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Sample records for fast pyrolysis oil

  1. 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...

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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...

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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...

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

    USDA-ARS?s Scientific Manuscript database

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

  16. 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.

  17. 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.

  18. 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...

  19. 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 ...

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  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. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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...

  12. 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.

  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 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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...

  1. 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.

  2. 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

  3. 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

  4. 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

  5. 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

  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. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  16. 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.

  17. 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...

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Corrosivity Of Pyrolysis Oils

    SciTech Connect

    Keiser, James R; Bestor, Michael A; Lewis Sr, Samuel Arthur; Storey, John Morse

    2011-01-01

    Pyrolysis oils from several sources have been analyzed and used in corrosion studies which have consisted of exposing corrosion coupons and stress corrosion cracking U-bend samples. The chemical analyses have identified the carboxylic acid compounds as well as the other organic components which are primarily aromatic hydrocarbons. The corrosion studies have shown that raw pyrolysis oil is very corrosive to carbon steel and other alloys with relatively low chromium content. Stress corrosion cracking samples of carbon steel and several low alloy steels developed through-wall cracks after a few hundred hours of exposure at 50 C. Thermochemical processing of biomass can produce solid, liquid and/or gaseous products depending on the temperature and exposure time used for processing. The liquid product, known as pyrolysis oil or bio-oil, as produced contains a significant amount of oxygen, primarily as components of water, carboxylic acids, phenols, ketones and aldehydes. As a result of these constituents, these oils are generally quite acidic with a Total Acid Number (TAN) that can be around 100. Because of this acidity, bio-oil is reported to be corrosive to many common structural materials. Despite this corrosive nature, these oils have the potential to replace some imported petroleum. If the more acidic components can be removed from this bio-oil, it is expected that the oil could be blended with crude oil and then processed in existing petroleum refineries. The refinery products could be transported using customary routes - pipelines, barges, tanker trucks and rail cars - without a need for modification of existing hardware or construction of new infrastructure components - a feature not shared by ethanol.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC

    PubMed Central

    2016-01-01

    Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13C nuclear magnetic resonance (13C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. 13C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (≈30%) and carbohydrate (≈27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (≈35%) and aromatic (≈30%) carbons, while rapeseed cake-based bio-oil had great portions of alkyl carbons (≈82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil. PMID:27668136

  16. Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using (13)C NMR and Comprehensive GC × GC.

    PubMed

    Negahdar, Leila; Gonzalez-Quiroga, Arturo; Otyuskaya, Daria; Toraman, Hilal E; Liu, Li; Jastrzebski, Johann T B H; Van Geem, Kevin M; Marin, Guy B; Thybaut, Joris W; Weckhuysen, Bert M

    2016-09-06

    Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative (13)C nuclear magnetic resonance ((13)C NMR) combined with comprehensive two-dimensional gas chromatography (GC × GC) was used to characterize fast pyrolysis bio-oils originated from pinewood, wheat straw, and rapeseed cake. The combination of both techniques provided new information on the chemical composition of bio-oils for further upgrading. (13)C NMR analysis indicated that pinewood-based bio-oil contained mostly methoxy/hydroxyl (≈30%) and carbohydrate (≈27%) carbons; wheat straw bio-oil showed to have high amount of alkyl (≈35%) and aromatic (≈30%) carbons, while rapeseed cake-based bio-oil had great portions of alkyl carbons (≈82%). More than 200 compounds were identified and quantified using GC × GC coupled to a flame ionization detector (FID) and a time of flight mass spectrometer (TOF-MS). Nonaromatics were the most abundant and comprised about 50% of the total mass of compounds identified and quantified via GC × GC. In addition, this analytical approach allowed the quantification of high value-added phenolic compounds, as well as of low molecular weight carboxylic acids and aldehydes, which exacerbate the unstable and corrosive character of the bio-oil.

  17. Fast pyrolysis oil from pinewood chips co-processing with vacuum gas oil in an FCC unit for second generation fuel production

    SciTech Connect

    Pinho, Andrea de Rezende; de Almeida, Marlon B. B.; Mendes, Fabio Leal; Casavechia, Luiz Carlos; Talmadge, Michael S.; Kinchin, Christopher M.; Chum, Helena L.

    2016-10-15

    Raw bio-oil produced from fast pyrolysis of pine woodchips was co-processed with standard Brazilian vacuum gasoil (VGO) and tested in a 200 kg•h-1 fluid catalytic cracking (FCC) demonstration-scale unit using a commercial FCC equilibrium catalyst. Two different bio-oil/VGO weight ratios were used: 5/95 and 10/90. Co-processing of raw bio-oil in FCC was shown to be technically feasible. Bio-oil could be directly co-processed with a regular gasoil FCC feed up to 10 wt%. The bio-oil and the conventional gasoil were cracked into valuable liquid products such as gasoline and diesel range products. Most of the oxygen present in the bio-oil was eliminated as water and carbon monoxide as these yields were always higher than that of carbon dioxide. Product quality analysis shows that trace oxygenates, primarily alkyl phenols, in FCC gasoline and diesel products are present with or without co-processing oxygenated intermediates. The oxygenate concentrations increase with co-processing, but have not resulted in increased concerns with quality of fuel properties. The presence of renewable carbon was confirmed in gasoline and diesel cuts through 14C isotopic analysis, showing that renewable carbon is not only being converted into coke, CO, and CO2, but also into valuable refining liquid products. Thus, gasoline and diesel could be produced from lignocellulosic raw materials through a conventional refining scheme, which uses the catalytic cracking process. As a result, the bio-oil renewable carbon conversion into liquid products (carbon efficiency) was approximately 30%, well above the efficiency found in literature for FCC bio-oil upgrading.

  18. Fast pyrolysis oil from pinewood chips co-processing with vacuum gas oil in an FCC unit for second generation fuel production

    DOE PAGES

    Pinho, Andrea de Rezende; de Almeida, Marlon B. B.; Mendes, Fabio Leal; ...

    2016-10-15

    Raw bio-oil produced from fast pyrolysis of pine woodchips was co-processed with standard Brazilian vacuum gasoil (VGO) and tested in a 200 kg•h-1 fluid catalytic cracking (FCC) demonstration-scale unit using a commercial FCC equilibrium catalyst. Two different bio-oil/VGO weight ratios were used: 5/95 and 10/90. Co-processing of raw bio-oil in FCC was shown to be technically feasible. Bio-oil could be directly co-processed with a regular gasoil FCC feed up to 10 wt%. The bio-oil and the conventional gasoil were cracked into valuable liquid products such as gasoline and diesel range products. Most of the oxygen present in the bio-oil wasmore » eliminated as water and carbon monoxide as these yields were always higher than that of carbon dioxide. Product quality analysis shows that trace oxygenates, primarily alkyl phenols, in FCC gasoline and diesel products are present with or without co-processing oxygenated intermediates. The oxygenate concentrations increase with co-processing, but have not resulted in increased concerns with quality of fuel properties. The presence of renewable carbon was confirmed in gasoline and diesel cuts through 14C isotopic analysis, showing that renewable carbon is not only being converted into coke, CO, and CO2, but also into valuable refining liquid products. Thus, gasoline and diesel could be produced from lignocellulosic raw materials through a conventional refining scheme, which uses the catalytic cracking process. As a result, the bio-oil renewable carbon conversion into liquid products (carbon efficiency) was approximately 30%, well above the efficiency found in literature for FCC bio-oil upgrading.« less

  19. Production of bio-oil rich in acetic acid and phenol from fast pyrolysis of palm residues using a fluidized bed reactor: Influence of activated carbons.

    PubMed

    Jeong, Jae-Yong; Lee, Uen-Do; Chang, Won-Seok; Jeong, Soo-Hwa

    2016-11-01

    In this study, palm residues were pyrolyzed in a bench-scale (3kg/h) fast pyrolysis plant equipped with a fluidized bed reactor and bio-oil separation system for the production of bio-oil rich in acetic acid and phenol. Pyrolysis experiments were performed to investigate the effects of reaction temperature and the types and amounts of activated carbon on the bio-oil composition. The maximum bio-oil yield obtained was approximately 47wt% at a reaction temperature of 515°C. The main compounds produced from the bio-oils were acetic acid, hydroxyacetone, phenol, and phenolic compounds such as cresol, xylenol, and pyrocatechol. When coal-derived activated carbon was applied, the acetic acid and phenol yields in the bio-oils reached 21 and 19wt%, respectively. Finally, bio-oils rich in acetic acid and phenol could be produced separately by using an in situ bio-oil separation system and activated carbon as an additive. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. 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.

  1. 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.

  2. 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.

  3. 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...

  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, 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

  5. 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

  6. 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.

  7. 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.

  8. Fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst.

    PubMed

    Liu, Shiyu; Xie, Qinglong; Zhang, Bo; Cheng, Yanling; Liu, Yuhuan; Chen, Paul; Ruan, Roger

    2016-03-01

    This study investigated fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst. Effects of reaction temperature, CaO/HZSM-5 ratio, and corn stover/scum ratio on co-pyrolysis product fractional yields and selectivity were investigated. Results showed that co-pyrolysis temperature was selected as 550°C, which provides the maximum bio-oil and aromatic yields. Mixed CaO and HZSM-5 catalyst with the weight ratio of 1:4 increased the aromatic yield to 35.77 wt.% of feedstock, which was 17% higher than that with HZSM-5 alone. Scum as the hydrogen donor, had a significant synergistic effect with corn stover to promote the production of bio-oil and aromatic hydrocarbons when the H/C(eff) value exceeded 1. The maximum yield of aromatic hydrocarbons (29.3 wt.%) were obtained when the optimal corn stover to scum ratio was 1:2.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Methods and apparatuses for preparing upgraded pyrolysis oil

    DOEpatents

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

    2013-10-01

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

  15. 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

  16. 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

  17. 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

  18. 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...

  19. Results of the IEA Round Robin on Viscosity and Aging of Fast Pyrolysis Bio-oils: Long-Term Tests and Repeatability

    SciTech Connect

    Elliott, Douglas C.; Oasmaa, Anja; Meier, Dietrich; Preto, Fernando; Bridgwater, Anthony V.

    2012-11-06

    An international round robin study of the viscosity and aging of fast pyrolysis bio-oil has been undertaken recently and this work is an outgrowth from that effort. Two bio-oil samples were distributed to the laboratories for aging tests and extended viscosity studies. The accelerated aging test was defined as the change in viscosity of a sealed sample of bio-oil held for 24 h at 80 °C. The test was repeated 10 times over consecutive days to determine the repeatability of the method. Other bio-oil samples were placed in storage at three temperatures, 21 °C, 4 °C and -17 °C for a period up to a year to evaluate the change in viscosity. The variation in the results of the aging test was shown to be low within a given laboratory. Storage of bio-oil under refrigeration can minimize the amount of change in viscosity. The accelerated aging test gives a measure of change similar to that of 6-12 months of storage at room temperature. These results can be helpful in setting standards for use of bio-oil, which is just coming into the marketplace.

  20. 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.

  1. 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.

  2. 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.

  3. 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...

  4. 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.

  5. The conversion of chicken manure to bio-oil by fast pyrolysis. III. Analyses of chicken manure, bio-oils and char by Py-FIMS and Py-FDMS.

    PubMed

    Schnitzer, Morris I; Monreal, Carlos M; Jandl, Gerald

    2008-01-01

    Fast pyrolysis of chicken manure produced the following three fractions: bio-oil Fraction I, bio-oil Fraction II, and a char. In a previous investigation we analyzed each of the four materials by curie-point pyrolysis-gas chromatography/mass spectrometry (CpPy-FDMS). The objective of this article is to report on the analyses of the same chicken manure and the three fractions derived from it by fast pyrolysis. We now used pyrolysis-field ionization mass spectrometry (Py-FIMS) to characterize the three fractions. In addition, the two bio-oil materials were analyzed by pyrolysis-field desorption mass spectrometry (Py-FDMS). The use of both Py-FIMS and Py-FDMS produced signals over significantly wider mass ranges than did CpPy-GC/MS, and so allowed us to identify considerably larger numbers of constituents in each material. Individual compounds identified in the mass spectra were classified into the following twelve compound classes: (a) low molecular weight compounds (< m/z 62); (b) carbohydrates; (c) phenols + lignin monomers; (d) lignin dimers; (e) n-alkylbenzenes; (f) N-heterocyclics; (g) n-fatty acids; (h) n-alkanes; (i) alkenes; (j) sterols; (k) n-diols and (l) high molecular weight compounds (> m/z 562). Of special interest were the high abundances of low-molecular weight compounds in the two bio-oils which constituted close to one half of the two bio-oils. Prominent among these compounds were water, ammonia, acetic acid, acetamide, propyl radical, formamide and hydrogen cyanide. The main quantitative differences between the two bio-oils was that bio-oil Fraction I, as analyzed by the two mass spectrometric methods, contained lower concentrations of low-molecular weight compounds, carbohydrates, and N-heterocyclics than bio-oil Fraction II but was richer in lignin dimers, n-alkylbenzenes and aliphatics (n-fatty acids, n-alkanes, alkenes, and n-diols). Of special interest were the N-heterocyclics in the two bio-oils such as pyrazole, pyrazoline, substituted

  6. Fast microwave-assisted catalytic co-pyrolysis of lignin and low-density polyethylene with HZSM-5 and MgO for improved bio-oil yield and quality.

    PubMed

    Fan, Liangliang; Chen, Paul; Zhang, Yaning; Liu, Shiyu; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Ruan, Roger

    2017-02-01

    Fast microwave-assisted catalytic co-pyrolysis of lignin and low-density polyethylene (LDPE) with HZSM-5 and MgO was investigated. Effects of pyrolysis temperature, lignin to LDPE ratio, MgO to HZSM-5 ratio, and feedstock to catalyst ratio on the products yields and chemical profiles were examined. 500°C was the optimal co-pyrolysis temperature in terms of the maximum bio-oil yield. The proportion of aromatics increased with increasing LDPE content. In addition, with the addition of LDPE (lignin/LDPE=1/2), methoxyl group in the phenols was completely removed. A synergistic effect was found between lignin and LDPE. The proportion of aromatics increased and alkylated phenols decreased with increasing HZSM-5 to MgO ratio. The bio-oil yield increased with the addition of appropriate amount of catalyst and the proportion of alkylated phenols increased with increasing catalyst to feedstock ratio.

  7. Review of NMR characterization of pyrolysis oils

    DOE PAGES

    Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun; ...

    2016-08-24

    Here, pyrolysis of renewable biomass has been developed as a method to produce green fuels and chemicals in response to energy security concerns as well as to alleviate environmental issues incurred with fossil fuel usage. However, pyrolysis oils still have limited commercial application, mainly because unprocessed oils cannot be readily blended with current petroleum-based transportation fuels. To better understand these challenges, researchers have applied diverse characterization techniques in the development of bio-oil studies. In particular, nuclear magnetic resonance (NMR) is a key spectroscopic characterization method through analysis of bio-oil components. This review highlights the NMR strategies for pyrolysis oil characterizationmore » and critically discusses the applications of 1H, 13C, 31P, 19F, and two-dimensional (2-D NMR) analyses such as heteronuclear single quantum correlation (HSQC) in representative pyrolysis oil studies.« less

  8. Review of NMR characterization of pyrolysis oils

    SciTech Connect

    Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun; Adhikari, Sushil; Ragauskas, Arthur J.

    2016-08-24

    Here, pyrolysis of renewable biomass has been developed as a method to produce green fuels and chemicals in response to energy security concerns as well as to alleviate environmental issues incurred with fossil fuel usage. However, pyrolysis oils still have limited commercial application, mainly because unprocessed oils cannot be readily blended with current petroleum-based transportation fuels. To better understand these challenges, researchers have applied diverse characterization techniques in the development of bio-oil studies. In particular, nuclear magnetic resonance (NMR) is a key spectroscopic characterization method through analysis of bio-oil components. This review highlights the NMR strategies for pyrolysis oil characterization and critically discusses the applications of 1H, 13C, 31P, 19F, and two-dimensional (2-D NMR) analyses such as heteronuclear single quantum correlation (HSQC) in representative pyrolysis oil studies.

  9. Review of NMR characterization of pyrolysis oils

    SciTech Connect

    Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun; Adhikari, Sushil; Ragauskas, Arthur J.

    2016-08-24

    Here, pyrolysis of renewable biomass has been developed as a method to produce green fuels and chemicals in response to energy security concerns as well as to alleviate environmental issues incurred with fossil fuel usage. However, pyrolysis oils still have limited commercial application, mainly because unprocessed oils cannot be readily blended with current petroleum-based transportation fuels. To better understand these challenges, researchers have applied diverse characterization techniques in the development of bio-oil studies. In particular, nuclear magnetic resonance (NMR) is a key spectroscopic characterization method through analysis of bio-oil components. This review highlights the NMR strategies for pyrolysis oil characterization and critically discusses the applications of 1H, 13C, 31P, 19F, and two-dimensional (2-D NMR) analyses such as heteronuclear single quantum correlation (HSQC) in representative pyrolysis oil studies.

  10. 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.

  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. 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.

  13. Life-Cycle Assessment of Pyrolysis Bio-Oil Production*

    SciTech Connect

    Steele, Philip; Puettmann, Maureen E.; Penmetsa, Venkata Kanthi; Cooper, Jerome E.

    2012-07-01

    As part ofthe Consortium for Research on Renewable Industrial Materials' Phase I life-cycle assessments ofbiofuels, lifecycle inventory burdens from the production of bio-oil were developed and compared with measures for residual fuel oil. Bio-oil feedstock was produced using whole southern pine (Pinus taeda) trees, chipped, and converted into bio-oil by fast pyrolysis. Input parameters and mass and energy balances were derived with Aspen. Mass and energy balances were input to SimaPro to determine the environmental performance of bio-oil compared with residual fuel oil as a heating fuel. Equivalent functional units of 1 MJ were used for demonstrating environmental preference in impact categories, such as fossil fuel use and global warming potential. Results showed near carbon neutrality of the bio-oil. Substituting bio-oil for residual fuel oil, based on the relative carbon emissions of the two fuels, estimated a reduction in CO2 emissions by 0.075 kg CO2 per MJ of fuel combustion or a 70 percent reduction in emission over residual fuel oil. The bio-oil production life-cycle stage consumed 92 percent of the total cradle-to-grave energy requirements, while feedstock collection, preparation, and transportation consumed 4 percent each. This model provides a framework to better understand the major factors affecting greenhouse gas emissions related to bio-oil production and conversion to boiler fuel during fast pyrolysis.

  14. Bactericidal Mechanism of Bio-oil Obtained from Fast Pyrolysis of Pinus densiflora Against Two Foodborne Pathogens, Bacillus cereus and Listeria monocytogenes.

    PubMed

    Patra, Jayanta Kumar; Hwang, Hyewon; Choi, Joon Weon; Baek, Kwang-Hyun

    2015-06-01

    Foodborne bacteria are the leading cause of food spoilage and other related diseases. In the present study, the antibacterial activity of bio-oil (BO) manufactured by fast pyrolysis of pinewood sawdust (Pinus densiflora Siebold and Zucc.) against two disease-causing foodborne pathogens (Bacillus cereus and Listeria monocytogenes) was evaluated. BO at a concentration of 1000 μg/disc was highly active against both B. cereus (10.0-10.6 mm-inhibition zone) and L. monocytogenes (10.6-12.0-mm inhibition zone). The minimum inhibitory concentration (MIC) and minimum bactericidal concentration values of BO were 500 and 1000 μg/mL, respectively, for both pathogens. At the MIC concentration, BO exhibited an inhibitory effect on the viability of the bacterial pathogens. The mechanism of action of BO revealed its strong impairing effect on the membrane integrity of bacterial cells, which was confirmed by a marked release of 260-nm absorbing material, leakage of electrolytes and K(+) ions, and reduced capacity for osmoregulation under high salt concentration. Scanning electron microscopy clearly showed morphological alteration of the cell membrane due to the effect of BO. Overall, the results of this study suggest that BO exerts effective antibacterial potential against foodborne pathogens and can therefore potentially be used in food processing and preservation.

  15. Fungicidal values of bio-oils and their lignin-rich fractions obtained from wood/bark fast pyrolysis.

    PubMed

    Mohan, Dinesh; Shi, Jenny; Nicholas, Darrel D; Pittman, Charles U; Steele, Philip H; Cooper, Jerome E

    2008-03-01

    Pine wood, pine bark, oak wood and oak bark were pyrolyzed in an auger reactor. A total of 16 bio-oils or pyrolytic oils were generated at different temperatures and residence times. Two additional pine bio-oils were produced at the National Renewable Energy Laboratory in a fluidized-bed reactor at different temperatures. All these bio-oils were fractionated to obtain lignin-rich fractions which consist mainly of phenols and neutrals. The pyrolytic lignin-rich fractions were obtained by liquid-liquid extraction. Whole bio-oils and their lignin-rich fractions were studied as potential environmentally benign wood preservatives to replace metal-based CCA and copper systems that have raised environmental concerns. Each bio-oil and several lignin-rich fractions were tested for antifungal properties. Soil block tests were conducted using one brown-rot fungus (Gloeophyllum trabeum) and one white-rot fungus (Trametes versicolor). The lignin-rich fractions showed greater fungal inhibition than whole bio-oils for a impregnation solution 10% concentration level. Water repellence tests were also performed to study wood wafer swelling behavior before and after bio-oil and lignin-rich fraction treatments. In this case, bio-oil fractions did not exhibit higher water repellency than whole bio-oils. Comparison of raw bio-oils in soil block tests, with unleached wafers, at 10% and 25% bio-oil impregnation solution concentration levels showed excellent wood preservation properties at the 25% level. The good performance of raw bio-oils at higher loading levels suggests that fractionation to generate lignin-rich fractions is unnecessary. At this more effective 25% loading level in general, the raw bio-oils performed similarly. Prevention of leaching is critically important for both raw bio-oils and their fractions to provide decay resistance. Initial tests of a polymerization chemical to prevent leaching showed some success.

  16. 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)

  17. 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.

  18. Solar heated oil shale pyrolysis process

    NASA Technical Reports Server (NTRS)

    Qader, S. A. (Inventor)

    1985-01-01

    An improved system for recovery of a liquid hydrocarbon fuel from oil shale is presented. The oil shale pyrolysis system is composed of a retort reactor for receiving a bed of oil shale particules which are heated to pyrolyis temperature by means of a recycled solar heated gas stream. The gas stream is separated from the recovered shale oil and a portion of the gas stream is rapidly heated to pyrolysis temperature by passing it through an efficient solar heater. Steam, oxygen, air or other oxidizing gases can be injected into the recycle gas before or after the recycle gas is heated to pyrolysis temperature and thus raise the temperature before it enters the retort reactor. The use of solar thermal heat to preheat the recycle gas and optionally the steam before introducing it into the bed of shale, increases the yield of shale oil.

  19. CORROSIVITY AND COMPOSITION OF RAW AND TREATED PYROLYSIS OILS

    SciTech Connect

    Keiser, Jim; Howell, Michael; Connatser, Raynella M.; Lewis, Sam; Elliott, Douglas C.

    2012-10-14

    Fast pyrolysis offers a relatively low cost method of processing biomass to produce a liquid product that has the potential for conversion to several types of liquid fuels. The liquid product of fast pyrolysis, known as pyrolysis oil or bio-oil, contains a high oxygen content primarily in the form of water, carboxylic acids, phenols, ketones and aldehydes. These oils are typically very acidic with a Total Acid Number that is often in the range of 50 to 100, and previous studies have shown this material to be quite corrosive to common structural materials. Removal of at least some of the oxygen and conversion of this oil to a more useful product that is considerably less corrosive can be accomplished through a hydrogenation process. The product of such a treatment is considered to have the potential for blending with crude oil for processing in petroleum refineries. Corrosion studies and chemical analyses have been conducted using as produced bio-oil samples as well as samples that have been subjected to different levels of oxygen removal. Chemical analyses show treatment affected the concentrations of carboxylic acids contained in the oil, and corrosion studies showed a positive benefit of the oxygen removal. Results of these studies will be presented in this paper.

  20. A review of the chemical and physical mechanisms of the storage stability of fast pyrolysis bio-oils

    SciTech Connect

    Diebold, J.P.

    1999-01-27

    Understanding the fundamental chemical and physical aging mechanisms is necessary to learn how to produce a bio-oil that is more stable during shipping and storage. This review provides a basis for this understanding and identifies possible future research paths to produce bio-oils with better storage stability.

  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. 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.

  3. Indirect heating pyrolysis of oil shale

    DOEpatents

    Jones, Jr., John B.; Reeves, Adam A.

    1978-09-26

    Hot, non-oxygenous gas at carefully controlled quantities and at predetermined depths in a bed of lump oil shale provides pyrolysis of the contained kerogen of the oil shale, and cool non-oxygenous gas is passed up through the bed to conserve the heat

  4. 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.

  5. Determination of volatile organic compounds in eucalyptus fast pyrolysis bio-oil by full evaporation headspace gas chromatography.

    PubMed

    Kosinski Lima, Nathalya; Romualdo Lopes, André; Gimenes Guerrero, Palimecio; Itsuo Yamamoto, Carlos; Augusto Hansel, Fabricio

    2018-01-01

    This paper reports a full evaporation (FE) headspace gas chromatographic (HS-GC) method for the determination of the volatile organic compounds (VOCs) in bio-oil (i.e. methanol, ethanol, acetone, acetic acid and furfural). The method uses a 4μL sample of bio-oil in a headspace vial (ca. 20mL). Complete evaporation of the compounds was achieved after seven minutes at 90°C. The method showed good precision and accuracy for methanol, ethanol, acetone and acetic acid. The recovery of furfural was low (74.3%). The results showed that the protocol can be applied for the determination of methanol, ethanol, acetone and acetic acid in bio-oil. Detection limits ranged from 0.13 to 0.16μg. Acetic acid was the dominant analyte in the heavy bio-oil and light bio-oil analysis (113. 3 and 85.1µgmg(-1), respectively), followed by methanol, ethanol, and acetone. The polymerisation of furfural was suspected as the cause of its poor quantification. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. 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...

  7. 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...

  8. 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...

