-10-01

    This work describes the use of intermediate pyrolysis system to produce liquid, gaseous and solid fuels from pelletised wood and barley straw feedstock. Experiments were conducted in a pilot-scale system and all products were collected and analysed. The liquid products were separated into an aqueous phase and an organic phase (pyrolysis oil) under gravity. The oil yields were 34.1 wt.% and 12.0 wt.% for wood and barley straw, respectively. Analysis found that both oils were rich in heterocyclic and phenolic compounds and have heating values over 24 MJ/kg. The yields of char for both feedstocks were found to be about 30 wt.%, with heating values similar to that of typical sub-bituminous class coal. Gas yields were calculated to be approximately 20 wt.%. Studies showed that both gases had heating values similar to that of downdraft gasification producer gas. Analysis on product energy yields indicated the process efficiency was about 75%.

  20. Mechanistic evaluation of polychlorinated dibenzo-p-dioxin, dibenzofuran and naphthalene isomer fingerprints in microwave pyrolysis of biomass.

    PubMed

    Gao, Qiuju; Cieplik, Mariusz K; Budarin, Vitaliy L; Gronnow, Mark; Jansson, Stina

    2016-05-01

    Isomer distribution patterns of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs) were investigated in microwave-assisted pyrolysis (MAP) products of woody biomass. The feedstocks included bark and impregnated wood. The results indicated that isomer distributions in MAP are more selective compared to those reported from wood burning and waste incineration. Favored formation of 4-MoCDF and highly selective chlorine substitution at the 2,4-position observed during MAP suggested a preferred formation pathway of PCDFs involving (chloro)phenol precursors followed by subsequent chlorination. The PCDD distribution was dominated by isomers typically formed from chlorophenol condensation at relatively low temperature. The PCN isomer distributions showed a tendency for sequential chlorination from non-substituted naphthalene at successive positions. The presence of isomers such as 1-MoCDD, 4-MoCDF, 1,2,3-TriCN with low thermodynamic stability indicates that kinetic factors may be important in the MAP process.

  1. 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.

  2. 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.

  3. Flash Pyrolysis of Biomass with Reactive and Non-Reactive Gases: Summary Report for Period July 1983 through September 1984

    SciTech Connect

    Steinberg M.; Fallon, P.T.; Sundaram, M.S.

    1984-10-01

    The purpose of this program is to study the conversion of biomass to liquid and gaseous hydrocarbon fuels and chemical feedstocks by a flash or rapid pyrolysis technique. During this period of study pine wood was flash pyrolyzed in atmospheres of methane and helium at a pressure of 50 psi and at temperatures up to 1050 C. The 1-inch I.D. entrained downflow tubular reactor was used in these experiments. Product yields of methane, ethane, ethylene, BTX, carbon monoxide and carbon dioxide were determined as a function of temperature and gas to wood ratio. Of particular interest were the ethylene and BTX yields. These represented as much as 29.6% and 24.6% of the carbon contained in the feed wood respectively when flash pyrolyzing in methane (flash methanolysls) and 14.7% and 9.7% when pyrolyzing in helium. In the case of flash methanolysis of wood the yields of ethylene and benzene increased with increasing methane to wood feed ratios. In the case of flash pyrolysis in helium the yields of ethylene and BTX decreased with increasing helium gas to wood feed ratios. These results indicate a mechanism by which a free radical reactive species originating from the wood interacts with the methane pyrolyzing gas to produce an enhanced yield of ethylene and benzene. The flash methanolysis of lignin extract from wood produced lower yields of ethylene, indicating the yields mainly originate from the cellulosic fractions of the wood. Some work was also performed on substituting wood ash for sillca flour (Cab-O-Sil) to allow free flow of wood particles through the entrained flow reactor. Preliminary process design and analysis indicates an economically competitive process for the flash methanolysis of wood for the production of methanol, benzene and ethylene. Future plans include completing the studies on obtaining the process chemistry of the flash methanolysis of woods, to obtain a better understanding of the enhanced ethylene and benzene yield and to investigate other biomass

  4. 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 (PrSO3 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 % (C3 ) to 110 % (C12 ). Macroporous-mesoporous PrSO3 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.

  5. Determination of lead in biomass and products of the pyrolysis process by direct solid or liquid sample analysis using HR-CS GF AAS.

    PubMed

    Duarte, Álvaro T; Borges, Aline R; Zmozinski, Ariane V; Dessuy, Morgana B; Welz, Bernhard; de Andrade, Jailson B; Vale, Maria Goreti R

    2016-01-01

    A method has been developed for the determination of lead in biomass, bio-oil, pyrolysis aqueous phase, and biomass ashes by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) and direct solid or liquid sample analysis. All measurements were performed without chemical modifier and calibration could be carried out using aqueous standard solutions. A pyrolysis temperature of 800°C and an atomization temperature of 2200°C were applied. The limits of detection and quantification were, respectively, 0.5 µg kg(-1) and 2 µg kg(-1) using the analytical line at 217.001 nm and 6 µg kg(-1) and 19 µg kg(-1) at 283.306 nm. The precision, expressed as relative standard deviation, was between 3% and 10%, which is suitable for direct analysis. The lead concentrations found for the solid samples varied between 0.28 and 1.4 mg kg(-1) for biomass and between 0.25 and 2.3 mg kg(-1) for ashes, these values were much higher than those found for bio-oil (2.2-16.8 µg kg(-1)) and pyrolysis aqueous phase (3.2-18.5 µg kg(-1)). After the determination of lead in the samples, it was possible to estimate the relative distribution of this element in the fractions of the pyrolysis products, and it was observed that most of the lead present in the biomass was eliminated to the environment during the pyrolysis process, with a significant portion retained in the ashes.

  6. Mechanism of waste biomass pyrolysis: Effect of physical and chemical pre-treatments.

    PubMed

    Das, Oisik; Sarmah, Ajit K

    2015-12-15

    To impart usability in waste based biomass through thermo-chemical reactions, several physical and chemical pre-treatments were conducted to gain an insight on their mode of action, effect on the chemistry and the change in thermal degradation profiles. Two different waste biomasses (Douglas fir, a softwood and hybrid poplar, a hardwood) were subjected to four different pre-treatments, namely, hot water pre-treatment, torrefaction, acid (sulphuric acid) and salt (ammonium phosphate) doping. Post pre-treatments, the changes in the biomass structure, chemistry, and thermal makeup were studied through electron microscopy, atomic absorption/ultra violet spectroscopy, ion exchange chromatography, and thermogravimetry. The pre-treatments significantly reduced the amounts of inorganic ash, extractives, metals, and hemicellulose from both the biomass samples. Furthermore, hot water and torrefaction pre-treatment caused mechanical disruption in biomass fibres leading to smaller particle sizes. Torrefaction of Douglas fir wood yielded more solid product than hybrid poplar. Finally, the salt pre-treatment increased the activation energies of the biomass samples (especially Douglas fir) to a great extent. Thus, salt pre-treatment was found to bestow thermal stability in the biomass. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. 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.

  8. Genetic and Quantitative Trait Locus Analysis for Bio-Oil Compounds after Fast Pyrolysis in Maize Cobs

    PubMed Central

    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. PMID:26745365

  9. Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

    DOE PAGES

    Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; ...

    2016-05-19

    This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g–1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

  10. Characteristic of fly ash derived-zeolite and its catalytic performance for fast pyrolysis of Jatropha waste.

    PubMed

    Vichaphund, S; Aht-Ong, D; Sricharoenchaikul, V; Atong, D

    2014-01-01

    Fly ash from pulp and paper industries was used as a raw material for synthesizing zeolite catalyst. Main compositions of fly ash consisted of 41 wt%SiO2, 20 wt%Al2O3, 14 wt%CaO, and 8 wt% Fe2O3. High content of silica and alumina indicated that this fly ash has potential uses for zeolite synthesis. Fly ash was mixed with 1-3 M NaOH solution. Sodium silicate acting as silica source was added into the solution to obtain the initial SiO2/Al2O3 molar ratio of 23.9. The mixtures were then crystallized at 160 degrees C for 24 and 72 h. Zeolites synthesized after a long synthesis time of 72 h showed superior properties in terms of high crystallinity, less impurity, and small particle size. The catalytic activities of fly ash-derived zeolites were investigated via fast pyrolysis of Jatropha wastes using analytical pyrolysis-gas chromatograph/mass spectrometer (GC/MS). Pyrolysis temperature was set at 500 degrees C with Jatropha wastes to catalyst ratio of 1:1, 1:5, and 1:10. Results showed that higher amounts of catalyst have a positive effect on enhancing aromatic hydrocarbons as well as decreasing in the oxygenated and N-containing compounds. Zeolite Socony Mobil-5 (ZSM-5) treated with 3 M NaOH at 72 h showed the highest hydrocarbon yield of 97.4%. The formation of hydrocarbon led to the high heating value of bio-oils. In addition, the presence of ZSM-5 derived from fly ash contributed to reduce the undesirable oxygenated compounds such as aldehydes, acids, and ketones which cause poor quality of bio-oil to only 0.8% while suppressed N-compounds to 1.7%. Overall, the ZSM-5 synthesized from fly ash proved to be an effective catalyst for catalytic fast pyrolysis application.

  11. 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...

  12. Role of Pt during hydrodeoxygenation of biomass pyrolysis vapors over Pt/HBEA

    DOE PAGES

    Yung, Matthew M.; Foo, Guo Shiou; Sievers, Carsten

    2017-03-27

    1.3 wt% Pt/HBEA and HBEA were studied as catalysts for the hydrodeoxygenation of pine pyrolysis vapors at 500 °C. Both catalysts showed high initial conversion of oxygenated pyrolysis products into aromatic hydrocarbons, while Pt/HBEA showed higher stability in terms of hydrocarbon productivity and deferred breakthrough of oxygenated compounds. Among 1-, 2- and 3-ring aromatic hydrocarbons, Pt/HBEA had a significantly higher selectivity than HBEA towards unalkylated aromatics (e.g., benzene) as compared to the corresponding alkylated aromatics (e.g., toluene and xylene). Additionally, Pt addition to HBEA decreased coke deposition and improved resistance to pore and acid site blockage as determined by TPO,more » N2 physisorption, and NH3 TPD. The ability of Pt to promote cleavage and hydrogenation of methoxy and methyl groups was observed by increased methane production over Pt/HBEA relative to HBEA. A progressive decrease in the methane production over Pt/HBEA correlated with deactivation in terms of reduced benzene formation, breakthrough of oxygenated products, and increased formation of polynuclear aromatics and their degree of substitution, which indicate coke formation. In conclusion, the increased methane yield and suppressed coke formation with the addition of Pt is attributed to hydrogen spillover, through which hydrogen activated on Pt can subsequently migrate to the HBEA support to reverse the coke-forming hydrogen abstraction reaction.« less

  13. 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.

  14. 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.

  15. Polarized Matrix Infrared Spectra of Cyclopentadienone - AN Important Reactive Intermediate in Combustion and Biomass Pyrolysis

    NASA Astrophysics Data System (ADS)

    Ormond, Thomas; Ellison, Barney; Stanton, John F.

    2014-06-01

    A detailed vibrational analysis of the infrared spectra of cyclopentadienone (C5H4=O and C5D4=O) in rare gas matrices has been carried out. Ab initio coupled-cluster anharmonic force field calculations were used to guide the assignments. Flash pyrolysis of o-phenylene sulfite (C6H4O2SO and C6D4O2SO) was used to provide a molecular beam of cyclopentadienone entrained in the rare gas carrier. The beam was interrogated with time-of-flight photoionization mass spectrometry (TOF-PIMS), confirming the clean, intense production of C5H4=O. Matrix isolation infrared spectroscopy was coupled with 355 nm polarized UV for photo-orientation and linear dichroism experiments to determine the symmetries of the vibrations.

  16. Life Cycle Assessment of high ligno-cellulosic biomass pyrolysis coupled with anaerobic digestion.

    PubMed

    Righi, Serena; Bandini, Vittoria; Marazza, Diego; Baioli, Filippo; Torri, Cristian; Contin, Andrea

    2016-07-01

    A Life Cycle Assessment is conducted on pyrolysis coupled to anaerobic digestion to treat corn stovers and to obtain bioenergy and biochar. The analysis takes into account the feedstock treatment process, the fate of products and the indirect effects due to crop residue removal. The biochar is considered to be used as solid fuel for coal power plants or as soil conditioner. All results are compared with a corresponding fossil-fuel-based scenario. It is shown that the proposed system always enables relevant primary energy savings of non-renewable sources and a strong reduction of greenhouse gases emissions without worsening the abiotic resources depletion. Conversely, the study points out that the use of corn stovers for mulch is critical when considering acidification and eutrophication impacts. Therefore, removal of corn stovers from the fields must be planned carefully. Copyright © 2016. Published by Elsevier Ltd.