  9. Triacetonamine formation in a bio-oil from fast pyrolysis of sewage sludge using acetone as the absorption solvent.

    PubMed

    Cao, Jing-Pei; Zhao, Xiao-Yan; Morishita, Kayoko; Li, Liu-Yun; Xiao, Xian-Bin; Obara, Ryoji; Wei, Xian-Yong; Takarada, Takayuki

    2010-06-01

    A sewage sludge sample was pyrolyzed in a drop tube furnace at 500 degrees C and sweeping gas flow rate of 300cm(3)/min. Triacetonamine (TAA) was detected with GC/MS as major component in the resulting bio-oil using acetone as the absorption solvent and proven to be a product from the reaction of NH(3) in the bio-oil with the absorption solvent acetone. TAA yield increased with storage time and reached a level about 28.4% (% sludge fed, daf) after 175h. Since the reaction of pure NH(3) with acetone does not proceed, some species in the bio-oil must catalyze the reaction of NH(3) with acetone. TAA was isolated in a high yield (27.9%, daf) and high purity (80.4%) by column chromatography with different solvents, including mixed solvents, as eluants. The study revealed the possibility of sewage sludge as potential resource of TAA. Copyright 2010 Elsevier Ltd. All rights reserved.

  10. 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...

  11. 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.

  12. 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.

  13. 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.

  14. Production of bio-based phenolic resin and activated carbon from bio-oil and biochar derived from fast pyrolysis of palm kernel shells.

    PubMed

    Choi, Gyung-Goo; Oh, Seung-Jin; Lee, Soon-Jang; Kim, Joo-Sik

    2015-02-01

    A fraction of palm kernel shells (PKS) was pyrolyzed in a fluidized bed reactor. The experiments were performed in a temperature range of 479-555 °C to produce bio-oil, biochar, and gas. All the bio-oils were analyzed quantitatively and qualitatively by GC-FID and GC-MS. The maximum content of phenolic compounds in the bio-oil was 24.8 wt.% at ∼500 °C. The maximum phenol content in the bio-oil, as determined by the external standard method, was 8.1 wt.%. A bio-oil derived from the pyrolysis of PKS was used in the synthesis of phenolic resin, showing that the bio-oil could substitute for fossil phenol up to 25 wt.%. The biochar was activated using CO2 at a final activation temperature of 900 °C with different activation time (1-3 h) to produce activated carbon. Activated carbons produced were microporous, and the maximum surface area of the activated carbons produced was 807 m(2)/g.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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

  1. Fast pyrolysis of palm kernel shells: influence of operation parameters on the bio-oil yield and the yield of phenol and phenolic compounds.

    PubMed

    Kim, Seon-Jin; Jung, Su-Hwa; Kim, Joo-Sik

    2010-12-01

    Palm kernel shells were pyrolyzed in a pyrolysis plant equipped with a fluidized-bed reactor and a char-separation system. The influence of reaction temperature, feed size and feed rate on the product spectrum was also investigated. In addition, the effect of reaction temperature on the yields of phenol and phenolic compounds in the bio-oil was examined. The maximum bio-oil yield was 48.7 wt.% of the product at 490 degrees C. The maximum yield of phenol plus phenolic compounds amounted to about 70 area percentage at 475 degrees C. The yield of pyrolytic lignin after its isolation from the bio-oil was approximately 46 wt.% based on the water and ash free oil. The pyrolytic lignin was mainly composed of phenol, phenolic compounds and oligomers of coniferyl, sinapyl and p-coumaryl alcohols. From the result of a GPC analysis, the number average molecular weight and the weight average molecular weight were 325 and 463 g/mol, respectively.

  2. Methods and apparatuses for deoxygenating pyrolysis oil

    DOEpatents

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

    2017-09-12

    Methods and apparatuses are provided for deoxygenating pyrolysis oil. A method includes contacting a pyrolysis oil with a deoxygenation catalyst in a first reactor at deoxygenation conditions to produce a first reactor effluent. The first reactor effluent has a first oxygen concentration and a first hydrogen concentration, based on hydrocarbons in the first reactor effluent, and the first reactor effluent includes an aromatic compound. The first reactor effluent is contacted with a dehydrogenation catalyst in a second reactor at conditions that deoxygenate the first reactor effluent while preserving the aromatic compound to produce a second reactor effluent. The second reactor effluent has a second oxygen concentration lower than the first oxygen concentration and a second hydrogen concentration that is equal to or lower than the first hydrogen concentration, where the second oxygen concentration and the second hydrogen concentration are based on the hydrocarbons in the second reactor effluent.

  3. Effect of hydrothermal pretreatment on properties of bio-oil produced from fast pyrolysis of eucalyptus wood in a fluidized bed reactor.

    PubMed

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

    2013-06-01

    Eucalyptus wood powder was first subjected to hydrothermal pretreatment in a high-pressure reactor at 160-190°C, and subsequently fast pyrolyzed in a fluidized bed reactor at 500°C to obtain high quality bio-oil. This study focused on investigating effect of hydrothermal pretreatment on bio-oil properties. Hemicellulose and some metals were effectively removed from eucalyptus wood, while cellulose content was enhanced. No significant charring and carbonization of constituents was observed during hydrothermal pretreatment. Thus pretreated eucalyptus wood gave higher bio-oil yield than original eucalyptus wood. Chemical composition of bio-oil was examined by GC/MS and (13)C NMR analyses. Bio-oil produced from pretreated eucalyptus wood exhibited lower contents of ketones and acids, while much higher levoglucosan content than bio-oil produced from original eucalyptus wood, which would help to improve thermal stability of bio-oil and extract levoglucosan from bio-oil. Hydrothermal pretreatment also improved bio-oil fuel quality through lowering water content and enhancing heating value.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. Preliminary Economics for the Production of Pyrolysis Oil from Lignin in a Cellulosic Ethanol Biorefinery

    SciTech Connect

    Jones, Susanne B.; Zhu, Yunhua

    2009-04-01

    Cellulosic ethanol biorefinery economics can be potentially improved by converting by-product lignin into high valued products. Cellulosic biomass is composed mainly of cellulose, hemicellulose and lignin. In a cellulosic ethanol biorefinery, cellulose and hemicellullose are converted to ethanol via fermentation. The raw lignin portion is the partially dewatered stream that is separated from the product ethanol and contains lignin, unconverted feed and other by-products. It can be burned as fuel for the plant or can be diverted into higher-value products. One such higher-valued product is pyrolysis oil, a fuel that can be further upgraded into motor gasoline fuels. While pyrolysis of pure lignin is not a good source of pyrolysis liquids, raw lignin containing unconverted feed and by-products may have potential as a feedstock. This report considers only the production of the pyrolysis oil and does not estimate the cost of upgrading that oil into synthetic crude oil or finished gasoline and diesel. A techno-economic analysis for the production of pyrolysis oil from raw lignin was conducted. comparing two cellulosic ethanol fermentation based biorefineries. The base case is the NREL 2002 cellulosic ethanol design report case where 2000 MTPD of corn stover is fermented to ethanol (NREL 2002). In the base case, lignin is separated from the ethanol product, dewatered, and burned to produce steam and power. The alternate case considered in this report dries the lignin, and then uses fast pyrolysis to generate a bio-oil product. Steam and power are generated in this alternate case by burning some of the corn stover feed, rather than fermenting it. This reduces the annual ethanol production rate from 69 to 54 million gallons/year. Assuming a pyrolysis oil value similar to Btu-adjusted residual oil, the estimated ethanol selling price ranges from $1.40 to $1.48 (2007 $) depending upon the yield of pyrolysis oil. This is considerably above the target minimum ethanol selling

  9. 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.

  10. 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.

  11. 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...

  12. 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...

  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. Processes for converting lignocellulosics to reduced acid pyrolysis oil

    DOEpatents

    Kocal, Joseph Anthony; Brandvold, Timothy A

    2015-01-06

    Processes for producing reduced acid lignocellulosic-derived pyrolysis oil are provided. In a process, lignocellulosic material is fed to a heating zone. A basic solid catalyst is delivered to the heating zone. The lignocellulosic material is pyrolyzed in the presence of the basic solid catalyst in the heating zone to create pyrolysis gases. The oxygen in the pyrolysis gases is catalytically converted to separable species in the heating zone. The pyrolysis gases are removed from the heating zone and are liquefied to form the reduced acid lignocellulosic-derived pyrolysis oil.

  15. CONVERTING PYROLYSIS OILS TO RENEWABLE TRANSPORT FUELS: PROCESSING CHALLENGES & OPPORTUNITIES

    SciTech Connect

    Holmgren, Jennifer; Nair, Prabhakar N.; Elliott, Douglas C.; Bain, Richard; Marinangelli, Richard

    2008-03-11

    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. UOP, in partnership with U.S. Government labs, NREL and PNNL, is developing an alternate route using cellulosic feedstocks. The waste biomass is first subjected to 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.

  16. 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.

  17. Stabilization of Softwood-Derived Pyrolysis Oils for Continuous Bio-oil Hydroprocessing

    SciTech Connect

    Olarte, Mariefel V.; Zacher, Alan H.; Padmaperuma, Asanga B.; Burton, Sarah D.; Job, Heather M.; Lemmon, Teresa L.; Swita, Marie S.; Rotness, Leslie J.; Neuenschwander, Gary N.; Frye, John G.; Elliott, Douglas C.

    2015-10-15

    The use of fast pyrolysis as a potential renewable liquid transportation fuel alternative to crude oil depends on successful catalytic upgrading to produce a refinery-ready product with oxygen content and qualities (i.e. specific functional group or compound content) that is compatible with the product’s proposed insertion point. Catalytic upgrading of bio-oil requires high temperature and pressure, while similar to crude oil hydrotreating, is not as straightforward for the thermally unstable pyrolysis oil. For years, a two-temperature zone, downflow trickle bed reactor was the state-of-the art for continuous operation. However, pressure excursion due to plug formation still occurred, typically at the high temperature transition zone, leading to a process shutdown within 140 h. Recently, a bio-oil pre-treatment process, together with a robust commercial catalyst, was found to be enabling the continuous operation of the two-zone hydroprocessing system. Here, we report the results on pre-treating bio-oil at 413 K and 8.4 MPa of flowing H2 (500 L H2/L bio-oil, 0.5 L bio-oil/L catalyst bed) and the attempts to characterize this oil product to understand the chemistry which enabled the long-term processing of bio-oil.

  18. 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.

  19. Combustion fundamentals of pyrolysis oil based fuels

    SciTech Connect

    Calabria, R.; Chiariello, F.; Massoli, P.

    2007-04-15

    The combustion behavior of emulsions of pyrolysis oil in commercial diesel oil was studied. The emulsions were different in terms of concentration and size of the dispersed phase. The study was carried out in a single droplet combustion chamber. The size of droplets varied between 400 {mu}m and 1200 {mu}m. They were suspended to a bare thermocouple and, hence, their temperature during combustion was measured. High-speed digital shadowgraphy was used to follow droplets evolution. The main features of the droplet combustion were recognized. The general combustion behavior of emulsions is intermediate with respect to pure PO and commercial diesel oil. Emulsion droplets underwent strong swelling and microexplosion phenomena. However, under the investigated conditions, the microexplosions were ineffective in destroying droplets. The size distribution of the dispersed PO droplets in the range 3-10 {mu}m was not effective either for determining the overall thermal behavior or for the efficacy of the microexplosions. The homogeneous combustion phase resulted identical for emulsions and diesel oil despite the emulsions composition (i.e., concentration of oil, surfactant and co-surfactant, as well as the size of the oil droplets in the emulsion) and the different structure of the flame and also its time and spatial evolution. (author)

  20. 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.

  1. Evaluation of Pyrolysis Oil as Carbon Source for Fungal Fermentation.

    PubMed

    Dörsam, Stefan; Kirchhoff, Jennifer; Bigalke, Michael; Dahmen, Nicolaus; Syldatk, Christoph; Ochsenreither, Katrin

    2016-01-01

    Pyrolysis oil, a complex mixture of several organic compounds, produced during flash pyrolysis of organic lignocellulosic material was evaluated for its suitability as alternative carbon source for fungal growth and fermentation processes. Therefore several fungi from all phyla were screened for their tolerance toward pyrolysis oil. Additionally Aspergillus oryzae and Rhizopus delemar, both established organic acid producers, were chosen as model organisms to investigate the suitability of pyrolysis oil as carbon source in fungal production processes. It was observed that A. oryzae tolerates pyrolysis oil concentrations between 1 and 2% depending on growth phase or stationary production phase, respectively. To investigate possible reasons for the low tolerance level, eleven substances from pyrolysis oil including aldehydes, organic acids, small organic compounds and phenolic substances were selected and maximum concentrations still allowing growth and organic acid production were determined. Furthermore, effects of substances to malic acid production were analyzed and compounds were categorized regarding their properties in three groups of toxicity. To validate the results, further tests were also performed with R. delemar. For the first time it could be shown that small amounts of phenolic substances are beneficial for organic acid production and A. oryzae might be able to degrade isoeugenol. Regarding pyrolysis oil toxicity, 2-cyclopenten-1-on was identified as the most toxic compound for filamentous fungi; a substance never described for anti-fungal or any other toxic properties before and possibly responsible for the low fungal tolerance levels toward pyrolysis oil.

  2. Evaluation of Pyrolysis Oil as Carbon Source for Fungal Fermentation

    PubMed Central

    Dörsam, Stefan; Kirchhoff, Jennifer; Bigalke, Michael; Dahmen, Nicolaus; Syldatk, Christoph; Ochsenreither, Katrin

    2016-01-01

    Pyrolysis oil, a complex mixture of several organic compounds, produced during flash pyrolysis of organic lignocellulosic material was evaluated for its suitability as alternative carbon source for fungal growth and fermentation processes. Therefore several fungi from all phyla were screened for their tolerance toward pyrolysis oil. Additionally Aspergillus oryzae and Rhizopus delemar, both established organic acid producers, were chosen as model organisms to investigate the suitability of pyrolysis oil as carbon source in fungal production processes. It was observed that A. oryzae tolerates pyrolysis oil concentrations between 1 and 2% depending on growth phase or stationary production phase, respectively. To investigate possible reasons for the low tolerance level, eleven substances from pyrolysis oil including aldehydes, organic acids, small organic compounds and phenolic substances were selected and maximum concentrations still allowing growth and organic acid production were determined. Furthermore, effects of substances to malic acid production were analyzed and compounds were categorized regarding their properties in three groups of toxicity. To validate the results, further tests were also performed with R. delemar. For the first time it could be shown that small amounts of phenolic substances are beneficial for organic acid production and A. oryzae might be able to degrade isoeugenol. Regarding pyrolysis oil toxicity, 2-cyclopenten-1-on was identified as the most toxic compound for filamentous fungi; a substance never described for anti-fungal or any other toxic properties before and possibly responsible for the low fungal tolerance levels toward pyrolysis oil. PMID:28066378

  3. 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.

  4. 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.

  5. 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.

  6. [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.

  7. 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.

  8. [Components of oil sludge and their influence on pyrolysis behaviors].

    PubMed

    Song, Wei; Liu, Jian-Guo; Nie, Yong-Feng

    2008-07-01

    Based on property analysis of oil sludge and its main components (mineral oil and minerals), pyrolysis process and releasing behavior of non-condensed gas of oil sludge and its main components were studied by thermogravimetric analysis-fourier transform infrared spectroscopy (TG-FTIR) and tubular resistance furnace, respectively. The results indicated that, (1) Oil sludge was characterized as relatively high heating value (15 422.41 kJ/kg), higher mineral content (61.57%) mainly composed of quartz. Mineral oil component had good thermal conversion property and adhered close with mineral in oil sludge. (2) Pyrolysis process of oil sludge included 5 stages: water volatilization and gas desorption (50-180 degrees C), light oil volatilization (180-370 degrees C), heavy oil pyrolysis (370-500 degrees C), semi-coke charring (500-600 degrees C) and mineral decomposition (higher than 600 degrees C). (3) Minerals influenced oil pyrolysis by surface function and enhancing heating conductivity, meanwhile minor elements in mineral oil could bring mineral decomposition temperature down. (4) Minerals affected the releasing behavior of non-condensed gas from mineral oil pyrolysis and resulted in lower total production and higher H2 production.

  9. Validation Results for Core-Scale Oil Shale Pyrolysis

    SciTech Connect

    Staten, Josh; Tiwari, Pankaj

    2015-03-01

    This report summarizes a study of oil shale pyrolysis at various scales and the subsequent development a model for in situ production of oil from oil shale. Oil shale from the Mahogany zone of the Green River formation was used in all experiments. Pyrolysis experiments were conducted at four scales, powdered samples (100 mesh) and core samples of 0.75”, 1” and 2.5” diameters. The batch, semibatch and continuous flow pyrolysis experiments were designed to study the effect of temperature (300°C to 500°C), heating rate (1°C/min to 10°C/min), pressure (ambient and 500 psig) and size of the sample on product formation. Comprehensive analyses were performed on reactants and products - liquid, gas and spent shale. These experimental studies were designed to understand the relevant coupled phenomena (reaction kinetics, heat transfer, mass transfer, thermodynamics) at multiple scales. A model for oil shale pyrolysis was developed in the COMSOL multiphysics platform. A general kinetic model was integrated with important physical and chemical phenomena that occur during pyrolysis. The secondary reactions of coking and cracking in the product phase were addressed. The multiscale experimental data generated and the models developed provide an understanding of the simultaneous effects of chemical kinetics, and heat and mass transfer on oil quality and yield. The comprehensive data collected in this study will help advance the move to large-scale in situ oil production from the pyrolysis of oil shale.

  10. Catalytic partial oxidation of pyrolysis oils

    NASA Astrophysics Data System (ADS)

    Rennard, David Carl

    2009-12-01

    This thesis explores the catalytic partial oxidation (CPO) of pyrolysis oils to syngas and chemicals. First, an exploration of model compounds and their chemistries under CPO conditions is considered. Then CPO experiments of raw pyrolysis oils are detailed. Finally, plans for future development in this field are discussed. In Chapter 2, organic acids such as propionic acid and lactic acid are oxidized to syngas over Pt catalysts. Equilibrium production of syngas can be achieved over Rh-Ce catalysts; alternatively mechanistic evidence is derived using Pt catalysts in a fuel rich mixture. These experiments show that organic acids, present in pyrolysis oils up to 25%, can undergo CPO to syngas or for the production of chemicals. As the fossil fuels industry also provides organic chemicals such as monomers for plastics, the possibility of deriving such species from pyrolysis oils allows for a greater application of the CPO of biomass. However, chemical production is highly dependent on the originating molecular species. As bio oil comprises up to 400 chemicals, it is essential to understand how difficult it would be to develop a pure product stream. Chapter 3 continues the experimentation from Chapter 2, exploring the CPO of another organic functionality: the ester group. These experiments demonstrate that equilibrium syngas production is possible for esters as well as acids in autothermal operation with contact times as low as tau = 10 ms over Rh-based catalysts. Conversion for these experiments and those with organic acids is >98%, demonstrating the high reactivity of oxygenated compounds on noble metal catalysts. Under CPO conditions, esters decompose in a predictable manner: over Pt and with high fuel to oxygen, non-equilibrium products show a similarity to those from related acids. A mechanism is proposed in which ethyl esters thermally decompose to ethylene and an acid, which decarbonylates homogeneously, driven by heat produced at the catalyst surface. Chapter 4

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

    NASA Astrophysics Data System (ADS)

    Abdullah, Nurhayati; Sulaiman, Fauziah; Aliasak, Zalila

    2013-05-01

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

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. Maximizing the stability of pyrolysis oil/diesel fuel emulsions

    USDA-ARS?s Scientific Manuscript database

    Several emulsions consisting of biomass pyrolysis oil (bio-oil) in diesel fuel were produced and analyzed for stability over time. An ultrasonic probe was used to generate microscopic droplets of bio-oil suspended in diesel fuel, and this emulsion was stabilized using surfactant chemicals. The most...

  17. 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.

  18. 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...

  19. 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 ...

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

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

    PubMed Central

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

    2016-01-01

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

  9. 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.

  10. Upgrading of Intermediate Bio-Oil Produced by Catalytic Pyrolysis

    SciTech Connect

    Abdullah, Zia; Chadwell, Brad; Taha, Rachid; Hindin, Barry; Ralston, Kevin

    2015-06-30

    The objectives of this project were to (1) develop a process to upgrade catalytic pyrolysis bio-oil, (2) investigate new upgrading catalysts suited for upgrading catalytic pyrolysis bio-oil, (3) demonstrate upgrading system operation for more than 1,000 hours using a single catalyst charge, and (4) produce a final upgraded product that can be blended to 30 percent by weight with petroleum fuels or that is compatible with existing petroleum refining operations. This project has, to the best of our knowledge, for the first time enabled a commercially viable bio-oil hydrotreatment process to produce renewable blend stock for transportation fuels.

  11. 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.

  12. The Influence of Process Conditions on the Chemical Composition of Pine Wood Catalytic Pyrolysis Oils

    DOE PAGES

    Pereira, J.; Agblevor, F. A.; Beis, S. H.

    2012-01-01

    Pine wood samples were used as model feedstock to study the properties of catalytic fast pyrolysis oils. The influence of two commercial zeolite catalysts (BASF and SudChem) and pretreatment of the pine wood with sodium hydroxide on pyrolysis products were investigated. The pyrolysis oils were first fractionated using column chromatography and characterized using GC-MS. Long chain aliphatic hydrocarbons, levoglucosan, aldehydes and ketones, guaiacols/syringols, and benzenediols were the major compounds identified in the pyrolysis oils. The catalytic pyrolysis increased the polycyclic hydrocarbons fraction. Significant decreases in phthalate derivatives using SudChem and long chain aliphatics using BASF catalyst were observed. Significant amountsmore » of aromatic heterocyclic hydrocarbons and benzene derivatives were formed, respectively, using BASF and SudChem catalysts. Guaiacyl/syringyl and benzenediols derivatives were partly suppressed by the zeolite catalysts, while the sodium hydroxide treatment enriched phenolic derivatives. Zeolite catalyst and sodium hydroxide were employed together; they showed different results for each catalyst.« less

  13. Production of valuable hydrocarbons by flash pyrolysis of oil shale

    DOEpatents

    Steinberg, M.; Fallon, P.T.

    1985-04-01

    A process for the production of gas and liquid hydrocarbons from particulated oil shale by reaction with a pyrolysis gas at a temperature of from about 700/sup 0/C to about 1100/sup 0/C, at a pressure of from about 400 psi to about 600 psi, for a period of about 0.2 second to about 20 seconds. Such a pyrolysis gas includes methane, helium, or hydrogen. 3 figs., 3 tabs.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. Sulfonation of phenols extracted from the pyrolysis oil of oil palm shells for enhanced oil recovery.

    PubMed

    Awang, Mariyamni; Seng, Goh Meng

    2008-01-01

    The cost of chemicals prohibits many technically feasible enhanced oil recovery methods to be applied in oil fields. It is shown that by-products from oil palm processing can be a source of valuable chemicals. Analysis of the pyrolysis oil from oil palm shells, a by-product of the palm oil industry, reveals a complex mixture of mainly phenolic compounds, carboxylic acids, and aldehydes. The phenolic compounds were extracted from the pyrolysis oil by liquid-liquid extraction using alkali and an organic solvent and analyzed, indicating the presence of over 93% phenols and phenolic compounds. Simultaneous sulfonation and alkylation of the pyrolysis oil was carried out to produce surfactants for application in oil fields. The lowest measured surface tension and critical micelle concentration was 30.2 mNm(-1) and 0.22 wt%, respectively. Displacement tests showed that 7-14% of the original oil in place was recovered by using a combination of surfactants and xanthan (polymer) as additives.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. Kinetic Study on Pyrolysis of Oil Palm Frond

    NASA Astrophysics Data System (ADS)

    Soon, V. S. Y.; Chin, B. L. F.; Lim, A. C. R.

    2016-03-01

    The pyrolysis of oil palm frond is studied using thermogravimetric analysis (TGA) equipment. The present study investigates the thermal degradation behaviour and determination of the kinetic parameters such as the activation energy (EA ) and pre-exponential factor (A) values of oil palm frond under pyrolysis condition. The kinetic data is produced based on first order rate of reaction. In this study, the experiments are conducted at different heating rates of 10, 20, 30, 40 and 50 K/min in the temperature range of 323-1173 K under non-isothermal condition. Argon gas is used as an inert gas to remove any entrapment of gases in the TGA equipment.

  4. 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

  5. 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.

  6. 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

  7. 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.

  8. Resources recovery of oil sludge by pyrolysis: Kinetics study

    SciTech Connect

    Shie, J.L.; Chang, C.Y.; Lin, J.P.; Wu, C.H.; Lee, D.J.

    1999-07-01

    Oil sludge, if unused, is one of the major industrial wastes needed to be treated for the petroleum refinery plant or petrochemical industry. It contains a large amount of combustibles with high heating values. The treatment of waste oil sludge by burning has certain benefit; however, it cannot provide the useful resource efficiently. On the other hand, the conversion of oil sludge to lower molecule weight organic compounds by pyrolysis not only solves the disposal problem but also matches the appeal of resource utilization. The major sources of oil sludge include the oil storage tank sludge, the biological sludge, the dissolve air flotation (DAF) scum, the American Petroleum Institute (API) separator sludge and the chemical sludge. In this study, the oil sludge from the oil storage tank of a typical petroleum refinery plant located in the northern Taiwan is used as the raw material of pyrolysis. Its heating value of dry basis and low heating value of wet basis are about 10,681 k cal/kg and 5,870 k cal/kg, respectively. The removal of the moisture of oil sludge significantly increases its heating value. The pyrolysis of oil sludge is conducted by the use of nitrogen as the carrier gas in the temperature range of 380 {approximately} 1,073 K and at various constant heating rates of 5.2, 12.8 and 21.8 K/min. The pyrolytic reaction is significant in 450 {approximately} 800 K and complex. For the sake of simplicity and engineering use, a one-reaction kinetic model is proposed for the pyrolysis of oil sludge, and is found to satisfactorily fit the experimental data. The activation energy, reaction order and frequency factor of the corresponding pyrolysis reaction in nitrogen for oil sludge are 78.22 kJ/mol, 2.92 and 9.48 105 l/min, respectively. These results are very useful for the proper design of the pyrolysis system of the oil sludge under investigation.

  9. 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.

  10. The use of tyre pyrolysis oil in diesel engines.

    PubMed

    Murugan, S; Ramaswamy, M C; Nagarajan, G

    2008-12-01

    Tests have been carried out to evaluate the performance, emission, and combustion characteristics of a single cylinder direct injection diesel engine fueled with 10%, 30%, and 50% of tyre pyrolysis oil (TPO) blended with diesel fuel (DF). The TPO was derived from waste automobile tyres through vacuum pyrolysis. The combustion parameters such as heat release rate, cylinder peak pressure, and maximum rate of pressure rise also analysed. Results showed that the brake thermal efficiency of the engine fueled with TPO-DF blends increased with an increase in blend concentration and reduction of DF concentration. NO(x), HC, CO, and smoke emissions were found to be higher at higher loads due to the high aromatic content and longer ignition delay. The cylinder peak pressure increased from 71 bars to 74 bars. The ignition delays were longer than with DF. It is concluded that it is possible to use tyre pyrolysis oil in diesel engines as an alternate fuel in the future.

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

    SciTech Connect

    Yang, Haiping; Chen, Hanping; Zheng, Chuguang; Yan, Rong; Lee, Dong Ho; Liang, David Tee

    2006-09-15

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

  12. Extraction and hydrolysis of levoglucosan from pyrolysis oil.

    PubMed

    Bennett, Nicole M; Helle, Steve S; Duff, Sheldon J B

    2009-12-01

    Fermentable sugar obtained from lignocellulosic material exhibits great potential as a renewable feedstock for the production of bio-ethanol. One potentially viable source of fermentable sugars is pyrolysis oil, commonly called bio-oil. Depending on the type of lignocellulosic material and the operating conditions used for pyrolysis, bio-oil can contain upwards of 10 wt% of 1,6-anhydro-beta-D-glucopyranose (levoglucosan, LG), an anhydrosugar that can be hydrolyzed to glucose. This research investigated the extraction of levoglucosan from pyrolysis oil via phase separation, the acid-hydrolysis of the levoglucosan into glucose, and the subsequent fermentation of this hydrolysate into ethanol. Optimal selection of water-to-oil ratio, temperature and contact time yielded an aqueous phase containing a levoglucosan concentration of up to 87 g/L, a yield of 7.8 wt% of the bio-oil. Hydrolysis conditions of 125 degrees C, 44 min and 0.5 M H(2)SO(4) resulted in a maximum glucose yield of 216% (when based on original levoglucosan), inferring other precursors of glucose were present in the aqueous phase. The aqueous phase contained solutes which inhibited fermentation, however, up to 20% hydrolysate solutions were efficiently fermented (yield=0.46 g EtOH/g glucose; productivity=0.55 g/L h) using high yeast inoculums (1 g/L in flask) and micro-aerophilic conditions.

  13. Pyrolysis of spill oils adsorbed on zeolites with product oils recycling.

    PubMed

    Tsai, Chun-Kuo; Liao, Chang-Yu; Wang, H Paul; Chien, Yi-Chi; Jou, Chih-Ju G

    2008-01-01

    Experimentally, a feasibility study for adsorption and catalytic pyrolysis of spill oils on Cu/ZSM-5 for recycling of light oils has been conducted in the present work. The adsorption and pyrolysis of model compounds such as heptane, toluene, and diesel (to stimulate the spill oils) on Cu/ZSM-5 have been investigated on a continuous fixed-bed reactor. By component fitted X-ray absorption near edge structural (XANES) spectroscopy, catalytic active species such as metallic copper (Cu) (77-84%) and Cu(2)O (6-7%) are found in the channels of ZSM-5 during pyrolysis of heptane or toluene. Pyrolysis of diesel effected by Cu/ZSM-5 yields gas (C(1)-C(5)) (32%) and light oil (68%) that can be used as auxiliary fuels.

  14. Hydrous pyrolysis of crude oil in gold-plated reactors

    USGS Publications Warehouse

    Curiale, J.A.; Lundegard, P.D.; Kharaka, Y.K.

    1992-01-01

    Crude oils from Iraq and California have been pyrolyzed under hydrous conditions at 200 and 300??C for time periods up to 210 days, in gold-plated reactors. Elemental (vanadium, nickel), stable isotopic (carbon), and molecular (n-alkanes, acyclic isoprenoids, steranes, terpanes and aromatic steroid hydrocarbons) analyses were made on the original and pyrolyzed oils. Various conventional crude oil maturity parameters, including 20S/(20S + 20R)-24-ethylcholestane ratios and the side-chain-length distribution of aliphatic and aromatic steroidal hydrocarbons, were measured in an effort to assess the modification of molecular maturity parameters in clay-free settings, similar to those encountered in "clean" reservoirs. Concentrations of vanadium and nickel in the Iraq oil decrease significantly and the V/(V + Ni) ratio decreases slightly, with increasing pyrolysis time/temperature. Whole oil carbon isotope ratios remain fairly constant during pyrolysis, as do hopane/sterane ratios and carbon number distribution of 5??(H),14??(H),17??(H),20R steranes. These latter three parameters are considered maturity-invariant. The ratios of short side-chain components to long side-chain components of the regular steranes [C21/(C21 + C29R)] and the triaromatic steroid hydrocarbons [C21/(C21 + C28)] vary systematically with increasing pyrolysis time, indicating that these parameters may be useful as molecular maturity parameters for crude oils in clay-free reservoir rocks. In addition, decreases in bisnorhopane/hopane ratio with increasing pyrolysis time, in a clay-free and kerogen-free environment, suggest that the distribution of these compounds is controlled by either differential thermal stabilities or preferential release from a higher-molecular weight portion of the oil. ?? 1992.

  15. 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.

  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. 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.

  1. Hybrid thermochemical processing: fermentation of pyrolysis-derived bio-oil.

    PubMed

    Jarboe, Laura R; Wen, Zhiyou; Choi, DongWon; Brown, Robert C

    2011-09-01

    Thermochemical processing of biomass by fast pyrolysis provides a nonenzymatic route for depolymerization of biomass into sugars that can be used for the biological production of fuels and chemicals. Fermentative utilization of this bio-oil faces two formidable challenges. First is the fact that most bio-oil-associated sugars are present in the anhydrous form. Metabolic engineering has enabled utilization of the main anhydrosugar, levoglucosan, in workhorse biocatalysts. The second challenge is the fact that bio-oil is rich in microbial inhibitors. Collection of bio-oil in distinct fractions, detoxification of bio-oil prior to fermentation, and increased robustness of the biocatalyst have all proven effective methods for addressing this inhibition.

  2. 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.

  3. The direct pyrolysis and catalytic pyrolysis of Nannochloropsis sp. residue for renewable bio-oils.

    PubMed

    Pan, Pan; Hu, Changwei; Yang, Wenyan; Li, Yuesong; Dong, Linlin; Zhu, Liangfang; Tong, Dongmei; Qing, Renwei; Fan, Yong

    2010-06-01

    Nannochloropsis sp. (a kind of green microalga) residue was pyrolyzed without catalyst or with different amount of HZSM-5 catalyst in a fixed bed reactor in nitrogen flow. The effects of pyrolysis parameters such as temperature and catalyst-to-material ratio on product yields were studied. The bio-oils obtained were analyzed by elemental, GC-MS and FTIR analysis. The results indicated that the bio-oils from catalytic pyrolysis of Nannochloropsis sp. residue (BOCP) had lower oxygen content (19.5 wt.%) and higher heating-value (32.7 MJ kg(-1)) than those obtained from direct pyrolysis (BODP) which had an oxygen content of 30.1 wt.% and heating-value of 24.6 MJ kg(-1). The BODP mainly consisted of long carbon chain compounds with various terminal groups (LCTG), while the BOCP mainly consisted of aromatic hydrocarbons. These properties of bio-oils demonstrated that the Nannochloropsis sp. residue can be used as a renewable energy resource and chemical feedstock.

  4. Pyrolysis of poppy capsule pulp for bio-oil production.

    PubMed

    Hopa, Derya Yeşim; Yılmaz, Nazan; Alagöz, Oğuzhan; Dilek, Meltem; Helvacı, Ahmet; Durupınar, Ümit

    2016-12-01

    The feasibility of biofuel production via the pyrolysis of poppy capsule pulp, the main waste product of Afyon Alkoloid Factory, was investigated. The poppy capsule pulp was shown to have a high volatile matter content (ca. 76%). Pyrolysis experiments were carried out in the temperature range 400-550°C (heating rate 18°C min(-1) and holding time 20 min) under a nitrogen atmosphere. The chemical components of the bio-oil were characterized by Fourier transform infrared spectrometry and gas chromatography-mass spectrometry. The effects of pyrolysis temperature on the production efficiency and the calorific value of the bio-oil were investigated. The maximum bio-oil yield and its calorific value at 500°C were 23.6% and 31.6 MJ kg(-1), respectively. The latter value is close to that of many petroleum fractions. This high-energy bio-oil is therefore a clean fuel precursor and can be upgraded into higher quality fuels.

  5. Recent advances in hydrotreating of pyrolysis bio-oil and its oxygen-containing model compounds

    SciTech Connect

    Wang, Huamin; Male, Jonathan L.; Wang, Yong

    2013-05-01

    There is considerable world-wide interest in discovering renewable sources of energy that can substitute for fossil fuels. Lignocellulosic biomass, which is the most abundant and inexpensive renewable feedstock on the planet, has a great potential for sustainable production of fuels, chemicals, and carbon-based materials. Fast pyrolysis integrated with hydrotreating is one of the simplest, most cost-effective and most efficient processes to convert lignocellulosic biomass to liquid hydrocarbon fuels for transportation, which has attracted significant attention in recent decades. However, effective hydrotreating of pyrolysis bio-oil presents a daunting challenge to the commercialization of biomass conversion via pyrolysis-hydrotreating. Specifically, development of active, selective, and stable hydrotreating catalysts is the bottleneck due to the poor quality of pyrolysis bio-oil feedstock (high oxygen content, molecular complexity, coking propensity, and corrosiveness). Significant research has been conducted to address the practical issues and provide the fundamental understanding of the hydrotreating/hydrodeoxygenation (HDO) of bio-oils and their oxygen-containing model compounds, including phenolics, furans, and carboxylic acids. A wide range of catalysts have been studied, including conventional Mo-based sulfide catalysts and noble metal catalysts, with the latter being the primary focus of the recent research because of their excellent catalytic performances and no requirement of environmentally unfriendly sulfur. The reaction mechanisms of HDO of model compounds on noble metal catalysts as well as their efficacy for hydrotreating or stabilization of bio-oil have been recently reported. This review provides a survey of the relevant literatures of recent 10 years about the advances in the understanding of the HDO chemistry of bio-oils and their model compounds mainly on noble metal catalysts.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Pore Scale Analysis of Oil Shale/Sands Pyrolysis

    SciTech Connect

    Lin, Chen-Luh; Miller, Jan

    2011-03-01

    There are important questions concerning the quality and volume of pore space that is created when oil shale is pyrolyzed for the purpose of producing shale oil. In this report, 1.9 cm diameter cores of Mahogany oil shale were pyrolyzed at different temperatures and heating rates. Detailed 3D imaging of core samples was done using multiscale X-ray computed tomography (CT) before and after pyrolysis to establish the pore structure. The pore structure of the unreacted material was not clear. Selected images of a core pyrolyzed at 400oC were obtained at voxel resolutions from 39 microns (Οm) to 60 nanometers (nm). Some of the pore space created during pyrolysis was clearly visible at these resolutions and it was possible to distinguish between the reaction products and the host shale rock. The pore structure deduced from the images was used in Lattice Boltzmann simulations to calculate the permeability in the pore space. The permeabilities of the pyrolyzed samples of the silicate-rich zone were on the order of millidarcies, while the permeabilities of the kerogen-rich zone after pyrolysis were very anisotropic and about four orders of magnitude higher.

  12. 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.

  13. 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

  14. 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...

  15. 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.

  16. 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.

  17. 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...

  18. 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.

  19. Ex-situ catalytic co-pyrolysis of lignin and polypropylene to upgrade bio-oil quality by microwave heating.

    PubMed

    Duan, Dengle; Wang, Yunpu; Dai, Leilei; Ruan, Roger; Zhao, Yunfeng; Fan, Liangliang; Tayier, Maimaitiaili; Liu, Yuhuan

    2017-10-01

    Microwave-assisted fast co-pyrolysis of lignin and polypropylene for bio-oil production was conducted using the ex-situ catalysis technology. Effects of catalytic temperature, feedstock/catalyst ratio, and lignin/polypropylene ratio on product distribution and chemical components of bio-oil were investigated. The catalytic temperature of 250°C was the most conducive to bio-oil production in terms of the yield. The bio-oil yield decreased with the addition of catalyst during ex-situ catalytic co-pyrolysis. When the feedstock/catalyst ratio was 2:1, the minimum char and coke values were 21.22% and 1.54%, respectively. The proportion of cycloalkanes decreased and the aromatics increased with the increasing catalyst loading. A positive synergistic effect was observed between lignin and polypropylene. The char yield dramatically deceased and the bio-oil yield improved during co-pyrolysis compared with those during lignin pyrolysis alone. The proportion of oxygenates dramatically and the minimum value of 6.74% was obtained when the lignin/polypropylene ratio was 1:1. Copyright © 2017. Published by Elsevier Ltd.

  20. 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).

  1. 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.

  2. Pyrolysis of sunflower seed hulls for obtaining bio-oils.

    PubMed

    Casoni, Andrés I; Bidegain, Maximiliano; Cubitto, María A; Curvetto, Nestor; Volpe, María A

    2015-02-01

    Bio-oils from pyrolysis of as received sunflower seed hulls (SSH), hulls previously washed with acid (SSHA) and hulls submitted to a mushroom enzymatic attack (BSSH) were analyzed. The concentration of lignin, hemicellulose and cellulose varied with the pre-treatment. The liquid corresponding to SSH presented a relatively high concentration of acetic acid and a high instability to storage. The bio-oil from SSHA showed a high concentration of furfural and an appreciable amount of levoglucosenone. Lignin was degraded upon enzymatic activity, for this reason BSSH led to the highest yield of bio-oil, with relative high concentration of acetic acid and stability to storage. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Influence of a glass wool hot vapour filter on yields and properties of bio-oil derived from rapid pyrolysis of paddy residues.

    PubMed

    Pattiya, Adisak; Suttibak, Suntorn

    2012-07-01

    This article reports experimental results of rapid or fast pyrolysis of rice straw (RS) and rice husk (RH) in a fluidised-bed reactor unit incorporated with a hot vapour filter. The objective of this research was to investigate the effects of pyrolysis temperatures and the use of glass wool hot vapour filtration on pyrolysis products. The results showed that the optimum pyrolysis temperatures for RS and RH were 405 and 452 °C, which gave maximum bio-oil yields of 54.1 and 57.1 wt.% on dry biomass basis, respectively. The use of the hot filter led to a reduction of 4-7 wt.% bio-oil yield. Nevertheless, the glass wool hot filtered bio-oils appeared to have better quality in terms of initial viscosity, solids content and ash content than the non-filtered ones. Copyright © 2012 Elsevier Ltd. All rights reserved.

  4. Isolation of levoglucosan from pyrolysis oil derived from cellulose

    DOEpatents

    Moens, L.

    1994-12-06

    High purity levoglucosan is obtained from pyrolysis oil derived from cellulose by: mixing pyrolysis oil with water and a basic metal hydroxide, oxide, or salt in amount sufficient to elevate pH values to a range of from about 12 to about 12.5, and adding an amount of the hydroxide, oxide, or salt in excess of the amount needed to obtain the pH range until colored materials of impurities from the oil are removed and a slurry is formed; drying the slurry azeotropically with methyl isobutyl ketone solvent to form a residue, and further drying the residue by evaporation; reducing the residue into a powder; continuously extracting the powder residue with ethyl acetate to provide a levoglucosan-rich extract; and concentrating the extract by removing ethyl acetate to provide crystalline levoglucosan. Preferably, Ca(OH)[sub 2] is added to adjust the pH to the elevated values, and then Ca(OH)[sub 2] is added in an excess amount needed. 3 figures.

  5. Isolation of levoglucosan from pyrolysis oil derived from cellulose

    DOEpatents

    Moens, Luc

    1994-01-01

    High purity levoglucosan is obtained from pyrolysis oil derived from cellulose by: mixing pyrolysis oil with water and a basic metal hydroxide, oxide, or salt in amount sufficient to elevate pH values to a range of from about 12 to about 12.5, and adding an amount of the hydroxide, oxide, or salt in excess of the amount needed to obtain the pH range until colored materials of impurities from the oil are removed and a slurry is formed; drying the slurry azeotropically with methyl isobutyl ketone solvent to form a residue, and further drying the residue by evaporation; reducing the residue into a powder; continuously extracting the powder residue with ethyl acetate to provide a levoglucosan-rich extract; and concentrating the extract by removing ethyl acetate to provide crystalline levoglucosan. Preferably, Ca(OH).sub.2 is added to adjust the pH to the elevated values, and then Ca(OH).sub.2 is added in an excess amount needed.

  6. 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.

  7. Co-processing of olive bagasse with crude rapeseed oil via pyrolysis.

    PubMed

    Uçar, Suat; Karagöz, Selhan

    2017-05-01

    The co-pyrolysis of olive bagasse with crude rapeseed oil at different blend ratios was investigated at 500ºC in a fixed bed reactor. The effect of olive bagasse to crude rapeseed oil ratio on the product distributions and properties of the pyrolysis products were comparatively investigated. The addition of crude rapeseed oil into olive bagasse in the co-pyrolysis led to formation of upgraded biofuels in terms of liquid yields and properties. While the pyrolysis of olive bagasse produced a liquid yield of 52.5 wt %, the highest liquid yield of 73.5 wt % was obtained from the co-pyrolysis of olive bagasse with crude rapeseed oil at a blend ratio of 1:4. The bio-oil derived from olive bagasse contained 5% naphtha, 10% heavy naphtha, 30% gas oil, and 55% heavy gas oil. In the case of bio-oil obtained from the co-pyrolysis of olive bagasse with crude rapeseed oil at a blend ratio of 1:4, the light naphtha, heavy naphtha, and light gas oil content increased. This is an indication of the improved characteristics of the bio-oil obtained from the co-processing. The heating value of bio-oil from the pyrolysis of olive bagasse alone was 34.6 MJ kg(-1) and the heating values of bio-oils obtained from the co-pyrolysis of olive bagasse with crude rapeseed oil ranged from 37.6 to 41.6 MJ kg(-1). It was demonstrated that the co-processing of waste biomass with crude plant oil is a good alternative to improve bio-oil yields and properties.

  8. Extraction of phenols from lignin microwave-pyrolysis oil using a switchable hydrophilicity solvent.

    PubMed

    Fu, Dongbao; Farag, Sherif; Chaouki, Jamal; Jessop, Philip G

    2014-02-01

    Microwave pyrolysis of lignin, an aromatic polymer byproduct from paper-pulping industry, produces char, gases, and lignin pyrolysis oil. Within the oil are valuable phenolic compounds such as phenol, guaiacol and catechol. In this work, we describe a method using switchable hydrophilicity solvents (SHS) to extract phenols as a mixture from lignin microwave-pyrolysis oil at the scale of 10 g of bio-oil. Even at this small scale, losses are small; 96% of the bio-oil was recovered in its three fractions, 72% of guaiacol and 70% of 4-methylguaiacol, the most abundant phenols in the bio-oil, were extracted and 91% of the solvent SHS was recovered after extraction. The starting material (lignin microwave-pyrolysis oil) and the three fractions resulted from SHS extraction were characterized by GC-MS and quantitative (13)C{(1)H} and (31)P{(1)H} NMR spectroscopy.

  9. Quality improvement of pyrolysis oil from waste rubber by adding sawdust

    SciTech Connect

    Wang, Wen-liang; Chang, Jian-min; Cai, Li-ping; Shi, Sheldon Q.

    2014-12-15

    Highlights: • Rubber-pyrolysis oil is difficult to be fuel due to high proportion of PAHs. • The efficiency of pyrolysis was increased as the percentage of sawdust increased. • The adding of sawdust improved pyrolysis oil quality by reducing the PAHs content. • Adding sawdust reduced nitrogen/sulfur in oil and was easier to convert to diesel. - Abstract: This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.

  10. 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

  11. 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.

  12. 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.

  13. Characterization and pyrolysis behavior of novel anthracene oil derivatives

    SciTech Connect

    P. Alvarez; M. Granda; J. Sutil; R. Menendez; J.J. Fernandez; J.A. Vina; T.J. Morgan; M. Millan; A.A. Herod; R. Kandiyoti

    2008-11-15

    The characterization and pyrolysis behavior of a set of pitches prepared from anthracene oil have been described. The pitches were obtained from four successive cycles of a sequential process that begins with blowing air through the heated anthracene oil, to bring about recombination reactions. Reaction products are distilled to give a pitch residue and a lighter fraction. Thermal treatment/distillation cycles of this reaction product yield a pitch and a distillate fraction (unreacted anthracene oil) during each subsequent stage. Products obtained during the process have been characterized by elemental analysis, Fourier transform infrared (FTIR) and ultraviolet (UV)-fluorescence spectroscopy, and size-exclusion chromatography (SEC). The pyrolytic behavior of the anthracene oil derivatives was examined using a thermogravimetric balance. Thermal treatment of the anthracene oil and its (distilled) reaction products at 440-460{degree}C under 5 bar pressure leads to a partially anisotropic pitch with the formation of a liquid crystal phase (mesophase). The formation and evolution of these mesophases were analyzed by optical microscopy. 25 refs., 9 figs., 3 tabs.

  14. Modeling a set of heavy oil aqueous pyrolysis experiments

    SciTech Connect

    Thorsness, C.B.; Reynolds, J.G.

    1996-11-01

    Aqueous pyrolysis experiments, aimed at mild upgrading of heavy oil, were analyzed using various computer models. The primary focus of the analysis was the pressure history of the closed autoclave reactors obtained during the heating of the autoclave to desired reaction temperatures. The models used included a means of estimating nonideal behavior of primary components with regard to vapor liquid equilibrium. The modeling indicated that to match measured autoclave pressures, which often were well below the vapor pressure of water at a given temperature, it was necessary to incorporate water solubility in the oil phase and an activity model for the water in the oil phase which reduced its fugacity below that of pure water. Analysis also indicated that the mild to moderate upgrading of the oil which occurred in experiments that reached 400{degrees}C or more using a FE(III) 2-ethylhexanoate could be reasonably well characterized by a simple first order rate constant of 1.7xl0{sup 8} exp(-20000/T)s{sup {minus}l}. Both gas production and API gravity increase were characterized by this rate constant. Models were able to match the complete pressure history of the autoclave experiments fairly well with relatively simple equilibria models. However, a consistent lower than measured buildup in pressure at peak temperatures was noted in the model calculations. This phenomena was tentatively attributed to an increase in the amount of water entering the vapor phase caused by a change in its activity in the oil phase.

  15. Quality improvement of pyrolysis oil from waste rubber by adding sawdust.

    PubMed

    Wang, Wen-liang; Chang, Jian-min; Cai, Li-ping; Shi, Sheldon Q

    2014-12-01

    This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG-FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis-gas chromatography (GC)-mass spectrometry (Py-GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. 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.

  17. 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.

  18. 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).

  19. 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...

  20. Combustion performance of pyrolysis oil/ethanol blends in a residential-scale oil-fired boiler

    USDA-ARS?s Scientific Manuscript database

    A 40 kWth oil-fired commercial boiler was fueled with blends of biomass pyrolysis oil (py-oil) and ethanol to determine the feasibility of using these blends as a replacement for fuel oil in home heating applications. An optimal set of test parameters was determined for the combustion of these blend...

  1. 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.

  2. 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.

  3. Design of pyrolysis reactor for production of bio-oil and bio-char simultaneously

    NASA Astrophysics Data System (ADS)

    Aladin, Andi; Alwi, Ratna Surya; Syarif, Takdir

    2017-05-01

    The residues from the wood industry are the main contributors to biomass waste in Indonesia. The conventional pyrolysis process, which needs a large energy as well as to produce various toxic chemical to the environment. Therefore, a pyrolysis unit on the laboratory scale was designed that can be a good alternative to achieve zero-waste and low energy cost. In this paper attempts to discuss design and system of pyrolysis reactor to produce bio-oil and bio-char simultaneously.

  4. 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.

  5. Formation of dl-limonene in used tire vacuum pyrolysis oils. [dipentene

    SciTech Connect

    Pakdel, H.; Roy, C.; Aubin, H.; Jean, G. ); Coulombe, S. )

    1991-09-01

    Tire recycling has become an important environmental issue recently due to the huge piles of tires that threaten the environment. Thermal decomposition of tire, a synthetic rubber material, enables the recovery of carbon black and liquid hydrocarbon oils. Both have potential economic values. Pyrolysis oils obtained under vacuum conditions contain a significant portion of a volatile, naptha-like fraction with an octane number similar to petroleum naphtha fraction, in addition, contains approximately 15% limonene. Potential applications of vacuum pyrolysis oil and carbon black have been investigated. However, the process economics is greatly influenced by the quality of the oil and carbon black products. This paper discusses limonene formation during used tire vacuum pyrolysis and its postulated reaction mechanism. The limonene separation method from pyrolysis oil, as well as its purification in laboratory scale, and structural characterization are discussed. Large-scale limonene separation and purification is under investigation.

  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. Effect of pyrolysis temperature on characteristics and aromatic contaminants adsorption behavior of magnetic biochar derived from pyrolysis oil distillation residue.

    PubMed

    Li, Hao; Mahyoub, Samah Awadh Ali; Liao, Wenjie; Xia, Shuqian; Zhao, Hechuan; Guo, Mengya; Ma, Peisheng

    2017-01-01

    The magnetic biochars were easily fabricated by thermal pyrolysis of Fe(NO3)3 and distillation residue derived from rice straw pyrolysis oil at 400, 600 and 800°C. The effects of pyrolysis temperature on characteristics of magnetic biochars as well as adsorption capacity for aromatic contaminants (i.e., anisole, phenol and guaiacol) were investigated carefully. The degree of carbonization of magnetic biochars become higher as pyrolysis temperature increasing. The magnetic biochar reached the largest surface area and pore volume at the pyrolysis temperature of 600°C due to pores blocking in biochar during pyrolysis at 800°C. Based on batch adsorption experiments, the used adsorbent could be magnetically separated and the adsorption capacity of anisole on magnetic biochars was stronger than that of phenol and guaiacol. The properties of magnetic biochar, including surface area, pore volume, aromaticity, grapheme-like-structure and iron oxide (γ-Fe2O3) particles, showed pronounced effects on the adsorption performance of aromatic contaminants.

  8. Formation of degradation products from the pyrolysis of tall oil fatty acids with kraft lignin

    SciTech Connect

    Traitler, H.; Kratzl, K.

    1980-01-01

    Pyrolysis of tall oil fatty acids containing kraft lignin at 160-280 degrees with or without exclusion of O resulted in formation of alkylbenzenes, carboxylic acids, and hydrocarbons, as determined by gas chomatography. In the pyrolysis, ring cleavage of dehydroabietic acids could not be observed, and no cyclic fatty acids could be detected.

  9. 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.