  17. Polycyclic aromatic hydrocarbons (PAHs) in bio-crudes from induction-heating pyrolysis of biomass wastes.

    PubMed

    Tsai, Wen-Tien; Mi, Hsiao-Hsuan; Chang, Yuan-Ming; Yang, Shyh-Yu; Chang, Jeng-Hung

    2007-03-01

    The aim of this work was to prepare the bio-crudes from agricultural wastes (i.e., rice straw, rice husk, sugarcane bagasse and coconut shell) by using induction-heating pyrolysis at specified conditions. The quantitative analysis of 21 priority pollutant polycyclic aromatic hydrocarbons (PAHs) in bio-crudes examined using gas chromatography/mass spectrometry (GC/MS) revealed that the PAHs in bio-crudes were primarily dominant in the low molecular weight (LMW) PAHs, including naphthalene (1.10-2.45 mg/L) and acenaphthene (0.72-7.61 mg/L). However, by considering carcinogenic potency, the bio-crudes from rice husk and sugarcane bagasse contained higher contents of benzo[a]pyrene (BaP) (0.52 and 0.92 mg/L, respectively) as compared to those from rice straw and coconut shell.

  18. Fractionation and identification of organic nitrogen species from bio-oil produced by fast pyrolysis of sewage sludge.

    PubMed

    Cao, Jing-Pei; Zhao, Xiao-Yan; Morishita, Kayoko; Wei, Xian-Yong; Takarada, Takayuki

    2010-10-01

    Pyrolysis of sewage sludge was performed at 500 degrees C and a sweeping gas flow rate of 300 cm(3)/min in a drop tube furnace. Liquid fraction (i.e., bio-oil) from the sewage sludge pyrolysis was separated by silica-gel column chromatography (SGCC) with different solvents, including mixed solvents, as eluants. A series of alkanenitriles (C(13)-C(18)), oleamide, alkenenitrile, fatty acid amides and aromatic nitrogen species were fractionated from the bio-oil by SGCC and analyzed with a gas chromatography/mass spectrometry (GC/MS). Most of the GC/MS-detectable organic nitrogen species (ONSs) are lactams, amides and N-heterocyclic compounds, among which acetamide is the most abundant. N-heterocyclics with 1-3 rings, including pyrrole, pyridine, indole, benzoimidazole, carbazole, norharman and harman, were observed. The lactams detected include pyrrolidin-2-one, succinimide, phathalimide, glutarimide, piperidin-2-one and 3-isobutylhexahydropyrrolo[1,2-a]pyrazine-1,4-dione, all of which should be formed via decarboxylation and cyclization of gamma- and delta-amino acids. Such a procedure provides an effective approach to fractionation and identification of ONSs from bio-oil produced by fast pyrolysis of sewage sludge. Copyright 2010 Elsevier Ltd. All rights reserved.

  19. 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.

  20. p-n Heterojunction of doped graphene films obtained by pyrolysis of biomass precursors.

    PubMed

    Latorre-Sánchez, Marcos; Primo, Ana; Atienzar, Pedro; Forneli, Amparo; García, Hermenegildo

    2015-02-25

    Nitrogen-doped graphene [(N)G] obtained by pyrolysis at 900 °C of nanometric chitosan films exhibits a Hall effect characteristic of n-type semiconductors. In contrast, boron-doped graphene [(B)G] obtained by pyrolysis of borate ester of alginate behaves as a p-type semiconductor based also on the Hall effect. A p-n heterojunction of (B)G-(N)G films is built by stepwise coating of a quartz plate using a mask. The heterojunction is created by the partial overlapping of the (B)G-(N)G films. Upon irradiation with a xenon lamp of aqueous solutions of H(2) PtCl(6) and MnCl(2) in contact with the heterojunction, preferential electron migration from (B)G to (N)G with preferential location of positive holes on (B)G is established by observation in scanning electron microscopy of the formation of Pt nanoparticles (NP) on (N)G and MnO(2) NP on (B)G. The benefits of the heterojunction with respect to the devices having one individual component as a consequence of the electron migration through the p-n heterojunction are illustrated by measuring the photocurrent in the (B)G-(N)G heterojunction (180% current enhancement with respect to the dark current) and compared it to the photocurrent of the individual (B)G (15% enhancement) and (N)G (55% enhancement) components. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5

    SciTech Connect

    Yung, Matthew M.; Stanton, Alexander R.; Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; Magrini, Kimberly A.

    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 some 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 temperature

  2. Multiscale Evaluation of Catalytic Upgrading of Biomass Pyrolysis Vapors on Ni- and Ga-Modified ZSM-5

    SciTech Connect

    Yung, Matthew M.; Stanton, Alexander R.; Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; Magrini, Kimberly A.

    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 some 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 temperature

  3. 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

  4. Pyrolysis Oil Biorefinery.

    PubMed

    Meier, Dietrich

    2017-03-14

    In biorefineries several conversion processes for biomasses may be applied to obtain maximum value from the feed materials. One viable option is the liquefaction of lignocellulosic feedstocks or residues by fast pyrolysis. The conversion technology requires rapid heating of the biomass particles along with rapid cooling of the hot vapors and aerosols. The main product, bio-oil, is obtained in yields of up to 75 wt% on a dry feed basis, together with by-product char and gas which are used within the process to provide the process heat requirements; there are no waste streams other than flue gas and ash. Bio-oils from fast pyrolysis have a great potential to be used as renewable fuel and/or a source for chemical feedstocks. Existing technical reactor designs are presented together with actual examples. Bio-oil characterization and various options for bio-oil upgrading are discussed based on the potential end-use. Existing and potential utilization alternatives for bio-oils are presented with respect to their use for heat and power generation as well as chemical and material use.

  5. 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.

  6. Effect of torrefaction on structure and fast pyrolysis behavior of corncobs.

    PubMed

    Zheng, Anqing; Zhao, Zengli; Chang, Sheng; Huang, Zhen; Wang, Xiaobo; He, Fang; Li, Haibin

    2013-01-01

    Pretreatment of corncobs using torrefaction was conducted in an auger reactor at 250-300 °C and residence times of 10-60 min. The torrefied corncobs were fast pyrolyzed in a bubbling fluidized bed reactor at 470 °C to obtain high-quality bio-oil. The heating value and pH of the bio-oil improved when the torrefaction as pretreatment was applied; however, increasing bio-oil yield penalties were observed with increasing torrefaction severity. Fourier transform infrared Spectroscopy (FTIR) and quantitative solid (13)C nuclear magnetic resonance spectrometry (NMR) analysis of torrefied corncobs showed that the devolatilization, crosslinking and charring of corncobs during torrefaction could be responsible for the bio-oil yield penalties. Gas chromatography-mass spectrometry (GC-MS) analysis showed that the acetic acid and furfural contents of the bio-oil decreased with torrefaction temperature or residence time. The results showed that torrefaction is an effective method of pretreatment for improving bio-oil quality if the crosslinking and charring of biomass can be restricted. Copyright © 2012 Elsevier Ltd. All rights reserved.