  10. 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

  11. Production of higher quality bio-oils by in-line esterification of pyrolysis vapor

    SciTech Connect

    Hilten, Roger Norris; Das, Keshav; Kastner, James R; Bibens, Brian P

    2014-12-02

    The disclosure encompasses in-line reactive condensation processes via vapor phase esterification of bio-oil to decease reactive species concentration and water content in the oily phase of a two-phase oil, thereby increasing storage stability and heating value. Esterification of the bio-oil vapor occurs via the vapor phase contact and subsequent reaction of organic acids with ethanol during condensation results in the production of water and esters. The pyrolysis oil product can have an increased ester content and an increased stability when compared to a condensed pyrolysis oil product not treated with an atomized alcohol.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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

  17. The effect of clay catalyst on the chemical composition of bio-oil obtained by co-pyrolysis of cellulose and polyethylene

    SciTech Connect

    Solak, Agnieszka; Rutkowski, Piotr

    2014-02-15

    Highlights: • Non-catalytic and catalytic fast pyrolysis of cellulose/polyethylene blend was carried out in a laboratory scale reactor. • Optimization of process temperature was done. • Optimization of clay catalyst type and amount for co-pyrolysis of cellulose and polyethylene was done. • The product yields and the chemical composition of bio-oil was investigated. - Abstract: Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 – montmorillonite K10, KSF – montmorillonite KSF, B – Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500 °C with heating rate of 100 °C/s to produce bio-oil with high yield. The pyrolytic oil yield was in the range of 41.3–79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst.

  18. Utilization of palm oil sludge through pyrolysis for bio-oil and bio-char production.

    PubMed

    Thangalazhy-Gopakumar, Suchithra; Al-Nadheri, Wail Mohammed Ahmed; Jegarajan, Dinesh; Sahu, J N; Mubarak, N M; Nizamuddin, S

    2015-02-01

    In this study, pyrolysis technique was utilized for converting palm oil sludge to value added materials: bio-oil (liquid fuel) and bio-char (soil amendment). The bio-oil yield obtained was 27.4±1.7 wt.% having a heating value of 22.2±3.7 MJ/kg and a negligible ash content of 0.23±0.01 wt.%. The pH of bio-oil was in alkaline region. The bio-char yielded 49.9±0.3 wt.%, which was further investigated for sorption efficiency by adsorbing metal (Cd(2+) ions) from water. The removal efficiency of Cd(2+) was 89.4±2%, which was almost similar to the removal efficiency of a commercial activated carbon. The adsorption isotherm was well described by Langmuir model. Therefore, pyrolysis is proved as an efficient tool for palm oil sludge management, where the waste was converted into valuable products.

  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. 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.

  1. 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.

  2. Investigation of the ROPE copyright (Recycle Oil Pyrolysis and Extraction) process performance on Sunnyside tar sand

    SciTech Connect

    Cha, C.Y.; Johnson, L.A. Jr.; Guffey, F.D.

    1990-07-01

    The main objectives of this research were to determine the optimum pyrolysis temperature for Sunnyside tar sand and to verify the operability and efficiency of the ROPE process at steady-state conditions for production of feedstock materials. The experiments were conducted in the 2-inch screw pyrolysis reactor (SPR). Four 24-hour tests and one 105-hour test were performed in the 2-inch SPR using Sunnyside tar sand. The 24-hour tests were designed to predict the optimum pyrolysis temperature for oil yield. The 105-hour test was conducted to confirm the optimum pyrolysis temperature with sufficient operating time to reach steady-state conditions with respect to product compositions. The following conclusions can be drawn from the Sunnyside tar sand 2-inch SPR tests: (1) Sunnyside tar sand can be processed without any major operational difficulty by the ROPE process. (2) Oil yields greater than Fischer assay were obtained during the 2-inch SPR tests. Oil yield greater than 80 wt % of the bitumen was obtained from the 105-hr test. (3) The ratio of heavy oil to light product oil is strongly dependent upon the pyrolysis temperature and increases with a decrease in the reaction temperature. The gas yield increases with the increase in pyrolysis temperature but the residual carbon in the spent sand decreases with the increase in pyrolysis temperature, reaches the minimum at 675{degrees}F, and then increases with further increase in the pyrolysis temperature. ROPE process product oils from Sunnyside tar sand have market application as blending stocks for the production of diesel fuels, but they are not suited for the production of unleaded gasoline or high-density aviation turbine fuels. 3 refs., 3 figs., 17 tabs.

  3. 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.

  4. Investigating the use of phenolic rich fraction of pyrolysis bio-oils as an adhesive system

    NASA Astrophysics Data System (ADS)

    Sahaf, Amir

    Fast pyrolysis allows converting of up to 75 % of biomass into a crude bio-oil, which can be separated into a phenolic rich fraction (PRF) via ethyl acetate extraction while a sugar rich fraction preferentially concentrates in the aqueous phase. Rheological and thermal characterization of heat treated PRF from pyrolysis of Douglas Fir is performed using cone and plate rheology set up, dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The results show that this material demonstrates a unique thermoplastic behavior with low Tg and softening point that can be systematically manipulated through changes in thermal history. As these materials are good candidates for development of hot melt adhesives, lap shear tests were also performed using wood stripes to evaluate their mechanical properties as an adhesive. Optimization of properties of the PRF is sought in this study through polymer blending with other bio-degradable thermoplastic poly(epsilon-caprolactone) (PCL) and poly(lactic acid) (PLA). Blends of PRF/PCL and PRF/PLA of different ratios are prepared by solvent casting and melt blending and thermally and thermomechanically characterized for their miscibility and phase behavior. Presence of molecular interactions are furthur investigated using Fourier transform infrared spectoscopy (FTIR). The blends show complete miscibility based on their Tg and melting points and significant improvement in shear strength is observed. Mechanisms leading to changes in properties are described and a physical model is proposed. The blend systems have good potential to be used as a thermoplastic bio degradable adhesives with satisfactoty properies.

  5. 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.

  6. Kinetics of coffee industrial residue pyrolysis using distributed activation energy model and components separation of bio-oil by sequencing temperature-raising pyrolysis.

    PubMed

    Chen, Nanwei; Ren, Jie; Ye, Ziwei; Xu, Qizhi; Liu, Jingyong; Sun, Shuiyu

    2016-12-01

    This study was carried out to investigate the kinetics of coffee industrial residue (CIR) pyrolysis, the effect of pyrolysis factors on yield of bio-oil component and components separation of bio-oil. The kinetics of CIR pyrolysis was analyzed using distributed activation energy model (DAEM), based on the experiments in thermogravimetric analyzer (TGA), and it indicated that the average of activation energy (E) is 187.86kJ·mol(-1). The bio-oils were prepared from CIR pyrolysis in vacuum tube furnace, and its components were determined by gas chromatography/mass spectrometry (GC-MS). Among pyrolysis factors, pyrolysis temperature is the most influential factor on components yield of bio-oil, directly concerned with the volatilization and yield of components (palmitic acid, linoleic acid, oleic acid, octadecanoic acid and caffeine). Furthermore, a new method (sequencing temperature-raising pyrolysis) was put forward and applied to the components separation of bio-oil. Based on experiments, a solution of components separation of bio-oil was come out. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Development of a new peat-based oil sorbent using peat pyrolysis.

    PubMed

    Klavins, Maris; Porshnov, Dmitry

    2013-01-01

    The growing use and transport of crude oil and oil products has led to increasing numbers of oil spillages of various scales. Oil sorbents have been extensively used for remediation of the consequences of such accidents. The aim of this study is to investigate the possible use of peat and its thermal treatment products for oil sorption. Peat as an oil sorbent has poor buoyancy characteristics, relatively low oil sorption capacity and low hydrophobicity. However, thermal treatment (low-temperature pyrolysis and synthesis of peat-based activated coal) helps to significantly improve its sorptive characteristics. Peat is a potential material for oil sorption because it has such advantages as low cost, biodegradability and relatively high parameters of specific surface area and porosity. The processes and structural changes taking place during low-temperature pyrolysis have been studied by means of IR spectroscopy, thermogravimetry and scanning electron microscopy.

  8. Method and apparatus for producing pyrolysis oil having improved stability

    DOEpatents

    Baird, Lance A.; Brandvold, Timothy A.; Muller, Stefan

    2016-12-27

    Methods and apparatus to improve hot gas filtration to reduce the liquid fuel loss caused by prolonged residence time at high temperatures are described. The improvement can be obtained by reducing the residence time at elevated temperature by reducing the temperature of the pyrolysis vapor, by reducing the volume of the pyrolysis vapor at the elevated temperature, by increasing the volumetric flow rate at constant volume of the pyrolysis vapor, or by doing a combination of these.

  9. A Novel Energy-Efficient Pyrolysis Process: Self-pyrolysis of Oil Shale Triggered by Topochemical Heat in a Horizontal Fixed Bed

    NASA Astrophysics Data System (ADS)

    Sun, You-Hong; Bai, Feng-Tian; Lü, Xiao-Shu; Li, Qiang; Liu, Yu-Min; Guo, Ming-Yi; Guo, Wei; Liu, Bao-Chang

    2015-02-01

    This paper proposes a novel energy-efficient oil shale pyrolysis process triggered by a topochemical reaction that can be applied in horizontal oil shale formations. The process starts by feeding preheated air to oil shale to initiate a topochemical reaction and the onset of self-pyrolysis. As the temperature in the virgin oil shale increases (to 250-300°C), the hot air can be replaced by ambient-temperature air, allowing heat to be released by internal topochemical reactions to complete the pyrolysis. The propagation of fronts formed in this process, the temperature evolution, and the reaction mechanism of oil shale pyrolysis in porous media are discussed and compared with those in a traditional oxygen-free process. The results show that the self-pyrolysis of oil shale can be achieved with the proposed method without any need for external heat. The results also verify that fractured oil shale may be more suitable for underground retorting. Moreover, the gas and liquid products from this method were characterised, and a highly instrumented experimental device designed specifically for this process is described. This study can serve as a reference for new ideas on oil shale in situ pyrolysis processes.

  10. A Novel Energy-Efficient Pyrolysis Process: Self-pyrolysis of Oil Shale Triggered by Topochemical Heat in a Horizontal Fixed Bed

    PubMed Central

    Sun, You-Hong; Bai, Feng-Tian; Lü, Xiao-Shu; Li, Qiang; Liu, Yu-Min; Guo, Ming-Yi; Guo, Wei; Liu, Bao-Chang

    2015-01-01

    This paper proposes a novel energy-efficient oil shale pyrolysis process triggered by a topochemical reaction that can be applied in horizontal oil shale formations. The process starts by feeding preheated air to oil shale to initiate a topochemical reaction and the onset of self-pyrolysis. As the temperature in the virgin oil shale increases (to 250–300°C), the hot air can be replaced by ambient-temperature air, allowing heat to be released by internal topochemical reactions to complete the pyrolysis. The propagation of fronts formed in this process, the temperature evolution, and the reaction mechanism of oil shale pyrolysis in porous media are discussed and compared with those in a traditional oxygen-free process. The results show that the self-pyrolysis of oil shale can be achieved with the proposed method without any need for external heat. The results also verify that fractured oil shale may be more suitable for underground retorting. Moreover, the gas and liquid products from this method were characterised, and a highly instrumented experimental device designed specifically for this process is described. This study can serve as a reference for new ideas on oil shale in situ pyrolysis processes. PMID:25656294

  11. A novel energy-efficient pyrolysis process: self-pyrolysis of oil shale triggered by topochemical heat in a horizontal fixed bed.

    PubMed

    Sun, You-Hong; Bai, Feng-Tian; Lü, Xiao-Shu; Li, Qiang; Liu, Yu-Min; Guo, Ming-Yi; Guo, Wei; Liu, Bao-Chang

    2015-02-06

    This paper proposes a novel energy-efficient oil shale pyrolysis process triggered by a topochemical reaction that can be applied in horizontal oil shale formations. The process starts by feeding preheated air to oil shale to initiate a topochemical reaction and the onset of self-pyrolysis. As the temperature in the virgin oil shale increases (to 250-300°C), the hot air can be replaced by ambient-temperature air, allowing heat to be released by internal topochemical reactions to complete the pyrolysis. The propagation of fronts formed in this process, the temperature evolution, and the reaction mechanism of oil shale pyrolysis in porous media are discussed and compared with those in a traditional oxygen-free process. The results show that the self-pyrolysis of oil shale can be achieved with the proposed method without any need for external heat. The results also verify that fractured oil shale may be more suitable for underground retorting. Moreover, the gas and liquid products from this method were characterised, and a highly instrumented experimental device designed specifically for this process is described. This study can serve as a reference for new ideas on oil shale in situ pyrolysis processes.

  12. 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 ...

  13. 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.

  14. 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....

  15. 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.

  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. 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.

  18. 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).

  19. 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.

  20. Preliminary Investigation for Engine Performance by Using Tire-Derived Pyrolysis Oil-Diesel Blended Fuels

    NASA Astrophysics Data System (ADS)

    Rofiqul, Islam M.; Haniu, Hiroyuki; Alam, Beg R.; Takai, Kazunori

    In the first phase of the present study, the pyrolysis oil derived from light automotive tire waste has been characterized including fuel properties, elemental analyses, FT-IR, 1H-NMR, GC-MS and distillation. The studies on the oil show that it can be used as liquid fuel with a gross calorific value (GCV) of 42.00 MJ/kg and empirical formula of CH1.27O0.025N0.006. In the second phase of the investigation, the performance of a diesel engine was studied blending the pyrolysis oil with diesel fuel in different ratios. The experimental results show that the bsfc of pyrolysis oil-diesel blended fuels slightly increases and hence the brake thermal efficiency decreases compared to those of neat diesel. The pyrolysis oil-diesel blends show lower carbon monoxide (CO) emission but higher oxides of nitrogen (NOx) emissions than those of neat diesel. However, NOx emissions with pyrolysis oil-diesel blended fuels reduced when EGR was applied.

  1. Composition of pyrolysis gas from oil shale at various stages of heating

    NASA Astrophysics Data System (ADS)

    Martemyanov, S. M.; Bukharkin, A. A.; Koryashov, I. A.; Ivanov, A. A.

    2017-05-01

    Underground, the pyrolytic conversion of an oil shale in the nearest future may become an alternative source of a fuel gas and a synthetic oil. The main scientific problem in designing this technology is to provide a methodology for determination of the optimal mode of heating the subterranean formation. Such a methodology must allow predicting the composition of the pyrolysis products and the energy consumption at a given heating rate of the subterranean formation. The paper describes the results of heating of the oil shale fragments in conditions similar to the underground. The dynamics of composition of the gaseous products of pyrolysis are presented and analyzed.

  2. Antioxidants from slow pyrolysis bio-oil of birch wood: Application for biodiesel and biobased lubricants

    USDA-ARS?s Scientific Manuscript database

    Birch wood was slowly pyrolyzed to produce bio-oil and biochar. Slow pyrolysis conditions including reaction temperature, residence time, and particle size of the feed were optimized to maximize bio-oil yield. Particle size had an insignificant effect, whereas yields of up to 56% were achieved using...

  3. Red Mud Catalytic Pyrolysis of Pinyon Juniper and Single-Stage Hydrotreatment of Oils

    SciTech Connect

    Agblevor, Foster A.; Elliott, Douglas C.; Santosa, Daniel M.; Olarte, Mariefel V.; Burton, Sarah D.; Swita, Marie; Beis, Sedat H.; Christian, Kyle; Sargent, Brandon

    2016-10-20

    Pinyon juniper biomass feedstocks, which cover a large acreage of rangeland in the western United States, are being eradicated and, therefore, considered as a convenient biomass feedstock for biofuel production. Pinyon juniper whole biomass (wood, bark, and leaves) were pyrolyzed in a pilot-scale bubbling fluidized-bed reactor at 450 °C, and the noncondensable gases were recycled to fluidize the reactor. Red mud was used as the in situ catalyst for the pyrolysis of the pinyon juniper biomass. The pyrolysis products were condensed in three stages, and products were analyzed for physicochemical properties. The condenser oil formed two phases with the aqueous fraction, whereas the electrostatic precipitator oils formed a single phase. The oil pH was 3.3; the higher heating value (HHV) was 28 MJ/kg; and the viscosity was less than 100 cP. There was a direct correlation between the viscosity of the oils and the alcohol/ether content of the oils, and this was also related to the aging rate of the oils. The catalytic pyrolysis oils were hydrotreated in a continuous single-stage benchtop hydrotreater to produce hydrocarbon fuels with a density of 0.80$-$0.82 cm3/g. The hydrotreater ran continuously for over 300 h with no significant catalyst deactivation or coke formation. This is the first time that such a long single-stage hydrotreatment has been demonstrated on biomass catalytic pyrolysis oils.

  4. Processing of Arroyo Grande tar sand using the Recycle Oil Pyrolysis and Extraction (ROPE copyright ) process

    SciTech Connect

    King, S.B.

    1989-12-01

    The objectives of this study are to (1) evaluate the applications of the ROPE{copyright} process to a California tar sand using the screw pyrolysis reactor-process development unit (SPR-PDU) reactor, (2) produce kinetics data for the recycle product oil-spent sand interaction, and (3) produce oil for end-use evaluation. 6 refs., 1 fig., 23 tabs.

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

    USDA-ARS?s Scientific Manuscript database

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

  6. 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.

  7. Factors affecting the yield of bio-oil from the pyrolysis of coconut shell.

    PubMed

    Gao, Yun; Yang, Yi; Qin, Zhanbin; Sun, Yi

    2016-01-01

    Coconut is a high-quality agricultural product of the Asia-Pacific region. In this paper, coconut shell which mainly composed of cellulose, hemicellulose, lignin was used as a raw material for coconut shell oil from coconut shell pyrolysis. The influence of the pyrolysis temperature, heating rate and particle size on coconut oil yield was investigated, and the effect of heating rate on coconut oil components was discussed. Experimental results show that the maximum oil yield of 75.74 wt% (including water) were obtained under the conditions that the final pyrolysis temperature 575 °C, heating rate 20 °C/min, coconut shell diameter about 5 mm. Thermal gravimetric analysis was used and it can be seen that coconut shell pyrolysis process can be divided into three stages: water loss, pyrolysis and pyrocondensation. The main components of coconut-shell oil are water (about 50 wt%), aromatic, phenolic, acid, ketone and ether containing compounds.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. A comparative study of bio-oils from pyrolysis of microalgae and oil seed waste in a fluidized bed.

    PubMed

    Kim, Sung Won; Koo, Bon Seok; Lee, Dong Hyun

    2014-06-01

    The pyrolysis of Scenedesmus sp. and Jatropha seedshell cake (JSC) was investigated under similar operating condition in a fluidized bed reactor for comparison of pyrolytic behaviors from different species of lipids-containing biomass. Microalgae showed a narrower main peak in differential thermogravimetric curve compared to JSC due to different constituents. Pyrolysis liquid yields were similar; liquid's oil proportion of microalgae is higher than JSC. Microalgae bio-oil was characterized by similar carbon and hydrogen contents and higher H/C and O/C molar ratios compared to JSC due to compositional difference. The pyrolytic oils from microalgae and JSC contained more oxygen and nitrogen and less sulfur than petroleum and palm oils. The pyrolytic oils showed high yields of fatty oxygenates and nitrogenous compounds. The microalgae bio-oil features in high concentrations of aliphatic compounds, fatty acid alkyl ester, alcohols and nitriles. Microalgae showed potentials for alternative feedstock for green diesel, and commodity and valuable chemicals.

  13. Characterization of top phase oil obtained from co-pyrolysis of sewage sludge and poplar sawdust.

    PubMed

    Zuo, Wu; Jin, Baosheng; Huang, Yaji; Sun, Yu

    2014-01-01

    To research the impact of adding sawdust on top phase oil, a sewage sludge and poplar sawdust co-pyrolysis experiment was performed in a fixed bed. Gas chromatography (GC)/mass spectrometry (MS) was used to analyze the component distribution of top phase oil. Higher heating value, viscosity, water content, and pH of the top phase oil product were determined. The highest top phase oil yield (5.13 wt%) was obtained from the mixture containing 15% poplar sawdust, while the highest oil yield (16.51 wt%) was obtained from 20% poplar sawdust. Top phase oil collected from the 15% mixture also has the largest amount of aliphatics and the highest higher heating value (28.6 MJ/kg). Possible reaction pathways were proposed to explain the increase in the types of phenols present in the top phase oil as the proportion of poplar sawdust used in the mixture increased. It can be concluded that synergetic reactions occurred during co-pyrolysis of sewage sludge and poplar sawdust. The results indicate that the high ash content of the sewage sludge may be responsible for the characteristic change in the top phase oil obtained from the mixtures containing different proportions of sewage sludge and poplar sawdust. Consequently, co-pyrolysis of the mixture containing 15 % poplar sawdust can increase the yield and the higher heating value of top phase oil.

  14. 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.

  15. Decaking of coal or oil shale during pyrolysis in the presence of iron oxides

    DOEpatents

    Rashid Khan, M.

    1988-05-05

    A method for producing a fuel from the pyrolysis of coal or oil shale in the presence of iron oxide in an inert gas atmosphere is described. The method includes the steps of pulverizing feed coal or oil shale, pulverizing iron oxide, mixing the pulverized feed and iron oxide, and heating the mixture in a gas atmosphere which is substantially inert to the mixture so as to form a product fuel, which may be gaseous, liquid and/or solid. The method of the invention reduces the swelling of coals, such as bituminous coal and the like, which are otherwise known to swell during pyrolysis. 4 figs., 8 tabs.

  16. Decaking of coal or oil shale during pyrolysis in the presence of iron oxides

    DOEpatents

    Khan, M. Rashid

    1989-01-01

    A method for producing a fuel from the pyrolysis of coal or oil shale in the presence of iron oxide in an inert gas atmosphere. The method includes the steps of pulverizing feed coal or oil shale, pulverizing iron oxide, mixing the pulverized feed and iron oxide, and heating the mixture in a gas atmosphere which is substantially inert to the mixture so as to form a product fuel, which may be gaseous, liquid and/or solid. The method of the invention reduces the swelling of coals, such as bituminous coal and the like, which are otherwise known to swell during pyrolysis.

  17. Catalytic pyrolysis of peat with additions of oil-slime and polymeric waste

    NASA Astrophysics Data System (ADS)

    Sulman, E.; Kosivtsov, Yu.; Sulman, M.; Alfyorov, V.; Lugovoy, Yu.; Chalov, K.; Misnikov, O.; Afanasjev, A.; Kumar, N.; Murzin, D.

    2012-09-01

    In this work the influence of natural and synthetic aluminosilicates, metal chlorides of iron subgroup on the peat low-temperature pyrolysis and co-pyrolysis of peat with oil-slime and polymeric waste was studied in variety of conditions (t = 350-650δC, catalyst loading: from 1 up to 30 % (wt.)). The use of bentonite clay (30 % (wt.)) at 460δC as a catalyst in peat pyrolysis resulted in increase of weight of gaseous and liquid products from 23 up to 30 % (wt.) and from 32 up to 45 % (wt.), respectively. Co-pyrolysis of peat and oil-slime in the presence of bentonite clay resulted in increase of gaseous product weight from 18 up to 26 % (wt.) and liquid fraction yield - from 45 up to 55 % (wt.) in comparison with precalculated value. The use of metal chlorides of iron subgroup (2 % (wt.) concentration) at 500 δC in the co-pyrolysis of peat and polymeric waste led to optimal conversion of substrate in desired products, 15 % increase of total weight of gaseous and liquid products formed during the pyrolysis process and simultaneous decrease of char formation.

  18. 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.

  19. 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.

  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. 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.

  2. Plastic waste to liquid oil through catalytic pyrolysis using natural and synthetic zeolite catalysts.

    PubMed

    Miandad, R; Barakat, M A; Rehan, M; Aburiazaiza, A S; Ismail, I M I; Nizami, A S

    2017-09-04

    This study aims to examine the catalytic pyrolysis of various plastic wastes in the presence of natural and synthetic zeolite catalysts. A small pilot scale reactor was commissioned to carry out the catalytic pyrolysis of polystyrene (PS), polypropylene (PP), polyethylene (PE) and their mixtures in different ratios at 450°C and 75min. PS plastic waste resulted in the highest liquid oil yield of 54% using natural zeolite and 50% using synthetic zeolite catalysts. Mixing of PS with other plastic wastes lowered the liquid oil yield whereas all mixtures of PP and PE resulted in higher liquid oil yield than the individual plastic feedstocks using both catalysts. The GC-MS analysis revealed that the pyrolysis liquid oils from all samples mainly consisted of aromatic hydrocarbons with a few aliphatic hydrocarbon compounds. The types and amounts of different compounds present in liquid oils vary with some common compounds such as styrene, ethylbenzene, benzene, azulene, naphthalene, and toluene. The FT-IR data also confirmed that liquid oil contained mostly aromatic compounds with some alkanes, alkenes and small amounts of phenol group. The produced liquid oils have high heating values (HHV) of 40.2-45MJ/kg, which are similar to conventional diesel. The liquid oil has potential to be used as an alternative source of energy or fuel production. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Linking ramped pyrolysis isotope data to oil content through PAH analysis

    NASA Astrophysics Data System (ADS)

    Pendergraft, Matthew A.; Dincer, Zeynep; Sericano, José L.; Wade, Terry L.; Kolasinski, Joanna; Rosenheim, Brad E.

    2013-12-01

    Ramped pyrolysis isotope (13C and 14C) analysis coupled with polycyclic aromatic hydrocarbon (PAH) analysis demonstrates the utility of ramped pyrolysis in screening for oil content in sediments. Here, sediments from Barataria Bay, Louisiana, USA that were contaminated by oil from the 2010 BP Deepwater Horizon spill display relationships between oil contamination, pyrolysis profiles, and isotopic composition. Sediment samples with low PAH concentrations are thermochemically stable until higher temperatures, while samples containing high concentrations of PAHs pyrolyze at low temperatures. High PAH samples are also depleted in radiocarbon (14C), especially in the fractions that pyrolyze at low temperatures. This lack of radiocarbon in low temperature pyrolyzates is indicative of thermochemically unstable, 14C-free oil content. This study presents a proof of concept that oil contamination can be identified by changes in thermochemical stability in organic material and corroborated by isotope analysis of individual pyrolyzates, thereby providing a basis for application of ramped pyrolysis isotope analysis to samples deposited in different environments for different lengths of time.

  4. 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.