  7. Pyrolysis of wetland biomass waste: Potential for carbon sequestration and water remediation.

    PubMed

    Cui, Xiaoqiang; Hao, Hulin; He, Zhenli; Stoffella, Peter J; Yang, Xiaoe

    2016-05-15

    Management of biomass waste is crucial to the efficiency and sustainable operation of constructed wetlands. In this study, biochars were prepared using the biomass of 22 plant species from constructed wetlands and characterized by BET-N2 surface area analysis, FTIR, TGA, SEM, EDS, and elemental compositions analysis. Biochar yields ranged from 32.78 to 49.02%, with mesopores dominating the pore structure of most biochars. The biochars had a R50 recalcitrance index of class C and the carbon sequestration potential of 19.4-28%. The aquatic plant biomass from all the Chinese constructed wetlands if made into biochars has the potential to sequester 11.48 Mt carbon yr(-1) in soils over long time periods, which could offset 0.4% of annual CO2 emissions from fossil fuel combustion in China. In terms of adsorption capacity for selected pollutants, biochar derived from Canna indica plant had the greatest adsorption capacity for Cd(2+) (98.55 mg g(-1)) and NH4(+) (7.71 mg g(-1)). Whereas for PO4(3-), Hydrocotyle verticillata derived biochar showed the greatest adsorption capacities (2.91 mg g(-1)). The results from this present study demonstrated that wetland plants are valuable feedstocks for producing biochars with potential application for carbon sequestration and contaminant removal in water remediation.

  8. The influence of recycling non-condensable gases in the fractional catalytic pyrolysis of biomass.

    PubMed

    Mante, Ofei D; Agblevor, F A; Oyama, S T; McClung, R

    2012-05-01

    In this study, the effect of recycling the non-condensable gases (NCG) in the catalytic pyrolysis of hybrid poplar using FCC catalyst was investigated. A 50mm bench scale fluidized bed reactor at 475°C with a weight hourly space velocity (WHSV) of 2h(-1) and a gas recycling capability was used for the studies. Model fluidizing gas mixtures of CO/N(2), CO(2)/N(2), CO/CO(2)/N(2) and H(2)/N(2) were used to determine their independent effects. Recycling of the NCG in the process was found to potentially increase the liquid yield and decrease char/coke yield. The model fluidizing gases increased the liquid yield and the CO(2)/N(2) fluidizing gas had the lowest char/coke yield. The (13)C-NMR analysis showed that recycling of NCG increases the aromatic fractions and decreases the methoxy, carboxylic and sugar fractions. Recycling of NCG increased the higher heating value and the pH of the bio-oil as well as decreased the viscosity and density.

  9. Fast Pyrolysis and Hydrotreating: 2015 State of Technology R&D and Projections to 2017

    SciTech Connect

    Jones, Susanne B.; Snowden-Swan, Lesley J.; Meyer, Pimphan A.; Zacher, Alan H.; Olarte, Mariefel V.; Wang, Huamin; Drennan, Corinne

    2016-03-01

    This report details the nth plant modeled results for experimentally demonstrated improvements to the upgrading of pyrolysis derived bio-oil as achieved during FY15 and compares them to the previous year. Also included is a brief update on university, national laboratory and commercial publications and demonstrations.

  10. 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.

  11. Consider Upgrading Pyrolysis Oils Into Renewale Fuels

    SciTech Connect

    Holmgren, J.; Marinangeli, R.; Nair, P.; Elliott, D.; Bain, R.

    2008-09-01

    To enable a sustained supply of biomass-based transportation fuels, the capability to process feedstocks outside the food chain must be developed. Significant industry efforts are underway to develop these new technologies, such as converting cellulosic wastes to ethanol. An alternate route being pursued involves using a fast pyrolysis operation to generate pyrolysis oil (pyoil for short). Current efforts are focused on developing a thermochemical platform to convert pyoils to renewable gasoline, diesel and jet fuel. The fuels produced will be indistinguishable from their fossil fuel counterparts and, therefore, will be compatible with existing transport and distribution infrastructure.

  12. 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.

  13. 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...

  14. Clean bio-oil production from fast pyrolysis of sewage sludge: effects of reaction conditions and metal oxide catalysts.

    PubMed

    Park, Hyun Ju; Heo, Hyeon Su; Park, Young-Kwon; Yim, Jin-Heong; Jeon, Jong-Ki; Park, Junhong; Ryu, Changkook; Kim, Seung-Soo

    2010-01-01

    Fast pyrolysis of sewage sludge was carried out under different reaction conditions, and its effects on bio-oil characteristics were studied. The effect of metal oxide catalysts on the removal of chlorine in the bio-oil was also investigated for four types of catalysts. The optimal pyrolysis temperature for bio-oil production was found to be 450 degrees C, while much smaller and larger feed sizes adversely influenced production. Higher flow and feeding rates were more effective but did not greatly affect bio-oil yields. The use of the product gas as the fluidizing medium gave an increased bio-oil yield. Metal oxide catalysts (CaO and La2O3) contributed to a slight decrease in bio-oil yield and an increase in water content but were significantly effective in removal of chlorine from the bio-oil. The fixed catalyst bed system exhibited a higher removal rate than when metal oxide-supported alumina was used as the fluidized bed material.

  15. 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.

  16. Catalytic Fast Pyrolysis of Lignin over High-Surface-Area Mesoporous Aluminosilicates: Effect of Porosity and Acidity.

    PubMed

    Custodis, Victoria B F; Karakoulia, Stamatia A; Triantafyllidis, Kostas S; van Bokhoven, Jeroen A

    2016-05-23

    Catalytic fast pyrolysis (CFP) of lignin with amorphous mesoporous aluminosilicates catalysts yields a high fraction of aromatics and a relatively low amount of char/coke. The relationship between the acidity and porosity of Al-MCM-41, Al-SBA-15, and Al-MSU-J with product selectivity during lignin CFP is determined. The acid sites (mild Brønsted and stronger Lewis) are able to catalyze pyrolysis intermediates towards fewer oxygenated phenols and aromatic hydrocarbons. A generalized correlation of the product selectivity and yield with the aluminum content and acidity of the mesoporous aluminosilicates is hard to establish. Zeolitic strong acid sites are not required to achieve high conversion and selectivity to aromatic hydrocarbon because nanosized MCM-41 produces a high liquid yield and selectivity. The two most essential parameters are diffusion, which is influenced by pore and grain size, and the active site, which may be mildly acidic, but is dominated by Lewis acid sites. Nanosized grains and mild acidity are essential ingredients for a good lignin CFP catalyst.