  5. Pyrolytic oil of banana (Musa spp.) pseudo-stem via fast process

    NASA Astrophysics Data System (ADS)

    Abdullah, Nurhayati; Sulaiman, Fauziah; Taib, Rahmad Mohd; Miskam, Muhamad Azman

    2015-04-01

    This study was an attempt to produce bio-oil from banana pseudo-stem, a waste of banana cultivation, using fast pyrolysis technology. The compositions were determined and the thermal degradation behaviour of the raw material was analyzed using Perkin-Elmer Simultaneous Thermal Analyzer (STA) 6000. A 300 g/h fluidized bed bench scale fast pyrolysis unit, assembled with double screw feeders and cyclones, operating at atmospheric pressure, was used to obtain the pyrolysis liquid. The study involves the impact of the following key variables; the reactor temperature in the range of 450-650 °C, and the residence time in the range of 1.00-3.00 s. The particle size was set at 224-400 µm. The properties of the liquid product were analyzed for calorific heating value, pH value, conductivity, water and char content. The basic functional groups of the compositions were also determined using FTIR. The properties of the liquid product were compared with other wood derived bio-oil. The pyrolysis liquids derived from banana pseudo-stem were found to be in an aqueous phase.

  6. Pyrolytic oil of banana (Musa spp.) pseudo-stem via fast process

    NASA Astrophysics Data System (ADS)

    Abdullah, Nurhayati; Sulaiman, Fauziah; Taib, Rahmad Mohd; Miskam, Muhamad Azman

    2015-04-01

    This study was an attempt to produce bio-oil from banana pseudo-stem, a waste of banana cultivation, using fast pyrolysis technology. The compositions were determined and the thermal degradation behaviour of the raw material was analyzed using Perkin-Elmer Simultaneous Thermal Analyzer.(STA) 6000. A 300 g/h fluidized bed bench scale fast pyrolysis unit, assembled with double screw feeders and cyclones, operating at atmospheric pressure, was used to obtain the pyrolysis liquid. The study involves the impact of the following key variables; the reactor temperature in the range of 450-650°C, and the residence time in the range of 1.00-3.00s. The particle size was set at 224-400µm. The properties of the liquid product were analyzed for calorific heating value, pH value, conductivity, water and char content. The basic functional groups of the compositions were also determined using FTIR. The properties of the liquid product were compared with other wood derived bio-oil. The pyrolysis liquids derived from banana pseudo-stem were found to be in an aqueous phase.

  7. Pyrolytic oil of banana (Musa spp.) pseudo-stem via fast process

    SciTech Connect

    Abdullah, Nurhayati; Sulaiman, Fauziah; Taib, Rahmad Mohd; Miskam, Muhamad Azman

    2015-04-24

    This study was an attempt to produce bio-oil from banana pseudo-stem, a waste of banana cultivation, using fast pyrolysis technology. The compositions were determined and the thermal degradation behaviour of the raw material was analyzed using Perkin-Elmer Simultaneous Thermal Analyzer (STA) 6000. A 300 g/h fluidized bed bench scale fast pyrolysis unit, assembled with double screw feeders and cyclones, operating at atmospheric pressure, was used to obtain the pyrolysis liquid. The study involves the impact of the following key variables; the reactor temperature in the range of 450–650 °C, and the residence time in the range of 1.00–3.00 s. The particle size was set at 224-400 µm. The properties of the liquid product were analyzed for calorific heating value, pH value, conductivity, water and char content. The basic functional groups of the compositions were also determined using FTIR. The properties of the liquid product were compared with other wood derived bio-oil. The pyrolysis liquids derived from banana pseudo-stem were found to be in an aqueous phase.

  8. Dynamic imaging of oil shale pyrolysis using synchrotron X-ray microtomography

    NASA Astrophysics Data System (ADS)

    Saif, Tarik; Lin, Qingyang; Singh, Kamaljit; Bijeljic, Branko; Blunt, Martin J.

    2016-07-01

    The structure and connectivity of the pore space during the pyrolysis of oil shales determines hydrocarbon flow behavior and ultimate recovery. We image the time evolution of the pore and microfracture networks during oil shale pyrolysis using synchrotron X-ray microtomography. Immature Green River (Mahogany Zone) shale samples were thermally matured under vacuum conditions at temperatures up to 500°C while being periodically imaged with a 2 µm voxel size. The structural transformation of both organic-rich and organic-lean layers within the shale was quantified. The images reveal a dramatic change in porosity accompanying pyrolysis between 390 and 400°C with the formation of micron-scale heterogeneous pores. With a further increase in temperature, the pores steadily expand resulting in connected microfracture networks that predominantly develop along the kerogen-rich laminations.

  9. 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.

  10. Molecular characterization and comparison of shale oils generated by different pyrolysis methods

    USGS Publications Warehouse

    Birdwell, Justin E.; Jin, Jang Mi; Kim, Sunghwan

    2012-01-01

    Shale oils generated using different laboratory pyrolysis methods have been studied using standard oil characterization methods as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI) and atmospheric photoionization (APPI) to assess differences in molecular composition. The pyrolysis oils were generated from samples of the Mahogany zone oil shale of the Eocene Green River Formation collected from outcrops in the Piceance Basin, Colorado, using three pyrolysis systems under conditions relevant to surface and in situ retorting approaches. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules and the distribution of nitrogen-containing compound classes. Comparison of FT-ICR MS results to other oil characteristics, such as specific gravity; saturate, aromatic, resin, asphaltene (SARA) distribution; and carbon number distribution determined by gas chromatography, indicated correspondence between higher average double bond equivalence (DBE) values and increasing asphaltene content. The results show that, based on the shale oil DBE distributions, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions, and under high pressure, moderate temperature conditions in the presence of water. We also report, for the first time in any petroleum-like substance, the presence of N4 class compounds based on FT-ICR MS data. Using double bond equivalence and carbon number distributions, structures for the N4 class and other nitrogen-containing compounds are proposed.

  11. Comparison of real waste (MSW and MPW) pyrolysis in batch reactor over different catalysts. Part II: contaminants, char and pyrolysis oil properties.

    PubMed

    Miskolczi, Norbert; Ateş, Funda; Borsodi, Nikolett

    2013-09-01

    Pyrolysis of real wastes (MPW and MSW) has been investigated at 500°C, 550°C and 600°C using Y-zeolite, β-zeolite, equilibrium FCC, MoO3, Ni-Mo-catalyst, HZSM-5 and Al(OH)3 as catalysts. The viscosity of pyrolysis oils could be decreased by the using of catalysts, especially by β-zeolite and MoO3. Both carbon frame and double bound isomerization was found in case of thermo-catalytic pyrolysis. Char morphology and texture analysis showed more coke deposits on the catalyst surface using MSW raw material. Pyrolysis oils had K, S, P Cl, Ca, Zn, Fe, Cr, Br and Sb as contaminants; and the concentrations of K, S, P, Cl and Br could be decreased by the using of catalysts.

  12. Rates and Mechanisms of Oil Shale Pyrolysis: A Chemical Structure Approach

    SciTech Connect

    Fletcher, Thomas; Pugmire, Ronald

    2015-01-01

    Three pristine Utah Green River oil shale samples were obtained and used for analysis by the combined research groups at the University of Utah and Brigham Young University. Oil shale samples were first demineralized and the separated kerogen and extracted bitumen samples were then studied by a host of techniques including high resolution liquid-state carbon-13 NMR, solid-state magic angle sample spinning 13C NMR, GC/MS, FTIR, and pyrolysis. Bitumen was extracted from the shale using methanol/dichloromethane and analyzed using high resolution 13C NMR liquid state spectroscopy, showing carbon aromaticities of 7 to 11%. The three parent shales and the demineralized kerogens were each analyzed with solid-state 13C NMR spectroscopy. Carbon aromaticity of the kerogen was 23-24%, with 10-12 aromatic carbons per cluster. Crushed samples of Green River oil shale and its kerogen extract were pyrolyzed at heating rates from 1 to 10 K/min at pressures of 1 and 40 bar and temperatures up to 1000°C. The transient pyrolysis data were fit with a first-order model and a Distributed Activation Energy Model (DAEM). The demineralized kerogen was pyrolyzed at 10 K/min in nitrogen at atmospheric pressure at temperatures up to 525°C, and the pyrolysis products (light gas, tar, and char) were analyzed using 13C NMR, GC/MS, and FTIR. Details of the kerogen pyrolysis have been modeled by a modified version of the chemical percolation devolatilization (CPD) model that has been widely used to model coal combustion/pyrolysis. This refined CPD model has been successful in predicting the char, tar, and gas yields of the three shale samples during pyrolysis. This set of experiments and associated modeling represents the most sophisticated and complete analysis available for a given set of oil shale samples.

  13. 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.

  14. Fractions composition study of the pyrolysis oil obtained from sewage sludge treatment plant.

    PubMed

    Silva, R V S; Romeiro, G A; Veloso, M C C; Figueiredo, M K-K; Pinto, P A; Ferreira, A F; Gonçalves, M L A; Teixeira, A M; Damasceno, R N

    2012-01-01

    In this work the parameters of Low Temperature Conversion--LTC were applied in a centrifuged sludge from a sewage treatment plant located in Rio de Janeiro, Brazil. Before the conversion, the sludge was dried and analyzed by TGA to observe its behavior with increasing temperature. The chemical composition of the crude pyrolysis oil was analyzed by FTIR, 1H NMR and GC-MS. The results showed that the oil is a mixture of hydrocarbons, oxygenated and nitrogenated compounds. Using a catalytic treatment it was possible to fractionate the oil where the predominant constituents were hydrocarbons showing that the cracking was effective. An important result was the difference between the calorific value of dry sludge (10 MJ kg(-1)), the pyrolysis oil (36 MJ kg(-1)) and one of the fractions separated by catalytic cracking (40 MJ kg(-1)) when compared with commercial diesel (45 MJ kg(-1)). Copyright © 2011 Elsevier Ltd. All rights reserved.

  15. Prospects of pyrolysis oil from plastic waste as fuel for diesel engines: A review

    NASA Astrophysics Data System (ADS)

    Mangesh, V. L.; Padmanabhan, S.; Ganesan, S.; PrabhudevRahul, D.; Reddy, T. Dinesh Kumar

    2017-05-01

    The purpose ofthis study is to review the existing literature about chemical recycling of plastic waste and its potential as fuel for diesel engines. This is a review covering on the field of converting waste plastics into liquid hydrocarbon fuels for diesel engines. Disposal and recycling of waste plastics have become an incremental problem and environmental threat with increasing demand for plastics. One of the effective measures is by converting waste plastic into combustible hydrocarbon liquid as an alternative fuel for running diesel engines. Continued research efforts have been taken by researchers to convert waste plastic in to combustible pyrolysis oil as alternate fuel for diesel engines. An existing literature focuses on the study of chemical structure of the waste plastic pyrolysis compared with diesel oil. Converting waste plastics into fuel oil by different catalysts in catalytic pyrolysis process also reviewed in this paper. The methodology with subsequent hydro treating and hydrocracking of waste plastic pyrolysis oil can reduce unsaturated hydrocarbon bonds which would improve the combustion performance in diesel engines as an alternate fuel.

  16. Varying relative degradation rates of oil in different forms and environments revealed by ramped pyrolysis.

    PubMed

    Pendergraft, Matthew A; Rosenheim, Brad E

    2014-09-16

    Degradation of oil contamination yields stabilized products by removing and transforming reactive and volatile compounds. In contaminated coastal environments, the processes of degradation are influenced by shoreline energy, which increases the surface area of the oil as well as exchange between oil, water, sediments, microbes, oxygen, and nutrients. Here, a ramped pyrolysis carbon isotope technique is employed to investigate thermochemical and isotopic changes in organic material from coastal environments contaminated with oil from the 2010 BP Deepwater Horizon oil spill. Oiled beach sediment, tar ball, and marsh samples were collected from a barrier island and a brackish marsh in southeast Louisiana over a period of 881 days. Stable carbon ((13)C) and radiocarbon ((14)C) isotopic data demonstrate a predominance of oil-derived carbon in the organic material. Ramped pyrolysis profiles indicate that the organic material was transformed into more stable forms. Our data indicate relative rates of stabilization in the following order, from fastest to slowest: high energy beach sediments > low energy beach sediments > marsh > tar balls. Oil was transformed most rapidly where shoreline energy and the rates of oil dispersion and exchange with water, sediments, microbes, oxygen, and nutrients were greatest. Still, isotope data reveal persistence of oil.

  17. 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.

  18. 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.

  19. Isothermal fluidised-bed pyrolysis of Australian oil shales in superheated steam

    SciTech Connect

    Wall, G.C.

    1984-04-01

    Samples of three Australian oil shales (Condor, Nagoorin, Rundle) were pyrolysed in steam at 450, 500 and 550/sup 0/C in a bench-scale fluidised-bed reactor at atmospheric pressure; the yields and compositions of the oils and gases produced were compared with corresponding results from Fischer assays. The maximum yield of oil occurred at 500/sup 0/C for all three shales. The yields (expressed as percentages of the Fischer assay yield at 500/sup 0/C max.) were: Rundle 110%; Condor 128%; Nagoorin 134%. The yields of oil from the Rundle and Condor shales were almost identical with those obtained by fluidised-bed pyrolysis in steam at a heating rate of 12/sup 0/C min/sup -1/. This suggests that flash heating has no effect on the oil yields from these shales and that the yield enhancement is due entirely to the effect of the sweep gas. Reduced coking was identified as the primary reason for the increased oil yields but reduced cracking also appeared to be significant for the Nagoorin oil shale. At 550/sup 0/C, the three shales yielded less oil than at 500/sup 0/C but the yield of pyrolysis gas increased considerably, suggesting that at this temperature oil cracking was significant.

  20. Mild pyrolysis of P3HB/Switchgrass blends for the production of bio-oil enriched with crotonic acid

    USDA-ARS?s Scientific Manuscript database

    The mild pyrolysis of switchgrass/poly-3-hydroxybutyrate (P3HB) blends that mimic P3HB-producing switchgrass lines was studied in a pilot scale fluidized bed reactor with the goal of simultaneously producing crotonic acid and switchgrass-based bio-oil. Factors such as pyrolysis temperature, residenc...

  1. 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.

  2. Porosity-Acidity Interplay in Hierarchical ZSM-5 Zeolites for Pyrolysis Oil Valorization to Aromatics.

    PubMed

    Puértolas, Begoña; Veses, Alberto; Callén, Maria Soledad; Mitchell, Sharon; García, Tomás; Pérez-Ramírez, Javier

    2015-10-12

    The properties of crude bio-oils attained by the pyrolysis of lignocellulosic biomass can be greatly enhanced by means of catalytic upgrading. Here, we demonstrate an efficient process concept coupling the production of pyrolysis oil from pine wood with a consecutive catalytic upgrading step over hierarchically structured ZSM-5 zeolites to attain aromatic-rich bio-oils. The selective upgrading of these complex mixtures is shown to be tightly connected to the extent of mesopore development and the density of Brønsted acid sites at the mesopore surface. A full product analysis enables elucidation of the impact of mesopore introduction and the acidic properties on the complex reaction network. The preferential occurrence of decarbonylation reactions in hierarchical zeolites versus dehydration transformations in the bulk counterparts is believed to be decisive in promoting increased aromatics formation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Pt/Al₂O₃-catalytic deoxygenation for upgrading of Leucaena leucocephala-pyrolysis oil.

    PubMed

    Payormhorm, Jiraporn; Kangvansaichol, Kunn; Reubroycharoen, Presert; Kuchonthara, Prapan; Hinchiranan, Napida

    2013-07-01

    The aim of this study was to improve the quality of bio-oil produced from the pyrolysis of Leucaena leucocephala trunks via catalytic deoxygenation using Pt/Al2O3 (Pt content=1.32% (w/w)). The minimum molar ratio of oxygen/carbon (O/C) at 0.14 was achieved when the amount of catalyst was 10% (w/w, bio-oil) and was applied under 4 bar of initial nitrogen pressure at 340°C for 1h. The reaction mechanism of the catalytic deoxygenation, in terms of reforming, water-gas shift and dehydration reactions, was proposed. To consider the effect of different biomass types on the efficiency of catalytic deoxygenation, the bio-oils obtained from the pyrolysis of sawdust, rice straw and green microalgae were likewise evaluated for direct comparison.

  4. Hydraulic fluids and jet engine oil: pyrolysis and aircraft air quality.

    PubMed

    van Netten, C; Leung, V

    2001-01-01

    Incidents of smoke in aircraft cabins often result from jet engine oil and/or hydraulic fluid that leaks into ventilation air, which can be subjected to temperatures that exceed 500 degrees C. Exposed flight-crew members have reported symptoms, including dizziness, nausea, disorientation, blurred vision, and tingling in the legs and arms. In this study, the authors investigated pyrolysis products of one jet engine oil and two hydraulic fluids at 525 degrees C. Engine oil was an important source of carbon monoxide. Volatile agents and organophosphate constituents were released from all the agents tested; however, the neurotoxin trimethyl propane phosphate was not found. The authors hypothesized that localized condensation of pyrolysis products in ventilation ducts, followed by mobilization when cabin heat demand was high, accounted for mid-flight incidents. The authors recommended that carbon monoxide data be logged continuously to capture levels during future incidents.

  5. Co-pyrolysis of corn cob and waste cooking oil in a fixed bed.

    PubMed

    Chen, Guanyi; Liu, Cong; Ma, Wenchao; Zhang, Xiaoxiong; Li, Yanbin; Yan, Beibei; Zhou, Weihong

    2014-08-01

    Corn cob (CC) and waste cooking oil (WCO) were co-pyrolyzed in a fixed bed. The effects of various temperatures of 500 °C, 550 °C, 600 °C and CC/WCO mass ratios of 1:0, 1:0.1, 1:0.5, 1:1 and 0:1 were investigated, respectively. Results show that co-pyrolysis of CC/WCO produce more liquid and less bio-char than pyrolysis of CC individually. Bio-oil and bio-char yields were found to be largely dependent on temperature and CC/WCO ratios. GC/MS of bio-oil show it consists of different classes and amounts of organic compounds other than that from CC pyrolysis. Temperature of 550 °C and CC/WCO ratio of 1:1 seem to be the optimum considering high bio-oil yields (68.6 wt.%) and good bio-oil properties (HHV of 32.78 MJ/kg). In this case, bio-char of 24.96 MJ/kg appears attractive as a renewable source, while gas with LHV of 16.06 MJ/Nm(3) can be directly used in boilers as fuel. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Carbon isotope analyses of n-alkanes released from rapid pyrolysis of oil asphaltenes in a closed system.

    PubMed

    Chen, Shasha; Jia, Wanglu; Peng, Ping'an

    2016-08-15

    Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  7. Generation of aliphatic acid anions and carbon dioxide by hydrous pyrolysis of crude oils

    USGS Publications Warehouse

    Kharaka, Y.K.; Lundegard, P.D.; Ambats, G.; Evans, William C.; Bischoff, J.L.

    1993-01-01

    Two crude oils with relatively high (0.60 wt%) and low (0.18 wt%) oxygen contents were heated in the presence of water in gold-plated reactors at 300??C for 2348 h. The high-oxygen oil was also heated at 200??C for 5711 h. The compositions of aqueous organic acid anions of the oils and of the headspace gases were monitored inn order to investigate the distribution of organic acids that can be generated from liquid petroleum. The oil with higher oxygen content generated about five times as much organic anions as the other oil. The dominant organic anions produced were acetate, propionate and butyrate. Small amounts of formate, succinate, methyl succinate and oxalate were also produced. The dominant oxygen-containing product was CO2, as has been observed in similar studies on the hydrous pyrolysis of kerogen. These results indicate that a significant portion (10-30%) of organic acid anions reported i be generated by thermal alteration of oils in reservoir rocks. The bulk of organic acid anions present in formation waters, however, is most likely generated by thermal alteration of kerogen in source rocks. Kerogen is more abundant than oil in sedimentary basins and the relative yields of organic acid anions reported from the hydrous pyrolysis of kerogen are much higher than the yields obtained for the two oils. ?? 1993.

  8. Process and economic model of in-field heavy oil upgrading using aqueous pyrolysis

    SciTech Connect

    Thorsness, C. B., LLNL

    1997-01-21

    A process and economic model for aqueous pyrolysis in-field upgrading of heavy oil has been developed. The model has been constructed using the ASPEN PLUS chemical process simulator. The process features cracking of heavy oil at moderate temperatures in the presence of water to increase oil quality and thus the value of the oil. Calculations with the model indicate that for a 464 Mg/day (3,000 bbl/day) process, which increases the oil API gravity of the processed oil from 13.5{degree} to 22.4{degree}, the required value increase of the oil would need to be at least $2.80/Mg{center_dot}{degree}API($0.40/bbl{center_dot}{degree}API) to make the process economically attractive. This level of upgrading has been demonstrated in preliminary experiments with candidate catalysts. For improved catalysts capable of having the coke make and increasing the pyrolysis rate, a required price increase for the oil as low as $1.34/Mg{center_dot}{degree}API ($0.21/bbl{center_dot}{degree}API)has been calculated.

  9. 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...

  10. Heat and mass transfer processes during the pyrolysis of antrim oil shale

    NASA Astrophysics Data System (ADS)

    Piccirelli, R. A.

    1980-07-01

    A model of simultaneous heat and mass transfer processes during the pyrolysis of slabs of consolidated Michigan oil shale is presented. The manner in which the transport processes control the yield of pyrolysis product is emphasized; the model parameters are selected to reflect the conditions expected during in situ retorting. A single reaction describes the generation of gaseous pyrolysis product; numerical solution of the model mass transport equations indicates that the pressure and velocity profiles within the shale due to generation of gaseous reaction products can be assumed to be in a quasi-steady state. It is concluded that while the bulk convective transport is not essential to the energy equation, it is important for product yield calculations; the solution also suggests that the heat transfer through the surface convective layer and into the shale slab is the rate limiting process.

  11. Study on pyrolysis gas in thermal extraction of Bai Yinhua lignite with industrial washing oil

    NASA Astrophysics Data System (ADS)

    Cui, Y. M.; Lian, X. P.; Zhao, F. Y.; Xu, Y. Q.; Hu, Y. Q.; Yuan, Z. K.; Hao, X. R.

    2016-08-01

    Industrial washing oil as solvent, pyrolysis gas produced from Bai Yinhua lignite during thermal extraction was studied by gas chromatography. The effects of temperature and solvent coal ration on coal pyrolysis gas were investigated. The results showed that: Pyrolysis gas produced mainly in CO, CO2, O2, H2, CH4, and so on, in which the total amount of oxygen containing compounds nearly 40%, significant effects of deoxidation was achieved. The increase of heat extraction temperature can significantly increase the degree of bond breaking and the gas formation rate, the gas yield and the rate of oxygen increase significantly, while the gas yield increases with the decrease of the solvent coal ration.

  12. 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.

  13. 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.

  14. Design and fabrication of a fixed-bed batch type pyrolysis reactor for pilot scale pyrolytic oil production in Bangladesh

    NASA Astrophysics Data System (ADS)

    Aziz, Mohammad Abdul; Al-khulaidi, Rami Ali; Rashid, MM; Islam, M. R.; Rashid, MAN

    2017-03-01

    In this research, a development and performance test of a fixed-bed batch type pyrolysis reactor for pilot scale pyrolysis oil production was successfully completed. The characteristics of the pyrolysis oil were compared to other experimental results. A solid horizontal condenser, a burner for furnace heating and a reactor shield were designed. Due to the pilot scale pyrolytic oil production encountered numerous problems during the plant’s operation. This fixed-bed batch type pyrolysis reactor method will demonstrate the energy saving concept of solid waste tire by creating energy stability. From this experiment, product yields (wt. %) for liquid or pyrolytic oil were 49%, char 38.3 % and pyrolytic gas 12.7% with an operation running time of 185 minutes.

  15. 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.

  16. 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.

  17. Ketonization of Model Pyrolysis Oil Solutions in a Plug Flow Reactor over a Composite Oxide of Fe, Ce, and Al

    USDA-ARS?s Scientific Manuscript database

    The stabilization and upgrading of pyrolysis oil requires the neutralization of the acidic components of the oil. The conversion of small organic acids, particularly acetic acid, to ketones is one approach to addressing the instability of the oils caused by low pH. In the ketonization reaction, acet...

  18. Pyrolysis of hornbeam (Carpinus betulus L.) sawdust: Characterization of bio-oil and bio-char.

    PubMed

    Moralı, Uğur; Yavuzel, Nazan; Şensöz, Sevgi

    2016-12-01

    Slow pyrolysis of hornbeam (Carpinus betulus L.) sawdust was performed to produce bio-oil and bio-char. The operational variables were as follows: pyrolysis temperature (400-600°C), heating rate (10-50°Cmin(-1)) and nitrogen flow rate (50-150cm(3)min(-1)). Physicochemical and thermogravimetric characterizations of hornbeam sawdust were performed. The characteristics of bio-oil and bio-char were analyzed on the basis of various spectroscopic and chromatographic techniques such as FTIR, GC-MS, 1H NMR, SEM, BET. Higher heating value, density and kinematic viscosity of the bio-oil with maximum yield of 35.28% were 23.22MJkg(-1), 1289kgm(-3) and 0.6mm(2)s(-1), respectively. The bio-oil with relatively high fuel potential can be obtained from the pyrolysis of the hornbeam sawdust and the bio-char with a calorific value of 32.88MJkg(-1) is a promising candidate for solid fuel applications that also contributes to the preservation of the environment.

  19. Insecticidal activity of bio-oil from the pyrolysis of straw from Brassica spp.

    PubMed

    Suqi, Liu; Cáceres, Luis A; Caceres, Luis; Schieck, Katie; McGarvey, Brian D; Booker, Christina J; McGarvey, Brian M; Yeung, Ken K-C; Pariente, Stephane; Briens, Cedric; Berruti, Franco; Scott, Ian M

    2014-04-23

    Agricultural crop residues can be converted through thermochemical pyrolysis to bio-oil, a sustainable source of biofuel and biochemicals. The pyrolysis bio-oil is known to contain many chemicals, some of which have insecticidal activity and can be a potential source of value-added pest control products. Brassicacae crops, cabbage, broccoli, and mustards, contain glucosinolates and isocyanates, compounds with recognized anti-herbivore activity. In Canada, canola Brassica napus straw is available from over 6 000 000 ha and mustard Brassica carinata and Brassica juncea straw is available from 200 000 ha. The straw can be converted by microbial lignocellulosic enzymes as a substrate for bioethanol production but can also be converted to bio-oil by thermochemical means. Straw from all three species was pyrolyzed, and the insecticidal components in the bio-oil were isolated by bioassay-guided solvent fractionation. Of particular interest were the mustard straw bio-oil aqueous fractions with insecticidal and feeding repellent activity to Colorado potato beetle larvae. Aqueous fractions further analyzed for active compounds were found not to contain many of the undesirable phenol compounds, which were previously found in other bio-oils seen in the dichloromethane (DCM) and ethyl acetate (EA) solvent phases of the present study. Identified within the most polar fractions were hexadecanoic and octadecanoic fatty acids, indicating that separation of these compounds during bio-oil production may provide a source of effective insecticidal compounds.