  17. Inactivation of E. coli O157:H7 in cultivable soil by fast and slow pyrolysis-generated biochar.

    PubMed

    Gurtler, Joshua B; Boateng, Akwasi A; Han, Yanxue Helen; Douds, David D

    2014-03-01

    An exploratory study was performed to determine the influence of fast pyrolysis (FP) and slow pyrolysis (SP) biochars on enterohemorrhagic Escherichia coli O157:H7 (EHEC) in soil. Soil + EHEC (inoculated at 7 log colony-forming units [CFU]/g of soil) + 1 of 12 types of biochar (10% total weight:weight in soil) was stored at 22°C and sampled for 8 weeks. FP switchgrass and FP horse litter biochars inactivated 2.8 and 2.1 log CFU/g more EHEC than no-biochar soils by day 14. EHEC was undetectable by surface plating at weeks 4 and 5 in standard FP switchgrass, FP oak, and FP switchgrass pellet biochars. Conversely, EHEC populations in no-biochar control samples remained as high as 5.8 and 4.0 log CFU/g at weeks 4 and 5, respectively. Additionally, three more SP hardwood pellet biochars (generated at 500°C for 1 h, or 2 h, or generated at 700°C for 30 min) inactivated greater numbers of EHEC than did the no-biochar control samples during weeks 4 and 5. These results suggest that biochar can inactivate E. coli O157:H7 in cultivable soil, which might mitigate risks associated with EHEC contamination on fresh produce.

  18. 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.

  19. Combustion, pyrolysis, gasification, and liquefaction of biomas

    NASA Astrophysics Data System (ADS)

    Reed, T. B.

    1980-09-01

    The advantages of biomass as a feedstock are examined and biomass conversion techniques are described. Combustion is the simplest method of producing heat from biomass, using either the traditional fixed bed combustion on a grate or the fluidized bed and suspended combustion techniques now being developed. Pyrolysis of biomass is a particularly attractive process if all three products gas, wood tars, and charcoal can be used. Gasification of biomass with air is perhaps the most flexible and best developed process for conversion of biomass to fuel, yielding a low energy gas that can be burned in existing gas/oil boilers or in engines. Oxygen gasification yields a gas with higher energy content that can be used in pipelines or to fire turbines. In addition, this gas can be used for producing methanol, ammonia, or gasoline by indirect liquefaction. Fast pyrolysis of biomass produces a gas rich in ethylene that can be used to make alcohols or gasoline. Finally, treatment of biomass with high pressure hydrogen can yield liquid fuels through direct liquefaction.

  20. 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.

  1. Application of mineral bed materials during fast pyrolysis of rice husk to improve water-soluble organics production.

    PubMed

    Li, R; Zhong, Z P; Jin, B S; Zheng, A J

    2012-09-01

    Fast pyrolysis of rice husk was performed in a spout-fluid bed to produce water-soluble organics. The effects of mineral bed materials (red brick, calcite, limestone, and dolomite) on yield and quality of organics were evaluated with the help of principal component analysis (PCA). Compared to quartz sand, red brick, limestone, and dolomite increased the yield of the water-soluble organics by 6-55% and the heating value by 16-19%. The relative content of acetic acid was reduced by 23-43% with calcite, limestone and dolomite when compared with quartz sand. The results from PCA showed all minerals enhanced the ring-opening reactions of cellulose into furans and carbonyl compounds rather than into monomeric sugars. Moreover, calcite, limestone, and dolomite displayed the ability to catalyze the degradation of heavy compounds and the demethoxylation reaction of guaiacols into phenols. Minerals, especially limestone and dolomite, were beneficial to the production of water-soluble organics.

  2. Optimization of a free-fall reactor for the production of fast pyrolysis bio-oil.

    PubMed

    Ellens, C J; Brown, R C

    2012-01-01

    A central composite design of experiments was performed to optimize a free-fall reactor for the production of bio-oil from red oak biomass. The effects of four experimental variables including heater set-point temperature, biomass particle size, sweep gas flow rate and biomass feed rate were studied. Heater set-point temperature ranged from 450 to 650 °C, average biomass particle size from 200 to 600 μm, sweep gas flow rate from 1 to 5 sL/min and biomass feed rate from 1 to 2 kg/h. Optimal operating conditions yielding over 70 wt.% bio-oil were identified at a heater set-point temperature of 575 °C, while feeding red oak biomass sized less than 300 μm at 2 kg/h into the 0.021 m diameter, 1.8m tall reactor. Sweep gas flow rate did not have significant effect on bio-oil yield over the range tested.

  3. 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, Jack R.; ...

    2017-08-01

    Catalytic hydroprocessing of pyrolysis oils from biomass produces hydrocarbons that can be considered 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. 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/Al2O3 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. These results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.« less

  4. 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/Al2O3 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

  5. Proceedings of the Biomass Pyrolysis Oil Properties and Combustion Meeting, 26-28 September 1994, Estes Park, Colorado

    SciTech Connect

    Milne, T.

    1995-01-01

    The increasing scale-up of fast pyrolysis in North America and Europe, as well as the exploration and expansion of markets for the energy use of biocrude oils that now needs to take place, suggested that it was timely to convene an international meeting on the properties and combustion behavior of these oils. A common understanding of the state-of-the-art and technical and other challenges which need to be met during the commercialization of biocrude fuel use, can be achieved. The technical issues and understanding of combustion of these oils are rapidly being advanced through R&D in the United States. Canada, Europe and Scandinavia. It is obvious that for the maximum economic impact of biocrude, it will be necessary to have a common set of specifications so that oils can be used interchangeably with engines and combustors which require minimal modification to use these renewable fuels. Fundamental and applied studies being pursued in several countries are brought together in this workshop so that we can arrive at common strategies. In this way, both the science and the commercialization are advanced to the benefit of all, without detracting from the competitive development of both the technology and its applications. This United States-Canada-Finland collaboration has led to the two and one half day specialists meeting at which the technical basis for advances in biocrude development is discussed. The goal is to arrive at a common agenda on issues that cross national boundaries in this area. Examples of agenda items are combustion phenomena, the behavior of trace components of the oil (N, alkali metals), the formation of NOx in combustion, the need for common standards and environmental safety and health issues in the handling, storage and transportation of biocrudes.

  6. Properties of Oxygenates Found in Upgraded Biomass Pyrolysis Oil as Components of Spark and Compression Ignition Engine Fuels

    DOE PAGES

    McCormick, Robert L.; Ratcliff, Matthew A.; Christensen, Earl; ...