  20. Study on vacuum pyrolysis of coffee industrial residue for bio-oil production

    NASA Astrophysics Data System (ADS)

    Chen, Nanwei; Ren, Jie; Ye, Ziwei; Xu, Qizhi; Liu, Jingyong; Sun, Shuiyu

    2017-03-01

    Coffee industrial residue (CIR) is a biomass with high volatile content (64.94 wt.%) and heating value (21.3 MJ·kg-1). This study was carried out to investigate the pyrolysis condition and products of CIR using thermogravimetric analyser (TGA) and vacuum tube furnace. The influence of pyrolysis temperature, time, pressure and heating rate on the yield of pyrolysis products were discussed. There was an optimal pyrolysis condition: CIR was heated from normal temperature to 400 °C for 60 min, with 10 °C·min-1 heating rate and a pressure of 30 kPaabs. In this condition, the yields of bio-oil, char and non-condensable gas were 42.29, 33.14 and 24.57 wt.%, respectively. The bio-oil contained palmitic acid (47.48 wt.%), oleic acid (17.45 wt.%), linoleic acid (11.34 wt.%), octadecanoic acid (7.62 wt.%) and caffeine (5.18 wt.%).

  1. Production of phenol-rich bio-oil during catalytic fixed-bed and microwave pyrolysis of palm kernel shell.

    PubMed

    Omoriyekomwan, Joy Esohe; Tahmasebi, Arash; Yu, Jianglong

    2016-05-01

    Catalytic fixed-bed and microwave pyrolysis of palm kernel shell using activated carbon (AC) and lignite char (LC) as catalysts and microwave receptors are investigated. The effects of process parameters including temperature and biomass:catalyst ratio on the yield and composition of pyrolysis products were studied. The addition of catalyst increased the bio-oil yield, but decreased the selectivity of phenol in fixed-bed. Catalytic microwave pyrolysis of PKS significantly enhanced the selectivity of phenol production. The highest concentration of phenol in bio-oil of 64.58 %(area) and total phenolics concentration of 71.24 %(area) were obtained at 500°C using AC. Fourier transform infrared spectroscopy (FTIR) results indicated that concentration of OH, CH, CO and CO functional groups in char samples decreased after pyrolysis. Scanning electron microscopy (SEM) analysis clearly indicated the development of liquid phase in biomass particles during microwave pyrolysis, and the mechanism is also discussed.

  2. 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

  3. 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

  4. Pyrolysis and combustion of oil palm stone and palm kernel cake in fixed-bed reactors.

    PubMed

    Razuan, R; Chen, Q; Zhang, X; Sharifi, V; Swithenbank, J

    2010-06-01

    The main objective of this research was to investigate the main characteristics of the thermo-chemical conversion of oil palm stone (OPS) and palm kernel cake (PKC). A series of combustion and pyrolysis tests were carried out in two fixed-bed reactors. The effects of heating rate at the temperature of 700 degrees C on the yields and properties of the pyrolysis products were investigated. The results from the combustion experiments showed that the burning rates increased with an increase in the air flow rate. In addition, the FLIC code was used to simulate the combustion of the oil palm stone to investigate the effect of primary air flow on the combustion process. The FLIC modelling results were in good agreement with the experimental data in terms of predicting the temperature profiles along the bed height and the composition of the flue gases.

  5. 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.

  6. 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.

  7. Production of hydrocarbon fuels from pyrolysis of soybean oils using a basic catalyst.

    PubMed

    Xu, Junming; Jiang, Jianchun; Sun, Yunjuan; Chen, Jie

    2010-12-01

    Triglycerides obtained from animals and plants have attracted great attention from researchers for developing an environmental friendly and high-quality fuel, free of nitrogen and sulfur. In the present work, the production of biofuel by catalytic cracking of soybean oil over a basic catalyst in a continuous pyrolysis reactor at atmospheric pressure has been studied. Experiments were designed to study the effect of different types of catalysts on the yield and acid value of the diesel and gasoline fractions from the pyrolytic oil. It was found that basic catalyst gave a product with relatively low acid number. These pyrolytic oils were also further reacted with alcohol in order to decrease their acid value. After esterification, the physico-chemical properties of these biofuels were characterized, and compared with Chinese specifications for conventional diesel fuels. The results showed that esterification of pyrolytic oil from triglycerides represents an alternative technique for producing biofuels from soybean oils with characteristics similar to those of petroleum fuels.

  8. Isolation of levoglucosan from lignocellulosic pyrolysis oil derived from wood or waste newsprint

    DOEpatents

    Moens, Luc

    1995-01-01

    A method is provided for preparing high purity levoglucosan from lignocellulosic pyrolysis oils derived from wood or waste newsprint. The method includes reducing wood or newsprint to fine particle sizes, treating the particles with a hot mineral acid for a predetermined period of time, and filtering off and drying resulting solid wood or newsprint material; pyrolyzing the dried solid wood or newsprint material at temperatures between about 350.degree. and 375.degree. C. to produce pyrolysis oils; treating the oils to liquid-liquid extraction with methyl isobutyl ketone to remove heavy tar materials from the oils, and to provide an aqueous fraction mixture of the oils containing primarily levoglucosan; treating the aqueous fraction mixtures with a basic metal salt in an amount sufficient to elevate pH values to a range of about 12 to about 12.5 and adding an amount of the salt in excess of the amount needed to obtain the pH range to remove colored materials of impurities from the oil and form a slurry, and freeze-drying the resulting slurry to produce a dry solid residue; and extracting the levoglucosan from the residue using ethyl acetate solvent to produce a purified crystalline levoglucosan.

  9. Isolation of levoglucosan from lignocellulosic pyrolysis oil derived from wood or waste newsprint

    DOEpatents

    Moens, L.

    1995-07-11

    A method is provided for preparing high purity levoglucosan from lignocellulosic pyrolysis oils derived from wood or waste newsprint. The method includes reducing wood or newsprint to fine particle sizes, treating the particles with a hot mineral acid for a predetermined period of time, and filtering off and drying resulting solid wood or newsprint material; pyrolyzing the dried solid wood or newsprint material at temperatures between about 350 and 375 C to produce pyrolysis oils; treating the oils to liquid-liquid extraction with methyl isobutyl ketone to remove heavy tar materials from the oils, and to provide an aqueous fraction mixture of the oils containing primarily levoglucosan; treating the aqueous fraction mixtures with a basic metal salt in an amount sufficient to elevate pH values to a range of about 12 to about 12.5 and adding an amount of the salt in excess of the amount needed to obtain the pH range to remove colored materials of impurities from the oil and form a slurry, and freeze-drying the resulting slurry to produce a dry solid residue; and extracting the levoglucosan from the residue using ethyl acetate solvent to produce a purified crystalline levoglucosan. 2 figs.

  10. Utilizing asphaltene pyrolysis to predict pyrolysis kinetics of heavy crude oil and extractable native bitumen

    SciTech Connect

    Reynolds, J.G.

    1992-01-07

    Selected heavy crude oils and extracted tar sand bitumens were separated into asphaltene and maltene fractions. The whole feeds and fractions were then examined by micropyrolysis at nominal constant heating rates from 1 to 50{degrees}C/min from temperatures of 250 to 650{degrees}C to establish evolution behavior, pyrolysate yields, and kinetics of evolution.

  11. Thermochemical Conversion of Sugarcane Bagasse into Bio-Crude Oils by Fluidized-Bed Pyrolysis Technology

    NASA Astrophysics Data System (ADS)

    Islam, Mohammad Rofiqul; Haniu, Hiroyuki; Islam, Mohammad Nurul; Uddin, Md. Shazib

    Thermochemical conversion of sugarcane bagasse into bio-crude oils by fluidized-bed reactor has been taken into consideration in this study. The bagasse in particle form was pyrolyzed in an externally heated 7cm diameter and 37.5cm high fluidized-bed reactor with nitrogen as a carrier gas. The reactor chamber and gas-preheater were heated by means of a renewable energy biomass source cylindrical heater. At a reactor bed temperature of 450°C for a feed particle size of 420-600µm and at a gas flow rate of 30 l/min, an oil yield of 48wt% of dry feed was obtained. The pyrolysis process temperature was found to have influenced on the product yields. Characterization of the whole pyrolysis liquids obtained at optimum operating conditions has been carried out including physical properties, elemental analyses, GCV, FT-IR, and 1H NMR analysis. The results show that pyrolysis of sugarcane bagasse waste is a good option for producing bio-crude oils to be used as alternative to petroleum fuels and valuable chemical feedstocks.

  12. Characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil.

    PubMed

    Song, Geum-Ju; Seo, Yong-Chil; Pudasainee, Deepak; Kim, In-Tae

    2010-07-01

    An attempt has been made to recover high-calorific fuel gas and useful carbonaceous residue by the electric arc pyrolysis of waste lubricating oil. The characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil were investigated in this study. The produced gas was mainly composed of hydrogen (35-40%), acetylene (13-20%), ethylene (3-4%) and other hydrocarbons, whereas the concentration of CO was very low. Calorific values of gas ranged from 11,000 to 13,000 kcal kg(-1) and the concentrations of toxic gases, such as NO(x), HCl and HF, were below the regulatory emissions limit. Gas chromatography-mass spectrometry (GC/MS) analysis of liquid-phase residues showed that high molecular-weight hydrocarbons in waste lubricating oil were pyrolyzed into low molecular-weight hydrocarbons and hydrogen. Dehydrogenation was found to be the main pyrolysis mechanism due to the high reaction temperature induced by electric arc. The average particle size of soot as carbonaceous residue was about 10 microm. The carbon content and heavy metals in soot were above 60% and below 0.01 ppm, respectively. The utilization of soot as industrial material resources such as carbon black seems to be feasible after refining and grinding. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

  13. Upgrading of heavy oil from the San Joaquin Valley of California by aqueous pyrolysis

    SciTech Connect

    Reynolds, J.G.; Murray, A.M.; Nuxoll, E.V.; Fox, G.A.

    1995-10-01

    Midway Sunset crude oil and well-head oil were treated at elevated temperatures in a closed system with the presence of water. Mild to moderate upgrading, as measured by increase in API gravity, was observed at 400{degrees}C or above. Reduced pressure operation exhibited upgrading activity comparable to upgrading under normal aqueous pyrolysis conditions. Reduced pressure operation was obtained by the use of specific blending methods, a surfactant, and the proper amount of water. The use of additives provided additional upgrading. The best of the minimum set tested was Co(II) 2-ethylhexanoate. Fe(III) 2-ethylhexanoate also showed some activity under certain conditions.

  14. 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.

  15. 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.

  16. 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.

  17. Influence of pyrolysis condition on switchgrass bio-oil yield and physicochemical properties.

    PubMed

    He, Ronghai; Ye, X Philip; English, Burton C; Satrio, Justinus A

    2009-11-01

    The poor and inconsistent physicochemical properties of bio-oil are inhibiting its industrialized production. We investigated the variability in properties of switchgrass bio-oil produced at three pyrolysis temperatures (T=450, 500, and 550 degrees C) and three feedstock moisture contents (MC=5%, 10%, and 15%) in a 3x3 factorial experiment in order to exploit opportunities to improve bio-oil properties through optimization of pyrolysis parameters. Results showed that even with the single type of feedstock and pyrolysis system, the two main factors and their interaction caused large variations in bio-oil yield and most of the measured physicochemical properties. Following improvements of bio-oil properties could be individually achieved by selecting an optimal pyrolysis condition (shown in parenthesis) comparing with the worst case: increase of bio-oil yield by more than twofold (MC=10%, T=450 degrees C), increase of pH by 20.4% from 2.74 to 3.3 (MC=10%, T=550 degrees C), increase of higher heating value by 18.1% from 16.6 to 19.6 MJ/kg (MC=10%, T=450 degrees C), decrease of density by 5.9% from 1.18 to 1.11 g/cm(3) (MC=5%, T=550 degrees C), decrease of water content by 36% from 31.4 to 20.1 wt.% (MC=5%, T=450 degrees C), decrease of viscosity by 40% from 28.2 to 17 centistokes (MC=5%, T=550 degrees C), decrease of solid content by 57% from 2.86 to 1.23 wt.% (MC=15%, T=550 degrees C), and decrease of ash content by 41.9% from 0.62 to 0.36 wt.% (MC=15%, T=550 degrees C). There is no single, clear-cut optimal condition that can satisfy the criteria for a bio-oil product with all the desired properties. Trade-offs should be balanced according to the usage of the end-products.

  18. 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.

  19. 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.

  20. 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.

  1. 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...

  2. 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...

  3. Element and PAH constituents in the residues and liquid oil from biosludge pyrolysis in an electrical thermal furnace.

    PubMed

    Chiang, Hung-Lung; Lin, Kuo-Hsiung; Lai, Nina; Shieh, Zhu-Xin

    2014-05-15

    Biosludge can be pyrolyzed to produce liquid oil as an alternative fuel. The content of five major elements, 22 trace elements and 16 PAHs was investigated in oven-dried raw material, pyrolysis residues and pyrolysis liquid products. Results indicated 39% carbon, 4.5% hydrogen, 4.2% nitrogen and 1.8% sulfur were in oven dried biosludge. Biosludge pyrolysis, carried out at temperatures from 400 to 800°C, corresponded to 34-14% weight in pyrolytic residues, 32-50% weight in liquid products and 31-40% weight in the gas phase. The carbon, hydrogen and nitrogen decreased and the sulfur content increased with an increase in the pyrolysis temperature at 400-800°C. NaP (2 rings) and AcPy (3 rings) were the major PAHs, contributing 86% of PAHs in oven-dried biosludge. After pyrolysis, the PAH content increased with the increase of pyrolysis temperature, which also results in a change in the PAH species profile. In pyrolysis liquid oil, NaP, AcPy, Flu and PA were the major species, and the content of the 16 PAHs ranged from 1.6 to 19 μg/ml at pyrolysis temperatures ranging from 400 to 800°C. Ca, Mg, Al, Fe and Zn were the dominant trace elements in the raw material and the pyrolysis residues. In addition, low toxic metal (Cd, V, Co, and Pb) content was found in the liquid oil, and its heat value was 7,800-9,500 kcal/kg, which means it can be considered as an alternative fuel.

  4. 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.

  5. The characteristics of bio-oil produced from the pyrolysis of three marine macroalgae.

    PubMed

    Bae, Yoon Ju; Ryu, Changkook; Jeon, Jong-Ki; Park, Junhong; Suh, Dong Jin; Suh, Young-Woong; Chang, Daejun; Park, Young-Kwon

    2011-02-01

    The pyrolysis of two brown macroalgae (Undaria pinnatifida and Laminaria japonica) and one red macroalgae (Porphyra tenera) was investigated for the production of bio-oil within the temperature range of 300-600°C. Macroalgae differ from lignocellulosic land biomass in their constitutional compounds and high N, S and ash contents. The maximum production of bio-oil was achieved at 500°C, with yields between 37.5 and 47.4 wt.%. The main compounds in bio-oils vary between macroalgae and are greatly different from those of land biomass, especially in the presence of many nitrogen-containing compounds. Of the gaseous products, CO(2) was dominant, while C(1)-C(4) hydrocarbons gradually increasing at 400°C and above. The pretreatment of macroalgae by acid washing effectively reduced the ash content. The pyrolysis of macroalgae offers a new opportunity for feedstock production; however, the utilization of bio-oil as a fuel product needs further assessment.

  6. Characterization of bio-oil and biochar from high-temperature pyrolysis of sewage sludge.

    PubMed

    Chen, Hongmei; Zhai, Yunbo; Xu, Bibo; Xiang, Bobin; Zhu, Lu; Qiu, Lei; Liu, Xiaoting; Li, Caiting; Zeng, Guangming

    2015-01-01

    The influence of temperature (550-850°C) on the characteristics of bio-oil and biochar from the pyrolysis of sewage sludge (SS) in a horizontal tube reactor was investigated. Results showed that when the pyrolysis temperature increased from 550°C to 850°C, the yield of bio-oil decreased from 26.16% (dry ash-free basis) to 20.78% (dry ash-free basis). Main components of bio-oil were phenols, esters, cholests, ketones, amides, indoles, and nitriles. Besides, the elevated heating rate of 25°C/min was demonstrated to favour the complete combustion of bio-oil. Moreover, caused by the increase in temperature, the yield of biochar decreased from 54.9 to 50.6 wt%, Brunauer-Emmet-Teller surface area increased from 48.51 to 81.28 m2/g. Furthermore, pH was increased from 5.93 of SS to 7.15-8.96 of biochar. The negative ζ-potential was also strengthened (-13.87 to -11.30 mV) and principal functional groups on the surface of biochar were -OH, C=O, C=C, -NO2, and S=O.

  7. Catalytic co-pyrolysis of waste vegetable oil and high density polyethylene for hydrocarbon fuel production.

    PubMed

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

    2017-03-01

    In this study, a ZrO2-based polycrystalline ceramic foam catalyst was prepared and used in catalytic co-pyrolysis of waste vegetable oil and high density polyethylene (HDPE) for hydrocarbon fuel production. The effects of pyrolysis temperature, catalyst dosage, and HDPE to waste vegetable oil ratio on the product distribution and hydrocarbon fuel composition were examined. Experimental results indicate that the maximum hydrocarbon fuel yield of 63.1wt. % was obtained at 430°C, and the oxygenates were rarely detected in the hydrocarbon fuel. The hydrocarbon fuel yield increased when the catalyst was used. At the catalyst dosage of 15wt.%, the proportion of alkanes in the hydrocarbon fuel reached 97.85wt.%, which greatly simplified the fuel composition and improved the fuel quality. With the augment of HDPE to waste vegetable oil ratio, the hydrocarbon fuel yield monotonously increased. At the HDPE to waste vegetable oil ratio of 1:1, the maximum proportion (97.85wt.%) of alkanes was obtained. Moreover, the properties of hydrocarbon fuel were superior to biodiesel and 0(#) diesel due to higher calorific value, better low-temperature low fluidity, and lower density and viscosity. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. A kinetic model for production of glucose by hydrolysis of levoglucosan and cellobiosan from pyrolysis oil.

    PubMed

    Helle, Steve; Bennett, Nicole M; Lau, Karen; Matsui, Justin H; Duff, Sheldon J B

    2007-11-26

    Anhydro sugars, produced during wood pyrolysis, can by hydrolyzed to sugars under acidic conditions. The acid hydrolysis of two common anhydro sugars in wood pyrolysis oils, levoglucosan (1,6-anhydro-beta-D-glucopyranose) and cellobiosan (beta-D-glucopyranosyl-(1-->4)-1,6-anhydro-D-glucopyranose), was investigated. Levoglucosan hydrolysis to glucose follows a first-order reaction, with an activation energy of 114 kJ mol(-1). For cellobiosan hydrolysis, 44% of the cellobiosan is hydrolyzed initially via the beta-(1-->4) glycosidic bond to form levoglucosan and glucose. The remaining cellobiosan is hydrolyzed initially at the 1,6 anhydro bond to form cellobiose. Both reactions are first order with respect to cellobiosan, with an activation energy of 99 kJ mol(-1). The intermediate levoglucosan and cellobiose are hydrolyzed to glucose.

  9. 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.

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

    PubMed

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

    2016-06-22

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

  11. 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

  12. [Effects of macrophytes pyrolysis bio-oil on Skeletonema costatum antioxidant enzyme activities].

    PubMed

    Yao, Yuan; Li, Feng-Min; Li, Yuan-Yuan; Shan, Shi; Li, Jie; Wang, Zhen-Yu

    2013-02-01

    In order to reveal the preliminary inhibition mechanisms of aquatic plants bio-oils on Skeletonema costatum, effects of Arundo donax L. 300 degees C, Ph. australis Trin. 400 degrees C and Typha orientalis Pres1 400 degrees C bio-oils on the concentration change of malondialdehyde (MDA) and the activity of antioxidant enzymes system (SOD, POD and CAT) were evaluated. The results showed that the higher Ihe Bio-oil concentrations, the higher the MDA contents in Skeletonema costatum was, and when the Bio-oil concentration was 10 mg.L-1 the MDA concentration increased with the reaction time. Superoxide dismutase (SOD) activity also increased with the increase of bio-oil concentration. For Arundo donax L 300 degrees C and Typha orientalis Presl 400 degrees C bio-oil, when the reaction time was longer, the S0D activity of Skeletonema costatum first increased and then decreased, and in both cases the maximum SOD activity was measured at 24 h. reaching 93.6 U (10(7) cells)-1 and 8.23 U (10(7) cells)-1, respectively. For Ph. australis Trin 400 degrees C bio-oil, the SOD activity kept increasing within 72 h. The peroxidase ( POD) activity of Skeletonema costatum also increased with the increase of bio-il concentrations. In the presence of Arundo donax L. 300 degrees C and Ph. australis Trin 400 degrees C bio-oil, the POD activity of Skeletonma, costatum first increased and then decreased, while with Typha orientalis Presl 400 degrees C bio-oil the POD activity increased with fluctuations. For all the three bio-oils, the catalase (CAT) activities increased first and then decreased when the reaction time was prolonged, and the higher the bio-oils concentration, the greater the CAT activity was. Pyrolysis bio-oils enhance the activity of antioxidant enzymes, leading to intracellular oxidative stress in the algae, which seems to be the main inhibitory mechanism for algae

  13. 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.

  14. 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.

  15. Investigation into the distribution of polycyclic aromatic hydrocarbons (PAHs) in wastewater sewage sludge and its resulting pyrolysis bio-oils.

    PubMed

    Hu, Yanjun; Li, Guojian; Yan, Mi; Ping, Chuanjuan; Ren, Jianli

    2014-03-01

    This study firstly investigated the distributions of 16 US EPA priority controlled polycyclic aromatic hydrocarbons (PAHs) in seven kinds of different wastewater sewage sludges and bio-oils from the sludge pyrolysis. A lab-scale tube furnace was used to simulate sludge pyrolysis and retrieve condensed oils. PAH determination was conducted with the extraction, concentration, and purification of PAHs in sludge samples and the resulting bio-oils, and then GC-MS analysis. Then, the factors influencing the distributions of different rings of PAHs in pyrolysis bio-oil, such as the chemical characteristics of raw sewage sludge and pyrolysis condition, were analyzed. It was noted that the total amount of PAHs in raw sludge is evidently varied with the sludge resource, with values ranging between 9.19 and 23.68 mg/kg. The middle molar weight (MMW) PAH distribution is dominant. PAH concentrations in sludge pyrolysis bio-oil were ranged from 13.72 to 48.9 mg/kg. The most abundant PAHs were the low molar weight (LMW) PAHs. It could be found that the concentration of LMW PAHs in bio-oil is correlated with MMW PAHs in raw sewage sludge at best, which the correlation coefficient is 0.607. For MMW and HMW (high molar weight) PAHs, they are significantly correlated with HMW PAHs in raw sewage sludge, which the correlation coefficients are 0.672 and 0.580, respectively. The concentration of LMW PAHs in bio-oil is also relatively significant and correlated with the volatile matter content of raw sludge. In addition, it was proved that final temperature and residence time have important influences on PAH generations during the pyrolysis of sewage sludge.

  16. 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.

  17. Jute stick pyrolysis for bio-oil production in fluidized bed reactor.

    PubMed

    Asadullah, M; Anisur Rahman, M; Mohsin Ali, M; Abdul Motin, M; Borhanus Sultan, M; Robiul Alam, M; Sahedur Rahman, M

    2008-01-01

    Pyrolysis of jute stick for bio-oil production has been investigated in a continuous feeding fluidized bed reactor at different temperatures ranging from 300 degrees C to 600 degrees C. At 500 degrees C, the yields of bio-oil, char and non-condensable gas were 66.70 wt%, 22.60 wt% and 10.70 wt%, respectively based on jute stick. The carbon based non-condensable gas was the mixture of carbon monoxide, carbon dioxide, methane, ethane, ethene, propane and propene. The density and viscosity of bio-oil were found to be 1.11 g/mL and 2.34 cP, respectively. The lower heating value (LHV) of bio-oil was found to be 18.2 5 MJ/kg. Since bio-oil contains some organic acids such as formic acid, acetic acid, etc., the pH and acid value of the bio-oil were found to be around 4 and 135 mg KOH/g, respectively. The water, lignin, solid and ash contents of bio-oil were determined and found to be around 15 wt%, 4.90 wt%, 0.02 wt% and 0.10 wt%, respectively.

  18. Comparision of real waste (MSW and MPW) pyrolysis in batch reactor over different catalysts. Part I: product yields, gas and pyrolysis oil properties.

    PubMed

    Ateş, Funda; Miskolczi, Norbert; Borsodi, Nikolett

    2013-04-01

    Pyrolysis of municipal solid waste (MSW) and municipal plastic waste (MPW) have been investigated in batch reactor at 500, 550 and 600°C both in absence and presence of catalysts (Y-zeolite, β-zeolite, equilibrium FCC, MoO3, Ni-Mo-catalyst, HZSM-5 and Al(OH)3). The effect of the parameters on the product properties was investigated. Products were characterized using gas-chromatography, GC/MS, (13)C NMR. Yields of volatile fractions increased, while reaction time necessity for the total cracking decreased in the presence of catalysts. Catalysts have productivity and selectivity in converting aliphatic hydrocarbons to aromatic and cyclic compounds in oil products. Gases from MSW consisted of hydrogen CO, CO2, while exclusively hydrogen and hydrocarbons were detected from MPW. Catalyst efficiency was higher using MPW than MSW. Pyrolysis oils contained aliphatic hydrocarbons, aromatics, cyclic compounds and less ketones, alcohols, acids or esters depending on the raw materials.

  19. 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.

  20. Baseline NO{sub x} emissions during combustion of wood-derived pyrolysis oils

    SciTech Connect

    Baxter, L.; Jenkins, B.; Winter, F.

    1995-01-01

    NO{sub x} emissions from two pyrolysis oils of similar origin and overall composition but differing nitrogen contents (0.12 and 0.32% of dry fuel) are determined in a pilot-scale combustor. No NO{sub x} reduction technology is employed in these tests, establishing the baseline or uncontrolled levels of NO{sub x}. Measured effluent oxygen concentrations range from near 0% to near 21%, with stoichiometric ratios ranging from 0 to 1. NO and NO{sub x} are measured separately and found to differ by insignificant ({approx}10--25 ppmv) amounts. Other relevant gas species (CO{sub 2}, CO, total hydrocarbons, and O{sub 2}) are also reported. Peak NO{sub x} emissions from these fuels vary from about 300 to around 650 ppmv, with lower levels associated with low nitrogen content fuels. Trends with stoichiometric ratio and fuel nitrogen content agree qualitatively with behavior from other nitrogen containing fuels, including biomass, coal, and petroleum oils. Nitrogen conversion efficiencies as a function of stoichiometric and fuel nitrogen content are observed to decrease with increasing fuel nitrogen content and increase with increasing oxygen content. Measurements of thermal, prompt, and fuel NO{sub x} contributes indicate that fuel NO{sub x} is the dominant formation mechanism for these fuels. These data suggest that NO{sub x} formed during combustion of pyrolysis oil lends itself to many of the same control technologies as are used in other nitrogen-containing fuel.