    2015-03-01

    We examined xxygenates present in partially hydroprocessed lignocellulosic-biomass pyrolysis oils for their impact on the performance properties of gasoline and diesel. These included: methyltetrahydrofuran, 2,5-dimethylfuran (DMF), 2-hexanone, 4-methylanisole, phenol, p-cresol, 2,4-xylenol, guaiacol, 4-methylguaiacol, 4-methylacetophenone, 4-propylphenol, and 4-propylguaiacol. Literature values indicate that acute toxicity for these compounds falls within the range of the components in petroleum-derived fuels. On the basis of the available data, 4-methylanisole and by extension other methyl aryl ethers appear to be the best drop-in fuel components for gasoline because they significantly increase research octane number and slightly reduce vapor pressure without significant negative fuel property effects. Amore » significant finding is that DMF can produce high levels of gum under oxidizing conditions. If the poor stability results observed for DMF could be addressed with a stabilizer additive or removal of impurities, it could also be considered a strong drop-in fuel candidate. The low solubility of phenol and p-cresol (and by extension, the two other cresol isomers) in hydrocarbons and the observation that phenol is also highly extractable into water suggest that these molecules cannot likely be present above trace levels in drop-in fuels. The diesel boiling range oxygenates all have low cetane numbers, which presents challenges for blending into diesel fuel. Moreover, there were some beneficial properties observed for the phenolic oxygenates in diesel, including increasing conductivity, lubricity, and oxidation stability of the diesel fuel. Oxygenates other than phenol and cresol, including other phenolic compounds, showed no negative impacts at the low blend levels examined here and could likely be present in an upgraded bio-oil gasoline or diesel blendstock at low levels to make a drop-in fuel. On the basis of solubility parameter theory, 4-methylanisole and

  7. Separation of phenols and furfural by pervaporation and reverse osmosis membranes from biomass--superheated steam pyrolysis-derived aqueous solution.

    PubMed

    Sagehashi, Masaki; Nomura, Tsuyoshi; Shishido, Hiromu; Sakoda, Akiyoshi

    2007-07-01

    The separation of valuable chemicals from raw products, where a great number of chemicals coexist, is the key technology in biomass refinery. In this study, the applicability of membrane separation of valuable chemicals from our currently developed portable superheated steam (SHS) biomass pyrolysis process was demonstrated. Phenols (phenol, p-cresol, guaiacol, methyl guaiacol, and ethyl guaiacol), furfural, and acetone were successfully separated by pervaporation using the silicone rubber membrane from model solutions and an actual SHS derived aqueous solution. The solution was also concentrated effectively by reverse osmosis separation using a polyamide membrane. When a high concentration of SHS solution was fed to the pervaporation process, a phase-separated permeate was obtained, which indicated that the reverse osmosis concentration combined with pervaporation separation is useful for the superheated steam process.

  8. Hydrodeoxygenation of fast-pyrolysis bio-oils from various feedstocks using carbon-supported catalysts

    USDA-ARS?s Scientific Manuscript database

    While much work has been accomplished in developing hydrodeoxygenation technologies for bio-oil upgrading, very little translation has occurred to other biomass feedstocks and feedstock processing technologies. In this paper, we sought to elucidate the relationships between the feedstock type and th...

  9. Effects of hot-water extraction on the thermochemical conversion of shrub willow via fast pyrolysis

    USDA-ARS?s Scientific Manuscript database

    Hot-water extraction (TM) (HWE) is a pretreatment technology designed to facilitate the subsequent hydrolysis of cellulose by removing the majority of the hemicellulose and ash content from the solid biomass. The HWE process generates salable sugars and other products as part of the process. The bio...

  10. Characterization and Catalytic Upgrading of Crude Bio-oil Produced by Hydrothermal Liquefaction of Swine Manure and Pyrolysis of Biomass

    NASA Astrophysics Data System (ADS)

    Cheng, Dan

    The distillation curve of crude bio-oil from glycerol-assisted hydrothermal liquefaction of swine manure was measured using an advanced distillation apparatus. The crude bio-oil had much higher distillation temperatures than diesel and gasoline and was more distillable than the bio-oil produced by the traditional liquefaction of swine manure and the pyrolysis of corn stover. Each 10% volumetric fraction was analyzed from aspects of its chemical compositions, chemical and physical properties. The appearance of hydrocarbons in the distillates collected at the temperature of 410.9°C and above indicated that the thermal cracking at a temperature from 410°C to 500°C may be a proper approach to upgrade the crude bio-oil produced from the glycerol-assisted liquefaction of swine manure. The effects of thermal cracking conditions including reaction temperature (350-425°C), retention time (15-60 min) and catalyst loadings (0-10 wt%) on the yield and quality of the upgraded oil were analyzed. Under the optimum thermal cracking conditions at 400°C, a catalyst loading of 5% by mass and the reaction time of 30 min, the yield of bio-oil was 46.14% of the mass of the crude bio-oil and 62.5% of the energy stored in the crude bio-oil was recovered in the upgraded bio-oil. The upgraded bio-oil with a heating value of 41.4 MJ/kg and viscosity of 3.6 cP was comparable to commercial diesel. In upgrading crude bio-oil from fast pyrolysis, converting organic acids into neutral esters is significant and can be achieved by sulfonated activated carbon/bio-char developed from fermentation residues. Acitivated carbon and bio-char were sulfonated by concentrated sulfuric acid at 150°C for 18 h. Sulfonation helped activated carbon/bio-char develop acid functional groups. Sulfonated activated carbon with BET surface area of 349.8 m2/g, was effective in converting acetic acid. Acetic acid can be effectively esterified by sulfonated activated carbon (5 wt%) at 78°C for 60 min with the

  11. 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

  12. 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.

  13. 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

  14. Biomass Thermochemical Conversion Program. 1983 Annual report

    SciTech Connect

    Schiefelbein, G.F.; Stevens, D.J.; Gerber, M.A.

    1984-08-01

    Highlights of progress achieved in the program of thermochemical conversion of biomass into clean fuels during 1983 are summarized. Gasification research projects include: production of a medium-Btu gas without using purified oxygen at Battelle-Columbus Laboratories; high pressure (up to 500 psia) steam-oxygen gasification of biomass in a fluidized bed reactor at IGT; producing synthesis gas via catalytic gasification at PNL; indirect reactor heating methods at the Univ. of Missouri-Rolla and Texas Tech Univ.; improving the reliability, performance, and acceptability of small air-blown gasifiers at Univ. of Florida-Gainesville, Rocky Creek Farm Gasogens, and Cal Recovery Systems. Liquefaction projects include: determination of individual sequential pyrolysis mechanisms at SERI; research at SERI on a unique entrained, ablative fast pyrolysis reactor for supplying the heat fluxes required for fast pyrolysis; work at BNL on rapid pyrolysis of biomass in an atmosphere of methane to increase the yields of olefin and BTX products; research at the Georgia Inst. of Tech. on an entrained rapid pyrolysis reactor to produce higher yields of pyrolysis oil; research on an advanced concept to liquefy very concentrated biomass slurries in an integrated extruder/static mixer reactor at the Univ. of Arizona; and research at PNL on the characterization and upgrading of direct liquefaction oils including research to lower oxygen content and viscosity of the product. Combustion projects include: research on a directly fired wood combustor/gas turbine system at Aerospace Research Corp.; adaptation of Stirling engine external combustion systems to biomass fuels at United Stirling, Inc.; and theoretical modeling and experimental verification of biomass combustion behavior at JPL to increase biomass combustion efficiency and examine the effects of additives on combustion rates. 26 figures, 1 table.