  1. Pyrolysis of azolla, sargassum tenerrimum and water hyacinth for production of bio-oil.

    PubMed

    Biswas, Bijoy; Singh, Rawel; Krishna, Bhavya B; Kumar, Jitendra; Bhaskar, Thallada

    2017-10-01

    Pyrolysis of azolla, sargassum tenerrimum and water hyacinth were carried out in a fixed-bed reactor at different temperatures in the range of 300-450°C in the presence of nitrogen (inert atmosphere). The objective of this study is to understand the effect of compositional changes of various aquatic biomass samples on product distribution and nature of products during slow pyrolysis. The maximum liquid product yield of azolla, sargassum tenerrimum and water hyacinth (38.5, 43.4 and 24.6wt.% respectively) obtained at 400, 450 and 400°C. Detailed analysis of the bio-oil and bio-char was investigated using (1)H NMR, FT-IR, and XRD. The characterization of bio-oil showed a high percentage of aliphatic functional groups and presence of phenolic, ketones and nitrogen-containing group. The characterization results showed that the bio-oil obtained from azolla, sargassum tenerrimum and water hyacinth can be potentially valuable as a fuel and chemicals. Copyright © 2017 Elsevier Ltd. All rights reserved.

  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. In-depth investigation on quantitative characterization of pyrolysis oil by 31P NMR

    DOE PAGES

    Ben, Haoxi; Ferrell, III, Jack R.

    2016-01-29

    The characterization of different heteroatom functional groups by employing 31P NMR has been developed for almost 30 years. In this study, an in-depth investigation of this commonly used method has been accomplished for the analysis of pyrolysis oil. Several commonly used internal standards for 31P NMR have been examined by in situ monitoring. The results indicated that endo-N-hydroxy-5-norbornene-2,3-dicarboximide (NHND) is not stable after a long period of storage or experiment (>12 hours), but both cyclohexanol and triphenylphosphine oxide (TPPO) can be used as internal standards if a long experiment or storage is required. The pyrolysis oil has also been investigatedmore » by both short time (16 hours) in situ monitoring and long time (14 days) ex situ monitoring. The results showed that aliphatic OH, carboxylic acids and water contents are not very stable after 2 hours, and thus a short time of preparation, storage, and experiment need to be considered to ensure a precise quantitative measurement. The decomposition products are still unclear, but some preliminary investigations for different acids, (e.g. formic acid) have been accomplished. The results indicated that the aromatic carboxylic acids (benzoic acid and vanillic acid) are more stable than formic acid and acetic acid. Interestingly, the formic acid will even decompose to some other compounds at the very beginning of the in situ monitoring test. Further characterization found that water is one of the major products for the decomposition of formic acid in the 31P NMR solution. Finally, as far as we know, this is the first report on such time-dependent changes when using 31P NMR to analyze the pyrolysis oil, and these results show that proper application of this method is essential to achieve reliable quantitative data.« less

  4. 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.

  5. Pyrolysis of safflower (Charthamus tinctorius L.) seed press cake in a fixed-bed reactor: part 2. Structural characterization of pyrolysis bio-oils.

    PubMed

    Sensöz, Sevgi; Angin, Dilek

    2008-09-01

    Biomass in the form of agricultural residues is becoming popular among new renewable energy sources, especially given its wide potential and abundant usage. Pyrolysis is the most important process among the thermal conversion processes of biomass. In this study, the various characteristics of bio-oils acquired under different pyrolysis conditions from safflower seed press cake (SPC) were identified. The elemental analyses and calorific values of the bio-oils were determined, and then the chemical compositions of the bio-oils were investigated using chromatographic and spectroscopic techniques such as column chromatography, (1)H NMR, FTIR and GC. The fuel properties of the bio-oil such as kinematic viscosity, flash point, density, water content and ASTM distillation were also determined. Chemical compositions of bio-oils showed that some quantities of hydrocarbons were present, while oxygenated and polar fractions dominated. The bio-oils obtained from safflower seed press cake were presented as an environmentally friendly feedstock candidate for biofuels and chemicals.

  6. 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.

  7. 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.

  8. 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

  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

    2016-01-01

    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.

  10. Physical and Chemical Properties of Bio-Oils From Microwave Pyrolysis of Corn Stover

    NASA Astrophysics Data System (ADS)

    Yu, Fei; Deng, Shaobo; Chen, Paul; Liu, Yuhuan; Wan, Yiqin; Olson, Andrew; Kittelson, David; Ruan, Roger

    This study was aimed to understand the physical and chemical properties of pyrolytic bio-oils produced from microwave pyrolysis of corn stover regarding their potential use as gas turbine and home heating fuels. The ash content, solids content, pH, heating value, minerals, elemental ratio, moisture content, and viscosity of the bio-oils were determined. The water content was approx 15.2 wt%, solids content 0.22 wt%, alkali metal content 12 parts per million, dynamic viscosity 185 mPa·s at 40°C, and gross high heating value 17.5 MJ/kg for a typical bio-oil produced. Our aging tests showed that the viscosity and water content increased and phase separation occurred during the storage at different temperatures. Adding methanol and/or ethanol to the bio-oils reduced the viscosity and slowed down the increase in viscosity and water content during the storage. Blending of methanol or ethanol with the bio-oils may be a simple and cost-effective approach to making the pyrolytic bio-oils into a stable gas turbine or home heating fuels.

  11. Physical and chemical properties of bio-oils from microwave pyrolysis of corn stover.

    PubMed

    Yu, Fei; Deng, Shaobo; Chen, Paul; Liu, Yuhuan; Wan, Yiqin; Olson, Andrew; Kittelson, David; Ruan, Roger

    2007-04-01

    This study was aimed to understand the physical and chemical properties of pyrolytic bio-oils produced from microwave pyrolysis of corn stover regarding their potential use as gas turbine and home heating fuels. The ash content, solids content, pH, heating value, minerals, elemental ratio, moisture content, and viscosity of the bio-oils were determined. The water content was approx 15.2 wt%, solids content 0.22 wt%, alkali metal content 12 parts per million, dynamic viscosity 185 mPa.s at 40 degrees C, and gross high heating value 17.5 MJ/kg for a typical bio-oil produced. Our aging tests showed that the viscosity and water content increased and phase separation occurred during the storage at different temperatures. Adding methanol and/or ethanol to the bio-oils reduced the viscosity and slowed down the increase in viscosity and water content during the storage. Blending of methanol or ethanol with the bio-oils may be a simple and cost-effective approach to making the pyrolytic bio-oils into a stable gas turbine or home heating fuels.

  12. 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.

  13. D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

    USGS Publications Warehouse

    Schimmelmann, A.; Lewan, M.D.; Wintsch, R.P.

    1999-01-01

    Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310-381??C), time (12-144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil-hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330??C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ~ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381 ??C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350??C for 72 h, or 330??C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115??C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected

  14. AN EVALUATION OF PYROLYSIS OIL PROPERTIES AND CHEMISTRY AS RELATED TO PROCESS AND UPGRADE CONDITIONS WITH SPECIAL CONSIDERATION TO PIPELINE SHIPMENT

    SciTech Connect

    Bunting, Bruce G; Boyd, Alison C

    2012-01-01

    One factor limiting the development of commercial biomass pyrolysis is challenges related to the transportation of the produced pyrolysis oil. The oil has different chemical and physical properties than crude oil, including more water and oxygen and has lower H/C ratio, higher specific gravity and density, higher acidity, and lower energy content. These differences could limit its ability to be transported by existing petroleum pipelines. Pyrolysis oil can also be treated, normally by catalytic hydrodeoxygenation, and approaches crude oil and petroleum condensates at higher severity levels. This improvement also results in lower liquid yield and high hydrogen consumption. Biomass resources for pyrolysis are expected to become plentiful and widely distributed in the future, mainly through the use of crop residuals and growing of energy crops such as perennial grasses, annual grasses, and woody crops. Crude oil pipelines are less well distributed and, when evaluated on a county level, could access about 18% of the total biomass supply. States with high potential include Texas, Oklahoma, California, and Louisiana. In this study, published data on pyrolysis oil was compiled into a data set along with bio-source source material, pyrolysis reactor conditions, and upgrading conditions for comparison to typical crude oils. Data of this type is expected to be useful in understanding the properties and chemistry and shipment of pyrolysis oil to refineries, where it can be further processed to fuel or used as a source of process heat.

  15. Pyrolysis of Woody Residue Feedstocks: Upgrading of Bio-Oils from Mountain-Pine-Beetle-Killed Trees and Hog Fuel

    SciTech Connect

    Zacher, Alan H.; Elliott, Douglas C.; Olarte, Mariefel V.; Santosa, Daniel M.; Preto, Fernando; Iisa, Kristiina

    2014-12-01

    Liquid transportation fuel blend-stocks were produced by pyrolysis and catalytic upgrading of woody residue biomass. Mountain pine beetle killed wood and hog fuel from a saw mill were pyrolyzed in a 1 kg/h fluidized bed reactor and subsequently upgraded to hydrocarbons in a continuous fixed bed hydrotreater. Upgrading was performed by catalytic hydrotreatment in a two-stage bed at 170°C and 405°C with a per bed LHSV between 0.17 and 0.19. The overall yields from biomass to upgraded fuel were similar for both feeds: 24-25% despite the differences in bio-oil (intermediate) mass yield. Pyrolysis bio-oil mass yield was 61% from MPBK wood, and subsequent upgrading of the bio-oil gave an average mass yield of 41% to liquid fuel blend stocks. Hydrogen was consumed at an average of 0.042g/g of bio-oil fed, with final oxygen content in the product fuel ranging from 0.31% to 1.58% over the course of the test. Comparatively for hog fuel, pyrolysis bio-oil mass yield was lower at 54% due to inorganics in the biomass, but subsequent upgrading of that bio-oil had an average mass yield of 45% to liquid fuel, resulting in a similar final mass yield to fuel compared to the cleaner MPBK wood. Hydrogen consumption for the hog fuel upgrading averaged 0.041 g/g of bio-oil fed, and the final oxygen content of the product fuel ranged from 0.09% to 2.4% over the run. While it was confirmed that inorganic laded biomass yields less bio-oil, this work demonstrated that the resultant bio-oil can be upgraded to hydrocarbons at a higher yield than bio-oil from clean wood. Thus the final hydrocarbon yield from clean or residue biomass pyrolysis/upgrading was similar.

  16. Pyrolysis of groundnut de-oiled cake and characterization of the liquid product.

    PubMed

    Agrawalla, Ankit; Kumar, Sachin; Singh, R K

    2011-11-01

    Renewable biomass is considered as an important energy resource all over the world and for an agriculture based economy like that of India, the future prospects of being able to convert widely available biomass materials into various forms of fuel is most attractive. In this study, pyrolysis of groundnut de-oiled cake was investigated with an aim of studying the physical and chemical characteristics of the bio-fuel produced and to determine its feasibility as a commercial fuel. Thermal pyrolysis of groundnut de-oiled cake was done in a semi-batch reactor at a temperature range of 200-500 °C and at a heating rate of 20 °C/min. The chemical analysis of the bio-fuel showed the presence of functional groups such as alkanes, alkenes, alkynes, aldehydes, ketones, carboxylic acids, esters, amines, nitriles, nitro compounds and aromatics rings. The physical properties of the bio-fuel obtained were close to that of diesel and petrol. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. Pyrolysis of Uinta Basin Oil Sands in fluidized bed and rotary kiln reactors

    SciTech Connect

    Nagpal, S.; Fletcher, J.V.; Hanson, F.V.

    1995-12-31

    A pilot-scale fluidized bed reactor (FBR) was used to pyrolyze the mined and crushed ore from the PR Spring oil sands deposit which is located in the Uinta Basin of Utah. Liquid yields of approximately 80 wt% of the bitumen fed to the reactor were obtained. This compares to 55-70 wt% obtained from smaller laboratory scale fluidized bed reactors and a pilot-scale rotary kiln. The product yields and distributions exhibited no discernable trends with reactor temperature or solids retention time. The liquid products obtained from the pilot-scale fluidized bed reactor were upgraded compared to the bitumen in terms of volatility, viscosity, molecular weight, and metals (Ni and V) content. The nitrogen and sulphur contents of the total liquid products were also reduced relative to the bitumen. A comparison of oil sands pyrolysis yields from a pilot scale FBR and a rotary kiln of the same diameter (15.2 cm) was made. Under similar pyrolysis conditions, the rotary kiln produced a slightly more upgraded product but at lower total liquid yields. Kinetic modeling of the various reactors indicates that the pilot-scale FBR product distributions may be explained using a simplified two-reaction scheme. It is proposed that secondary cracking is suppressed in the large diameter FBR due to elimination of slugging and the superior quality of fluidization in the reactor. More experimental studies with the rotary kiln and an economic evaluation will be required before concluding which reactor is preferred for the thermal recovery process.

  18. Steam reforming of fast pyrolysis-derived aqueous phase oxygenates over Co, Ni, and Rh metals supported on MgAl2O4

    DOE PAGES

    Xing, Rong; Dagle, Vanessa Lebarbier; Flake, Matthew; ...

    2016-02-03

    In this paper we examine the feasibility of steam reforming the mixed oxygenate aqueous fraction derived from fast pyrolysis bio-oils. Catalysts selective towards hydrogen formation and resistant to carbon formation utilizing feeds with relatively low steam-to-carbon (S/C) ratios are desired. Rh (5 wt%), Pt (5 wt%), Ru (5 wt%), Ir (5 wt%), Ni (15 wt%), and Co (15 wt%) metals supported on MgAl2O4 were evaluated for catalytic performance at 500 °C and 1 atm using a complex feed mixture comprising acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active and resistant to carbonmore » formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir).« less

  19. 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.

  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. 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.

  2. 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.

  3. Comparing biofuels obtained from pyrolysis, of soybean oil or soapstock, with traditional soybean biodiesel: Density, kinematic viscosity, and surface tensions

    USDA-ARS?s Scientific Manuscript database

    A product with diesel like properties was synthesized by a pyrolysis method, from either edible soybean oil, or an inedible soybean soapstock starting material (PD and SD, respectively). Some physical properties of the material were studied, neat, and in blends; with both high sulfur and low sulfur...

  4. Gas chromatographic-mass spectrometric study of the oil fractions produced by microwave-assisted pyrolysis of different sewage sludges.

    PubMed

    Domínguez, A; Menéndez, J A; Inguanzo, M; Bernad, P L; Pis, J J

    2003-09-19

    The pyrolysis of sewage sludge was studied in a microwave oven using graphite as microwave absorber. The pyrolysis temperature ranged from 800 to 1000 degrees C depending on the type of sewage sludge. A conventional electrical furnace was also employed in order to compare the results obtained with both methods. The pyrolysis oils were trapped in a series of condensers and their characteristics such as elemental analysis and calorific value were determined and compared with those of the initial sludge. The oil composition was analyzed by GC-MS. The oils from the microwave oven had n-alkanes and 1-alkenes, aromatic compounds, ranging from benzene derivatives to polycyclic aromatic hydrocarbons (PAHs), nitrogenated compounds, long chain aliphatic carboxylic acids, ketones and esters and also monoterpenes and steroids. The oil from the electric oven was composed basically of PAHs such as naphthalene, acenapthylene, phenanthrene, fluoranthene, benzo[a]anthracene, benzofluoranthenes, benzopyrenes, indenepyrene, benzo[ghi]perylene, and anthanthrene. In contrast, these compounds were not produced in the case of microwave-assisted pyrolysis.

  5. 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...

  6. 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.

  7. 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.

  8. Dual Layer Monolith ATR of Pyrolysis Oil for Distributed Synthesis Gas Production

    SciTech Connect

    Lawal, Adeniyi

    2012-09-29

    We have successfully demonstrated a novel reactor technology, based on BASF dual layer monolith catalyst, for miniaturizing the autothermal reforming of pyrolysis oil to syngas, the second and most critical of the three steps for thermochemically converting biomass waste to liquid transportation fuel. The technology was applied to aged as well as fresh samples of pyrolysis oil derived from five different biomass feedstocks, namely switch-grass, sawdust, hardwood/softwood, golden rod and maple. Optimization of process conditions in conjunction with innovative reactor system design enabled the minimization of carbon deposit and control of the H2/CO ratio of the product gas. A comprehensive techno-economic analysis of the integrated process using in part, experimental data from the project, indicates (1) net energy recovery of 49% accounting for all losses and external energy input, (2) weight of diesel oil produced as a percent of the biomass to be ~14%, and (3) for a demonstration size biomass to Fischer-Tropsch liquid plant of ~ 2000 daily barrels of diesel, the price of the diesel produced is ~$3.30 per gallon, ex. tax. However, the extension of catalyst life is critical to the realization of the projected economics. Catalyst deactivation was observed and the modes of deactivation, both reversible and irreversible were identified. An effective catalyst regeneration strategy was successfully demonstrated for reversible catalyst deactivation while a catalyst preservation strategy was proposed for preventing irreversible catalyst deactivation. Future work should therefore be focused on extending the catalyst life, and a successful demonstration of an extended (> 500 on-stream hours) catalyst life would affirm the commercial viability of the process.

  9. Microwave-assisted catalytic pyrolysis of switchgrass for improving bio-oil and biochar properties.

    PubMed

    Mohamed, Badr A; Kim, Chang Soo; Ellis, Naoko; Bi, Xiaotao

    2016-02-01

    Solid additives were used as a microwave absorber to improve the low microwave absorption rate of switchgrass going through pyrolysis, and as a catalyst to improve the bio-oil and biochar characteristics. The synergistic effects were manifested in the presence of a mixture of K3PO4 and clinoptilolite or bentonite compared with single catalyst, resulting in increased microwave absorption rate, and improved bio-oil and biochar quality. The sample of microwave heating switchgrass with 10wt.% K3PO4+10wt.% bentonite reached 400°C after 2.8min, compared with 28.8min through conventional heating, producing biochar with increase in BET surface area from 0.33m(2)/g to 76.3m(2)/g compared with conventional heating. Furthermore, water content of the bio-oil reduced from 22.7 to 15.0wt.% compared with biomass mixed with 20wt.% SiC, a chemically-inert microwave absorbing material used to increase microwave heating. Introducing catalysts showed a great potential for accelerating microwave heating and improving bio-oil and biochar qualities.

  10. Catalytic pyrolysis of oil fractions separated from food waste leachate over nanoporous acid catalysts.

    PubMed

    Kim, Seung-Soo; Heo, Hyeon Su; Kim, Sang Guk; Ryoo, Ryong; Kim, Jeongnam; Jeon, Jong-Ki; Park, Sung Hoon; Park, Young-Kwon

    2011-07-01

    Oil fractions, separated from food waste leachate, can be used as an energy source. Especially, high quality oil can be obtained by catalytic cracking. In this study, nanoporous catalysts such as Al-MCM-41 and mesoporous MFI type zeolite were applied to the catalytic cracking of oil fractions using the pyrolysis gas chromatography/mass spectrometry. Mesoporous MFI type zeolite showed better textural porosity than Al-MCM-41. In addition, mesoporous MFI type zeolite had strong Brönsted acidity while Al-MCM-41 had weak acidity. Significant amount of acid components in the food waste oil fractions were converted to mainly oxygenates and aromatics. As a result of its well-defined nanopores and strong acidity, the use of a mesoporous MFI type zeolite produced large amounts of gaseous and aromatic compounds. High yields of hydrocarbons within the gasoline range were also obtained in the case of mesoporous MFI type zeolite, whereas the use of Al-MCM-41, which exhibits relatively weak acidity, resulted in high yields of oxygenates and diesel range hydrocarbons.

  11. Application of nanostuctured materials as acid-catalysts in rice straw pyrolysis for bio-oil production

    NASA Astrophysics Data System (ADS)

    Dang, Phuong T.; Le, Hy G.; Dinh, Thang C.; Hoang, Thang V.; Bui, Linh H. T.; Hoang, Yen; Tran, Hoa K. T.; Vu, Tuan A.

    2008-12-01

    Rice straw, a waste agro-byproduct, which is abundant lignocellulose products from rice production, is a renewable energy sources in Vietnam. Bio-oil from rice straw is produced by thermal and catalytic pyrolysis using a fixed-bed reactor with heating rate 15oC/min, nitrogen as sweeping gas with flow rate 120ml/min. Final temperature of the pyrolysis reaction is a significantly influence on product yield. The gas yield increased and the solid yield decreased as the pyrolysis temperature increasing from 400oC to 600oC. The bio-oil yield reached a maximum of 48.3 % at the pyrolysis temperature of 550oC. Mesoporous Al-SBA-15 was used as acid catalyst in pyrolysis of rice straw. The obtained results showed that, in the presence of catalyst, yield of gas products increased, whereas liquid yield decreased and solid product remained the same as compared to the non-catalytic experiments. The effect of nanostructured catalysts on the product yields and distribution was investigated.

  12. Production of an alternative fuel by the co-pyrolysis of landfill recovered plastic wastes and used lubrication oils.

    PubMed

    Breyer, Sacha; Mekhitarian, Loucine; Rimez, Bart; Haut, B

    2017-02-01

    This work is a preliminary study for the development of a co-pyrolysis process of plastic wastes excavated from a landfill and used lubrication oils, with the aim to produce an alternative liquid fuel for industrial use. First, thermogravimetric experiments were carried out with pure plastics (HDPE, LDPE, PP and PS) and oils (a motor oil and a mixture of used lubrication oils) in order to highlight the interactions occurring between a plastic and an oil during their co-pyrolysis. It appears that the main decomposition event of each component takes place at higher temperatures when the components are mixed than when they are alone, possibly because the two components stabilize each other during their co-pyrolysis. These interactions depend on the nature of the plastic and the oil. In addition, co-pyrolysis experiments were led in a lab-scale reactor using a mixture of excavated plastic wastes and used lubrication oils. On the one hand, the influence of some key operating parameters on the outcome of the process was analyzed. It was possible to produce an alternative fuel for industrial use whose viscosity is lower than 1Pas at 90°C, from a plastic/oil mixture with an initial plastic mass fraction between 40% and 60%, by proceeding at a maximum temperature included in the range 350-400°C. On the other hand, the amount of energy required to successfully co-pyrolyze, in lab conditions, 1kg of plastic/oil mixture with an initial plastic mass fraction of 60% was estimated at about 8MJ. That amount of energy is largely used for the thermal cracking of the molecules. It is also shown that, per kg of mixture introduced in the lab reactor, 29MJ can be recovered from the combustion of the liquid resulting from the co-pyrolysis. Hence, this co-pyrolysis process could be economically viable, provided heat losses are addressed carefully when designing an industrial reactor. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Nannochloropsis algae pyrolysis with ceria-based catalysts for production of high-quality bio-oils.

    PubMed

    Aysu, Tevfik; Sanna, Aimaro

    2015-10-01

    Pyrolysis of Nannochloropsis was carried out in a fixed-bed reactor with newly prepared ceria based catalysts. The effects of pyrolysis parameters such as temperature and catalysts on product yields were investigated. The amount of bio-char, bio-oil and gas products, as well as the compositions of the resulting bio-oils was determined. The results showed that both temperature and catalyst had significant effects on conversion of Nannochloropsis into solid, liquid and gas products. The highest bio-oil yield (23.28 wt%) and deoxygenation effect was obtained in the presence of Ni-Ce/Al2O3 as catalyst at 500°C. Ni-Ce/Al2O3 was able to retain 59% of the alga starting energy in the bio-oil, compared to only 41% in absence of catalyst. Lower content of acids and oxygen in the bio-oil, higher aliphatics (62%), combined with HHV show promise for production of high-quality bio-oil from Nannochloropsis via Ni-Ce/Al2O3 catalytic pyrolysis.

  14. Liquid oil and residual characteristics of printed circuit board recycle by pyrolysis.

    PubMed

    Lin, Kuo-Hsiung; Chiang, Hung-Lung

    2014-04-30

    Non-metal fractions of waste printed circuit boards (PCBs) were thermally treated (200-500°C) under nitrogen atmosphere. Carbon, hydrogen, and nitrogen were determined by elemental analyzer, bromine by instrumental neutron activation analysis (INAA), phosphorus by energy dispersive X-ray spectrometer (EDX), and 29 trace elements by inductively coupled plasma atomic emission spectrometer (ICP-AES) and mass spectrometry (ICP-MS) for raw material and pyrolysis residues. Organic compositions of liquid oil were identified by GC (gas chromatography)-MS, trace element composition by ICP system, and 12 water-soluble ions by IC (ionic chromatography). Elemental content of carbon was >450 mg/g, oxygen 300 mg/g, bromine and hydrogen 60 mg/g, nitrogen 30 mg/g, and phosphorus 28 mg/g. Sulfur was trace in PCBs. Copper content was 25-28 mg/g, iron 1.3-1.7 mg/g, tin 0.8-1.0mg/g and magnesium 0.4-1.0mg/g; those were the main metals in the raw materials and pyrolytic residues. In the liquid products, carbon content was 68-73%, hydrogen was 10-14%, nitrogen was 4-5%, and sulfur was less than 0.05% at pyrolysis temperatures from 300 to 500°C. Phenol, 3-bromophenol, 2-methylphenol and 4-propan-2-ylphenol were major species in liquid products, accounting for >50% of analyzed organic species. Bromides, ammonium and phosphate were the main species in water sorption samples for PCB pyrolysis exhaust.

  15. 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

  16. 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

  17. Biochar potential evaluation of palm oil wastes through slow pyrolysis: Thermochemical characterization and pyrolytic kinetic studies.

    PubMed

    Lee, Xin Jiat; Lee, Lai Yee; Gan, Suyin; Thangalazhy-Gopakumar, Suchithra; Ng, Hoon Kiat

    2017-07-01

    This research investigated the potential of palm kernel shell (PKS), empty fruit bunch (EFB) and palm oil sludge (POS), abundantly available agricultural wastes, as feedstock for biochar production by slow pyrolysis (50mLmin(-1) N2 at 500°C). Various characterization tests were performed to establish the thermochemical properties of the feedstocks and obtained biochars. PKS and EFB had higher lignin, volatiles, carbon and HHV, and lower ash than POS. The thermochemical conversion had enhanced the biofuel quality of PKS-char and EFB-char exhibiting increased HHV (26.18-27.50MJkg(-1)) and fixed carbon (53.78-59.92%), and decreased moisture (1.03-2.26%). The kinetics of pyrolysis were evaluated by thermogravimetry at different heating rates (10-40°C). The activation energies determined by Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa models were similar, and comparable with literature data. The findings implied that PKS and EFB are very promising sources for biochars synthesis, and the obtained chars possessed significant biofuel potential. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Relationship between hydrous and ordinary pyrolysis

    SciTech Connect

    Burnham, A.K.