  15. Flash vacuum pyrolysis of lignin model compounds

    SciTech Connect

    Cooney, M.J.; Britt, P.F.; Buchanan, A.C. III

    1997-03-01

    Despite the extensive research into the pyrolysis of lignin, the underlying chemical reactions that lead to product formation are poorly understood. Detailed mechanistic studies on the pyrolysis of biomass and lignin under conditions relevant to current process conditions could provide insight into utilizing this renewable resource for the production of chemicals and fuel. Currently, flash or fast pyrolysis is the most promising process to maximize the yields of liquid products (up to 80 wt %) from biomass by rapidly heating the substrate to moderate temperatures, typically 500{degrees}C, for short residence times, typically less than two seconds. To provide mechanistic insight into the primary reaction pathways under process relevant conditions, we are investigating the flash vacuum pyrolysis (FVP) of lignin model compounds that contain a {beta}-ether. linkage and {alpha}- or {gamma}-alcohol, which are key structural elements in lignin. The dominant products from the FVP of PhCH{sub 2}CH{sub 2}OPh (PPE), PhC(OH)HCH{sub 2}OPh, and PhCH{sub 2}CH(CH{sub 2}OH)OPh at 500{degrees}C can be attributed to homolysis of the weakest bond in the molecule (C-O bond) or 1,2-elimination. Surprisingly, the hydroxy-substituent dramatically increases the decomposition of PPE. It is proposed that internal hydrogen bonding is accelerating the reaction.

  16. Catalytic pyrolysis-gc/ms of spirulina: evaluation of a highly proteinaceous biomass source for production of fuels and chemicals

    USDA-ARS?s Scientific Manuscript database

    Pyrolysis of microalgae offers a pathway towards the production of compounds derived from the thermal decomposition of triglycerides, proteins as well as lignocelluloses and their combinations thereof. When catalytically induced, this could lead to the production of fuels and chemicals including aro...

  17. Fast Pyrolysis Oil Stabilization: An Integrated Catalytic and Membrane Approach for Improved Bio-oils. Final Report

    SciTech Connect

    George W. Huber; Upadhye, Aniruddha A.; Ford, David M.; Bhatia, Surita R.; Badger, Phillip C.

    2012-10-19

    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 nominal 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. Experiments

  18. High performance thin layer chromatography determination of cellobiosan and levoglucosan in bio-oil obtained by fast pyrolysis of sawdust.

    PubMed

    Tessini, Catherine; Vega, Mario; Müller, Niels; Bustamante, Luis; von Baer, Dietrich; Berg, Alex; Mardones, Claudia

    2011-06-17

    In this work, high performance thin layer liquid chromatography (HTPLC) is applied to the determination of sugars in fast pyrolysis liquids (bio-oil) and fractions thereof. The proposed procedure allows the separation of anhydrosugar levoglucosan and cellobiosan, as well as glucose, arabinose, xylose and cellobiose. Pre-treatment and derivatization of samples are not necessary and volatile compounds present in bio-oil do not interfere with sugar analysis. The detrimental effect of the complex bio-oil matrix on columns and detector lifetime is avoided by using disposable HTPLC plates. Prior screening of glucose, present especially in aged and aqueous bio-oil fractions, is required to quantify cellobiosan without interference. Concentrations of levoglucosan and cellobiosan in bio-oil samples obtained from Pinus radiata sawdust were ranged between 1.27-2.26% and 0.98-1.96% respectively, while a bio-oil sample obtained from native wood contained a higher levoglucosan concentration. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Catalytic fast pyrolysis of mushroom waste to upgraded bio-oil products via pre-coked modified HZSM-5 catalyst.

    PubMed

    Wang, Jia; Zhong, Zhaoping; Ding, Kuan; Xue, Zeyu

    2016-07-01

    In this paper, HZSM-5 catalyst was modified by pre-coked to cover the strong external acid sites by methanol to olefins reaction, and the modified catalysts were then applied to conduct the catalyst fast pyrolysis of mushroom waste for upgraded bio-fuel production. Experiment results showed that the strong external acid sites and specific surface area decreased with pre-coked percentage increasing from 0% to 5.4%. Carbon yields of hydrocarbons increased at first and then decreased with a maximum value of 53.47%. While the obtained oxygenates presented an opposite variation tendency, and the minimum values could be reached when pre-coked percentage was 2.7%. Among the achieved hydrocarbons, toluene and p-xylene were found to be the main products, and the selectivity of p-xylene increased at first and then decreased with a maximum value of 34.22% when the pre-coked percentage was 1.3%, and the selectivity of toluene showed the opposite tendency with a minimum value of 25.47%. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Supply Chain Sustainability Analysis of Fast Pyrolysis and Hydrotreating Bio-Oil to Produce Hydrocarbon Fuels

    SciTech Connect

    Adom, Felix K.; Cai, Hao; Dunn, Jennifer B.; Hartley, Damon; Searcy, Erin; Tan, Eric; Jones, Sue; Snowden-Swan, Lesley

    2016-03-01

    The Department of Energy’s (DOE) Bioenergy Technology Office (BETO) aims at developing and deploying technologies to transform renewable biomass resources into commercially viable, high-performance biofuels, bioproducts and biopower through public and private partnerships (DOE, 2015). BETO and its national laboratory teams conduct in-depth techno-economic assessments (TEA) of technologies to produce biofuels. These assessments evaluate feedstock production, logistics of transporting the feedstock, and conversion of the feedstock to biofuel. There are two general types of TEAs. A design case is a TEA that outlines a target case for a particular biofuel pathway. It enables identification of data gaps and research and development needs, and provides goals and targets against which technology progress is assessed. On the other hand, a state of technology (SOT) analysis assesses progress within and across relevant technology areas based on actual experimental results relative to technical targets and cost goals from design cases, and includes technical, economic, and environmental criteria as available.

  1. 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.

  2. Process for fractionating fast-pyrolysis oils, and products derived therefrom

    DOEpatents

    Chum, Helena L.; Black, Stuart K.

    1990-01-01

    A process is disclosed for fractionating lignocellulosic materials fast-prolysis oils to produce phenol-containing compositions suitable for the manufacture of phenol-formaldehyde resins. The process includes admixing the oils with an organic solvent having at least a moderate solubility parameter and good hydrogen The United States Government has rights in this invention under Contract No. DE-AC02-83CH10093 between the United States Department of Energy and the Solar Energy Research Institute, a Division of the Midwest Research Institute.

  3. 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.

  4. Optimization and characterization of bio-oil produced by microwave assisted pyrolysis of oil palm shell waste biomass with microwave absorber.

    PubMed

    Mushtaq, Faisal; Abdullah, Tuan Amran Tuan; Mat, Ramli; Ani, Farid Nasir

    2015-08-01

    In this study, solid oil palm shell (OPS) waste biomass was subjected to microwave pyrolysis conditions with uniformly distributed coconut activated carbon (CAC) microwave absorber. The effects of CAC loading (wt%), microwave power (W) and N2 flow rate (LPM) were investigated on heating profile, bio-oil yield and its composition. Response surface methodology based on central composite design was used to study the significance of process parameters on bio-oil yield. The coefficient of determination (R(2)) for the bio-oil yield is 0.89017 indicating 89.017% of data variability is accounted to the model. The largest effect on bio-oil yield is from linear and quadratic terms of N2 flow rate. The phenol content in bio-oil is 32.24-58.09% GC-MS area. The bio-oil also contain 1,1-dimethyl hydrazine of 10.54-21.20% GC-MS area. The presence of phenol and 1,1-dimethyl hydrazine implies that the microwave pyrolysis of OPS with carbon absorber has the potential to produce valuable fuel products.

  5. 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...

  6. Evaluation of the impact of compositional differences in switchgrass genotypes on pyrolysis product yield

    USDA-ARS?s Scientific Manuscript database

    As a dedicated bioenergy crop, switchgrass is a major feedstock within the United States for biofuels production and can be converted to energy dense bio-oil through fast pyrolysis. Biomass compositional differences can influence the conversion efficiency and bio-oil product yield and quality. In ...

  7. 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.

  8. Bio-oil deoxygenation by catalytic pyrolysis: new catalysts for the conversion of biomass into densified and deoxygenated bio-oil.

    PubMed

    Sanna, Aimaro; Andrésen, John M

    2012-10-01

    This work proposes an innovative catalytic pyrolysis process that converts bio-refinery residues, such as spent grains, into intermediate bio-oil with improved properties compared to traditional bio-oils, which allows the use of existing crude-oil refinery settings for bio-oil upgrading into fuels. The integration of bio-oil into a crude-oil refinery would decrease the economic disadvantage of biomass compared to fossil fuels. The catalytic pyrolysis was able to produce bio-oil with a lower O and N content and high levels of aliphatics and H by using activated serpentine and olivine at 430-460 °C. The activated materials seem to be beneficial to the bio-oil energy content by increasing it from less than 20 MJ kg(-1) in the original biomass to 26 MJ kg(-1). Approximately 70-74 % of the starting energy remains in the bio-oil using activated olivine (ACOL) and activated serpentine (ACSE) at 430 °C, whereas only 52 % is retained using alumina (ALU) at the same temperature. There was a strong reduction of the O content in the bio-oils, and the deoxygenation power decreased in the following order: ACOL>ACSE>ALU. In particular, ACOL at 430-460 °C was able to reduce the O content of the bio-oil by 40 %. The oxygenated bio-oil macromolecules interact in the catalyst's active sites with the naturally present metallic species and undergo decarboxylation with the formation of C(5)-C(6) O-depleted species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Flash Vacuum Pyrolysis of Lignin Model Compounds: Reaction Pathways of Aromatic Methoxy Groups

    SciTech Connect

    Britt, P.F.; Buchanan, A.C., III; Martineau, D.R.

    1999-03-21

    Currently, there is interest in utilizing lignin, a major constituent of biomass, as a renewable source of chemicals and fuels. High yields of liquid products can be obtained from the flash or fast pyrolysis of biomass, but the reaction pathways that lead to product formation are not understood. To provide insight into the primary reaction pathways under process relevant conditions, we are investigating the flash vacuum pyrolysis (FVP) of lignin model compounds at 500 C. This presentation will focus on the FVP of {beta}-ether linkages containing aromatic methoxy groups and the reaction pathways of methoxy-substituted phenoxy radicals.

  10. Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

    SciTech Connect

    Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; Olarte, Mariefel V.; Armstrong, Beth L.; Meyer, III, Harry M.; Schwartz, Viviane; Soykal, I. Ilgaz

    2016-05-19

    This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt % and 0.01 mg KOH g–1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.

  11. Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

    SciTech Connect

    Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; Olarte, Mariefel V.; Armstrong, Beth L.; Meyer, III, Harry M.; Schwartz, Viviane; Soykal, I. Ilgaz

    2016-05-19

    This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt % and 0.01 mg KOH g–1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.

  12. Molybdenum Carbides, Active and In Situ Regenerable Catalysts in Hydroprocessing of Fast Pyrolysis Bio-Oil

    SciTech Connect

    Choi, Jae-Soon; Zacher, Alan H.; Wang, Huamin; Olarte, Mariefel V.; Armstrong, Beth L.; Meyer, Harry M.; Soykal, I. Ilgaz; Schwartz, Viviane

    2016-06-16

    We assessed molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60-h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt% and 0.01 mg KOH g-1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60-h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are promising catalytic materials which could lead to a significant cost reduction in hydroprocessing bio-oils. This paper highlights areas for future research which will be needed to further understand carbide structure-function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.

  13. 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.

  14. Techno-economic and uncertainty analysis of in situ and ex situ fast pyrolysis for biofuel production

    SciTech Connect

    Li, Boyan; Ou, Longwen; Dang, Qi; Meyer, Pimphan A.; Jones, Susanne B.; Brown, Robert C.; Wright, Mark

    2015-11-01

    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 ex 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.

  15. 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.

  16. 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.

  17. Enhancement of bio-oil production via pyrolysis of wood biomass by pretreatment with H2SO4.

    PubMed

    Kumagai, Shogo; Matsuno, Ryo; Grause, Guido; Kameda, Tomohito; Yoshioka, Toshiaki

    2015-02-01

    In this work, a Japanese cedar wood sample was treated during the first step at ambient temperature and atmospheric pressure using several concentrations of sulfuric acid (H2SO4) in a stirred flask. During this pretreatment C-O bonds of cellulose, hemicellulose, and lignin were cleaved. The second step involved the pyrolysis of the pretreated wood sample at 550 °C in a quartz glass tube reactor. A maximum oil yield of 46.8 wt% with the minimum char yield of 10.1 wt% was obtained by the treatment with 3 M H2SO4, whereas untreated wood samples resulted in a 30.1 wt% yield of oil. The main components in the oils were levoglucosan and tar. These results suggest that moderate acid pretreatment produced shorter chain units of cellulose, hemicellulose, and lignin, thereby facilitating the conversion into oil by pyrolysis. The results of thermogravimetry-mass spectroscopy supported the presence of shorter chain units in the pretreated wood samples.

  18. 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