    1993-06-01

    Pyrolysis results are reviewed briefly with the intent of drawing comparisons between open, high pressure, and hydrous pyrolysis. Empirically, the degree of pyrolysis severity to form volatile products in open pyrolysis is similar to that required to form an expelled oil phase in hydrous pyrolysis. The yields of hydrocarbons from open pyrolysis are close to those from hydrous pyrolysis, but hydrous pyrolysis tends to assist the separation of hydrocarbons from polar materials. Pressure has a small but measurable affect on the generation kinetics.

  19. Performance of the heavy fraction of pyrolysis oil derived from waste printed circuit boards in modifying asphalt.

    PubMed

    Yang, Fan; Sun, Shuiyu; Zhong, Sheng; Li, Shenyong; Wang, Yi; Wu, Jiaqi

    2013-09-15

    The focus of this research was the development of efficient and affordable asphalt modifiers. Pyrolysis oil was produced as a byproduct from the pyrolysis of waste printed circuit boards (WPCBs). The high boiling point fraction was separated from the pyrolysis oil through distillation and is referred to as the heavy fraction of pyrolysis oil (HFPO). The HFPO was tested as an asphalt modifier. Three asphalt modifiers were tested: HFPO; styrene-butadiene rubber (SBR); and HFPO + SBR (1:1). The physical properties and road performance of the three modified asphalts were measured and evaluated. The results have shown that when the amount of modifier was less than 10%, the HFPO modified asphalt had the highest softening point of the three. The dynamic stability (DS) and water resistance of the asphalt mixture with the HFPO modified asphalt was 10,161 cycles/mm and 87.2%, respectively. The DS was much larger than for the HFPO + SBR and SBR modified asphalt mixtures. These results indicate that using HFPO as an asphalt modifier has significant benefits not only for road engineering but also for resource recycling. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Review of the Pyrolysis Platform for Producing Bio-oil and Biochar: Technology, Logistics, and Potential Impacts on Greenhouse Gas Emissions, Water Quality, Soil Quality, and Agricultural Productivity

    USDA-ARS?s Scientific Manuscript database

    Pyrolysis is a relatively simple, inexpensive, and robust thermochemical technology for transforming biomass into bio-oil, biochar, and syngas. The robust nature of the pyrolysis technology, which allows considerable flexibility in both the type and quality of the biomass feedstock, combined with a ...

  1. Thermogravimetric investigation of the co-combustion between the pyrolysis oil distillation residue and lignite.

    PubMed

    Li, Hao; Xia, Shuqian; Ma, Peisheng

    2016-10-01

    Co-combustion of lignite with distillation residue derived from rice straw pyrolysis oil was investigated by non-isothermal thermogravimetric analysis (TGA). The addition of distillation residue improved the reactivity and combustion efficiency of lignite, such as increasing the weight loss rate at peak temperature and decreasing the burnout temperature and the total burnout. With increasing distillation residue content in the blended fuels, the synergistic interactions between distillation residue and lignite firstly increased and then decreased during co-combustion stage. Results of XRF, FTIR, (13)C NMR and SEM analysis indicated that chemical structure, mineral components and morphology of samples have great influence on the synergistic interactions. The combustion mechanisms and kinetic parameters were calculated by the Coats Redfern model, suggesting that the lowest apparent activation energy (120.19kJ/mol) for the blended fuels was obtained by blending 60wt.% distillation residue during main co-combustion stage.

  2. 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

  3. 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.

  4. 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.

  5. Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds.

    PubMed

    Mu, Wei; Ben, Haoxi; Du, Xiaotang; Zhang, Xiaodan; Hu, Fan; Liu, Wei; Ragauskas, Arthur J; Deng, Yulin

    2014-12-01

    Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst.

  6. Thermal characteristics analysis of microwaves reactor for pyrolysis of used cooking oil

    NASA Astrophysics Data System (ADS)

    Anis, Samsudin; Shahadati, Laily; Sumbodo, Wirawan; Wahyudi

    2017-03-01

    The research is objected to develop microwave reactor for pyrolysis of used cooking oil. The effect of microwave power as well as addition of char as absorber towards its thermal characteristic were investigated. Domestic microwave was modified and used to test the thermal characteristic of used cooking oil in the terms of temperature evolution, heating rate, and thermal efficiency. The samples were examined under various microwave power of 347W, 399W, 572W and 642W for 25 minutes of irradiation time. The char loading was tested in the level of 0, 50, and 100 g. Microwave reactor consists of microwave unit with a maximum power of 642W, a ceramic reactor, and a condenser equipped with temperature measurement system was successfully developed. It was found that microwave power and addition of absorber significantly influenced the thermal characteristic of microwave reactor. Under investigated condition, the optimum result was obtained at microwave power of 642W and 100 g of char. The condition was able to provide temperature of 480°C, heating rate of 18.2°C/min and thermal efficiency of 53% that is suitable to pyrolyze used cooking oil.

  7. Pyrolysis of de-oiled seed cake of Jatropha Curcas and catalytic steam reforming of pyrolytic bio-oil to hydrogen.

    PubMed

    Renny, Andrew; Santhosh, Viswanathan; Somkuwar, Nitin; Gokak, D T; Sharma, Pankaj; Bhargava, Sanjay

    2016-11-01

    The aim of this work was to study the pyrolysis of de-oiled seed cake of Jatropha Curcas and catalytic steam reforming of pyrolytic bio-oil to hydrogen. As per literature, presence of heavy nitrogenous and oxygenated compounds leads to catalyst deactivation. Here, an attempt has been made to tune pyrolytic reactions to optimize the N and O content of the pyrolytic bio-oil. Bio-oil conversion and hydrogen yield decreased as reaction progressed, which attributes to temporary loss of catalytic activity by blockage of catalyst pores by carbon deposition. Further, retention of steam reforming activity after repetitive steam activation suggests long-term catalyst usage.

  8. 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.

  9. A technical and economic evaluation of the pyrolysis of sewage sludge for the production of bio-oil.

    PubMed

    Kim, Y; Parker, W

    2008-03-01

    Pyrolysis to produce bio-oil from sewage sludge is a promising way, to not only improve the economical value, but also to reduce pollutants associated with sludge. The aim of this study was to evaluate the production of oil from primary, waste activated and digested sludges. The pyrolysis was performed in a laboratory-scale horizontal batch reactor. The operating temperature ranged from 250 degrees C to 500 degrees C, while a gas phase residence time of 20 min was maintained with 50 ml/min of nitrogen gas as a purge flow. The maximum oil yield was achieved with primary sludge at 500 degrees C. Temperature and volatile solids were the most important factors affecting the yield of oil and char, however, sludge type also affected both results. Pre-treatment of sludge with either acids, a base or a catalyst (zeolite) did not improve the quantity of oil produced. The economic values of the oil produced from primary, TWAS, and digested sludges were estimated as 9.9, 5.6, and 6.9 cent/kg-ds when the value of oil is 32 cent/kg-oil.

  10. Pyrolysis bio-oils as additives for vegetable oil based lubricants

    USDA-ARS?s Scientific Manuscript database

    Softwood and hardwood lignins, along with hardwood as such, were pyrolyzed to afford bio-oil distillates in which phenols were major products. Extraction with alkali gave a range of lignin-related phenols having molecular weights (MWs) from 110 to 344. Because vegetable oil based lubricants have dra...

  11. Fast co-pyrolysis of waste newspaper with high-density polyethylene for high yields of alcohols and hydrocarbons.

    PubMed

    Chen, Weimin; Shi, Shukai; Chen, Minzhi; Zhou, Xiaoyan

    2017-09-01

    Waste newspaper (WP) was first co-pyrolyzed with high-density polyethylene (HDPE) using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) to enhance the yields of alcohols and hydrocarbons. The effects of WP: HDPE feed ratio (100:0, 75:25, 50:50, 25:75, 0:100) and temperature (500-800°C) on products distribution were investigated and the interaction mechanism during co-pyrolysis was also proposed. Maximum yields of alcohols and hydrocarbons reached 85.88% (feed ratio 50:50wt.%, 600°C). Hydrogen supplements and deoxidation by HDPE and subsequently fragments recombination result in the conversion of aldehydes and ketones into branched hydrocarbons. Radicals from WP degradation favor the secondary crack for HDPE products resulting in the formation of linear hydrocarbons with low carbon number. Hydrocarbons with activated radical site from HDPE degradation were interacted with hydroxyl from WP degradation promoting the formation of linear long chain alcohols. Moreover, co-pyrolysis significantly enhanced condensable oil qualities, which were close to commercial diesel No. 0. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    DOE PAGES

    Xiong, Qingang; Robichaud, David J.

    2017-03-23

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

  13. Pyrolysis Oil Stabilization: Hot-Gas Filtration; Cooperative Research and Development Final Report, CRADA Number CRD-09-333

    SciTech Connect

    Baldwin, R.

    2012-07-01

    The hypothesis that was tested in this task was that separation of char, with its associated mineral matter from pyrolysis vapors before condensation, will lead to improved oil quality and stability with respect to storage and transportation. The metric used to evaluate stability in this case was a 10-fold reduction in the rate of increase of viscosity as determined by ASTM D445 (the accelerated aging test). The primary unit operation that was investigated for this purpose was hot-gas filtration. A custom-built heated candle filter system was fabricated by the Pall Corporation and furnished to NREL for this test campaign. This system consisted of a candle filter element in a containment vessel surrounded by heating elements on the external surface of the vessel. The filter element and housing were interfaced to NREL?s existing 0.5 MTD pyrolysis Process Development Unit (PDU). For these tests the pyrolysis reactor of the PDU was operated in the entrained-flow mode. The HGF test stand was installed on a slipstream from the PDU so that both hot-gas filtered oil and bio-oil that was not hot-gas filtered could be collected for purposes of comparison. Two filter elements from Pall were tested: (1) porous stainless steel (PSS) sintered metal powder; (2) sintered ceramic powder. An extremely sophisticated bio-oil condensation and collection system was designed and fabricated at NREL and interfaced to the filter unit.

  14. Speciation and environmental risk assessment of heavy metal in bio-oil from liquefaction/pyrolysis of sewage sludge.

    PubMed

    Yuan, Xingzhong; Leng, Lijian; Huang, Huajun; Chen, Xiaohong; Wang, Hou; Xiao, Zhihua; Zhai, Yunbo; Chen, Hongmei; Zeng, Guangming

    2015-02-01

    Liquefaction bio-oil (LBO) produced with ethanol (or acetone) as the solvent and pyrolysis bio-oil (PBO) produced at 550°C (or 850°C) from sewage sludge (SS) were produced, and were characterized and evaluated in terms of their heavy metal (HM) composition. The total concentration, speciation and leaching characteristic of HMs (Cu, Cr, Pb, Zn, Cd, and Ni) in both LBO and PBO were investigated. The total concentration and exchangeable fraction of Zn and Ni in bio-oils were at surprisingly high levels. Quantitative risk assessment of HM in bio-oils was performed by the method of risk assessment code (RAC), potential ecological risk index (PERI) and geo-accumulation index (GAI). Ni in bio-oil produced by pyrolysis at 850°C (PBO850) and Zn in bio-oil by liquefaction at 360°C with ethanol as solvent (LBO-360E) were evaluated to possess very high risk to the environment according to RAC. Additionally, Cd in PBO850 and LBO-360E were evaluated by PERI to have very high risk and high risk, respectively, while Cd in all bio-oils was assessed moderately contaminated according to GAI.

  15. Production and characterization of bio-oil from the pyrolysis of waste frying oil.

    PubMed

    Kraiem, Takwa; Hassen, Aida Ben; Belayouni, Habib; Jeguirim, Mejdi

    2017-04-01

    In this present work, the disposal of waste frying oil was explored. The experiment tests were performed under nitrogen (N2) atmosphere at 5 °C/min heating rate from the ambient temperature to 500 °C. In these operating conditions, the obtained pyrolitic liquid fraction was 76 wt% formed by 63.87 wt% of crude bio-oil and 12.13 wt% of aqueous fraction. The chemical characterization using FTIR, GC, and GC/MS has revealed that the bio-oil is a complex chemical mixture of linear saturated, unsaturated, and cyclic hydrocarbons and oxygenated compounds such as carboxylic acids, ketones, aldehydes, and alcohols. Moreover, the produced bio-oil can be considered as promising fuel with high calorific value (∼39 MJ/kg). However, the higher acidity (∼125 mg KOH/g sample) and viscosity (9.53 cSt at 40 °C) limit currently its direct use in engines. Therefore, although several promising results, further investigations are requested to improve the bio-oil quality in order to find an environmentally friendly issue to waste frying oil.

  16. Synthesis of Carbon Nano Materials Originated from Waste Cooking Oil Using a Nebulized Spray Pyrolysis

    NASA Astrophysics Data System (ADS)

    Arie, A. A.; Hadisaputra, L.; Susanti, R. F.; Devianto, H.; Halim, M.; Enggar, R.; Lee, J. K.

    2017-07-01

    Synthesis of nanocarbon on snake fruit-peel’s activated carbon from waste cooking oil palm was conducted by a nebulized spray pyrolysis process (NSP) by varying the processing temperature from 650 to 750 °C. Ferrocene was used as a catalyst with constant concentration of 0.015 g/ml of carbon source. The structure of nanocarbon was studied by using scanning electron microscope (SEM),x-ray diffraction (XRD), surface area analyzer and Raman spectroscopy. SEM results showed that the structures of carbon products was in the the form of carbon nanopsheres (CNS). XRD and Raman analysis confirmed the CNS structure. The carbon producs were then tested as electrode’s materials for lithium ion capacitors (LIC) by cyclic voltammetry (CV) instruments. From the CV results the specific capacitance was estimated as 79.57 F / g at a scan rate of 0.1 mV / s and voltage range from 2.5 - 4 V. This study shows that the nano carbons synthesized from the waste cooking oil can be used as prospective electrode materials for LIC.

  17. Performance Test on Compression Ignition Engine by Blending Ethanol and Waste Plastic Pyrolysis Oil with Cetane Additive

    NASA Astrophysics Data System (ADS)

    Padmanabhan, S.; Ganesan, S.; Jeswin Arputhabalan, J.; Chithrala, Varun; Ganesh Bairavan, P.

    2017-05-01

    The demand for diesel fuel is higher than that of petrol throughout the world hence seeking alternative to mineral diesel is a natural choice. Alternative fuels should be easily available at lower cost, environment friendly and fulfill energy needs without modifying engine’s operational parameters. Waste to energy is the trend in the selection of alternate fuels. In this work, Waste Plastic Pyrolysis oil (WPPO), Ethanol, Diesel blend with Cetane additive has been attempted as an alternative fuel. A Twin cylinder, Direct Injection engine was used to assess the engine performance and emission characteristics of waste plastic pyrolysis oil with cetane additive. Experimental results of blended plastic fuel and diesel fuel were compared.

  18. Pyrolysis of Mesua ferrea and Pongamia glabra seed cover: characterization of bio-oil and its sub-fractions.

    PubMed

    Bordoloi, Neonjyoti; Narzari, Rumi; Chutia, Rahul Singh; Bhaskar, Thallada; Kataki, Rupam

    2015-02-01

    In the present study, pyrolysis of Mesua ferrea seed cover (MFSC) and Pongamia glabra seed cover (PGSC) was performed to investigate the characteristics of bio-oil and its sub fractions. In a fixed bed reactor, the effect of temperature (range of 350-650 °C) on product yield and quality of solid product were monitored. The maximum bio-oil yield of 28.5 wt.% and 29.6 wt.% for PGSC and MFSC respectively was obtained at 550 °C at heating rate of 40 °C/min. The chemical composition of bio-oil and its sub fractions were investigated using FTIR and (1)H NMR. GC-MS was performed for both PGSC and MFSC bio-oils and their corresponding n-hexane fractions. The results showed that bio-oil from the feedstocks and its sub-fractions might be a potential source of renewable fuel and value added chemicals.

  19. Molecular characterization and comparison of shale oils generated by different pyrolysis methods using FT-ICR mass spectrometry

    USGS Publications Warehouse

    Jin, J.M.; Kim, S.; Birdwell, J.E.

    2011-01-01

    Fourier transform ion cyclotron resonance mass spectrometry (FT ICR-MS) was applied in the analysis of shale oils generated using two different pyrolysis systems under laboratory conditions meant to simulate surface and in situ oil shale retorting. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules. Comparison of FT ICR-MS results to standard oil characterization methods (API gravity, SARA fractionation, gas chromatography-flame ionization detection) indicated correspondence between the average Double Bond Equivalence (DBE) and asphaltene content. The results show that, based on the average DBE values and DBE distributions of the shale oils examined, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions and in the presence of water.

  20. Bio-oil production via catalytic pyrolysis of Anchusa azurea: Effects of operating conditions on product yields and chromatographic characterization.

    PubMed

    Aysu, Tevfik; Durak, Halil; Güner, Serkan; Bengü, Aydın Şükrü; Esim, Nevzat

    2016-04-01

    Pyrolysis of Anchusa azurea, a lignocellulosic gramineous plant, was carried out in a tubular, fixed-bed reactor in the presence of four catalysts (Ca(OH)2, Na2CO3, ZnCl2, Al2O3). The influences of pyrolysis parameters such as catalyst and temperature on the yields of products were studied. It was found that higher temperature resulted in lower liquid (bio-oil) and solid (bio-char) yields and higher gas yields. Catalysts effected the yields of products differently and the composition of bio-oils. Liquid yields were increased in the presence of Na2CO3, ZnCl2 and Al2O3 and decreased with Ca(OH)2. The highest bio-oil yield (34.05%) by weight including aqueous phase was produced with Na2CO3 catalyst at 450°C. The yields of products (bio-char, bio-oil and gas) and the compositions of the resulting bio-oils were determined by GC-MS, FT-IR and elemental analysis. GC-MS identified 124 and 164 different compounds in the bio-oils obtained at 350 and 550°C respectively.

  1. Distribution behavior and risk assessment of metals in bio-oils produced by liquefaction/pyrolysis of sewage sludge.

    PubMed

    Leng, Lijian; Yuan, Xingzhong; Huang, Huajun; Peng, Xin; Chen, Hongmei; Wang, Hou; Wang, Lele; Chen, Xiaohong; Zeng, Guangming

    2015-12-01

    The distribution behaviors of metals in bio-oils derived from sewage sludge (SS) by liquefaction with different solvents (ethanol, methanol, or acetone) and by pyrolysis at different temperatures (550-850 °C) were investigated. The concentrations of crust metals (K, Na, Ca, Mg, Fe, and Al) in bio-oils were much higher than those of the anthropogenic metals (Cu, Zn, Pb, Cd, Cr, Ni, V, Mn, Ba, Co, Ti, Sn, As, and Hg), but the anthropogenic metals were more inclined to distribute in bio-oil phase compared with crust metals. The anthropogenic metals in bio-oils can be divided in three groups in terms of the distribution similarities according to Cluster analysis: (A) Cu, Co, Ni, V, and Sn; (B) Cr, Ti, Mn, and Ba; (C) Pb, Cd, As, Hg, and Zn. Cu, Cr, Hg, Cd, V, Co, and Sn distributed in the liquefaction/pyrolysis bio-oils accounted for as high as 5-20% of the metals in SS and were evaluated "moderate enrichment" by the enrichment factors method. According to the potential ecological risk index (PERI) method, Hg presented very high risk, Cu presented moderate risk, and Cd presented low to moderate risk; and the overall risk levels of these bio-oils were very high risk (except P550, presented considerable risk).

  2. Characteristics of products from fast pyrolysis of fractions of waste square timber and ordinary plywood using a fluidized bed reactor.

    PubMed

    Jung, Su-Hwa; Kim, Seon-Jin; Kim, Joo-Sik

    2012-06-01

    Fractions of waste square timber and waste ordinary plywood were pyrolyzed in a pyrolysis plant equipped with a fluidized bed reactor and a dual char separation system. The maximum bio-oil yield of about 65 wt.% was obtained at reaction temperatures of 450-500 °C for both feed materials. For quantitative analysis of bio-oil, the relative response factor (RRF) of each component was calculated using an effective carbon number (ECN) that was multiplied by the peak area of each component detected by a GC-FID. The predominant compounds in the bio-oils were methyl acetate, acids, hydroxyacetone, furfural, non-aromatic ketones, levoglucosan and phenolic compounds. The WOP-derived bio-oil showed it to have relatively high nitrogen content. Increasing the reaction temperature was shown to have little effect on nitrogen removal. The ash and solid contents of both bio-oils were below 0.1 wt.% due to the excellent performance of the char separation system. Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. 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.

  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. 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...

  6. Rheological properties and tunable thermoplasticity of phenolic rich fraction of pyrolysis bio-oil.

    PubMed

    Sahaf, Amir; Laborie, Marie-Pierre G; Englund, Karl; Garcia-Perez, Manuel; McDonald, Armando G

    2013-04-08

    In this work we report on the preparation, characterization, and properties of a thermally treated lignin-derived, phenolic-rich fraction (PRF) of wood pyrolysis bio-oil obtained by ethyl acetate extraction. The PRF was characterized for viscoelastic and rheological behavior using dynamic mechanical analysis (DMA) and cone and plate rheology. A unique thermoplastic behavior was evidenced. Heat-treated PRFs acquire high modulus but show low temperatures of thermal flow which can be systematically manipulated through the thermal pretreatment. Loss of volatiles, changes in molecular weight, and glass transition temperature (Tg) were investigated using thermogravimetric analysis (TGA), mass spectrometry (MS), and differential scanning calorimetry (DSC), respectively. Underlying mechanisms for the thermal and rheological behavior are discussed with regard to interactions between pyrolytic lignin nanoparticles present in the system and the role of volatile materials on determining the properties of the material resembling in several aspects to colloidal suspension systems. Low thermal flow temperatures and reversible thermal effects can be attributed to association of pyrolytic lignin particles due to intermolecular interactions that are easily ruptured at higher temperatures. The thermoplastic behavior of PRF and its low Tg is of particular interest, as it gives opportunities for application of this fraction in several melt processing and adhesive technologies.

  7. Characterization of pitch prepared from pyrolysis fuel oil via electron beam irradiation

    NASA Astrophysics Data System (ADS)

    Kim, Hong Gun; Park, Mira; Kim, Hak-Yong; Kwac, Lee Ku; Shin, Hye Kyoung

    2017-06-01

    Pitch samples were obtained from pyrolysis fuel oil by thermal treatment for 2 h at 300 °C after electron beam irradiation (EBI) treatment and by thermal treatment alone for different temperature of 250 °C, 300 °C, and 350 °C. EBI treatment was found to be an effective treatment for preparing pitch compare to the pitch obtained without EBI treatment. These results were confirmed by Fourier transform infrared spectroscopy (FT-IR) and Carbon-13 nuclear magnetic resonance (13C NMR) analyses, which showed the increase in the intensities of peaks corresponding to aromatic compounds. In the matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) spectra, the amount of components with medium molecular weights in the pitch was found to increase with the temperature; likewise, in the case of the pitch obtained via EBI treatment, we found that the amount of components with higher molecular weight over 1000 (m/v) similarly increased. Further, the thermal stability and carbon yield at 850 °C of the pitch obtained by EBI were greater than those of samples subjected to thermal treatment at 250 and 300 °C.

  8. Production of aromatic green gasoline additives via catalytic pyrolysis of acidulated peanut oil soap stock.

    PubMed

    Hilten, R; Speir, R; Kastner, J; Das, K C

    2011-09-01

    Catalytic pyrolysis was used to generate gasoline-compatible fuel from peanut oil soap stock (PSS), a high free fatty acid feedstock, using a fixed-bed reactor at temperatures between 450 and 550°C with a zeolite catalyst (HZSM-5). PSS fed at 81 gh(-1) along with 100 mL min(-1) inert gas was passed across a 15 g catalyst bed (WHSV=5.4h(-1), gas phase residence time=34s). Results indicate that fuel properties of PSS including viscosity, heating value, and O:C ratio were improved significantly. For PSS processed at 500°C, viscosity was reduced from 59.6 to 0.9 mm(2)s(-1), heating value was increased from 35.8 to 39.3 MJL(-1), and the O:C ratio was reduced from 0.07 to 0.02. Aromatic gasoline components (e.g., BTEX), were formed in concentrations as high as 94% (v/v) in catalytically-cracked PSS with yields ranging from 22% to 35% (v/v of PSS feed).

  9. Antibacterial Effects of Pyrolysis Oil Against Salmonella Typhimurium and Escherichia coli.

    PubMed

    Patra, Jayanta Kumar; Das, Gitishree; Choi, Joon Weon; Baek, Kwang-Hyun

    2016-01-01

    Many issues have been found to be related to food preservation and food contamination caused by various pathogenic bacteria in recent years. Many antibacterial agents act efficiently against Gram-positive foodborne bacteria; however, they are less effective against Gram-negative foodborne bacteria. In the present study, an attempt has been made to evaluate the antibacterial activity of pyrolysis oil manufactured from Pinus densiflora (PLO) against two Gram-negative foodborne pathogenic bacteria, Salmonella Typhimurium and Escherichia coli O157:H7. PLO possessed potent antibacterial activity against both foodborne pathogenic bacteria, as indicated by inhibition zones of 10.33-12.33 mm and minimum inhibitory concentration and minimum bactericidal concentration values of 250-500 μg/mL and 500-1000 μg/mL, respectively. PLO at the minimum inhibitory concentration exhibited an inhibitory effect on the viability of the bacterial pathogens with leakage of 260 nm absorbing materials, an increase in the relative electrical conductivity, and loss of salt tolerance capacity. PLO exhibited promising antibacterial activity against both of the Gram-negative foodborne pathogenic bacteria and thus it can be utilized in the food sector and pharmaceutical industries for the development of antibiotics and preservatives.

  10. 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...

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Diamondoid hydrocarbons as a molecular proxy for thermal maturity and oil cracking: Geochemical models from hydrous pyrolysis

    USGS Publications Warehouse

    Wei, Z.; Moldowan, J.M.; Zhang, S.; Hill, R.; Jarvie, D.M.; Wang, Hongfang; Song, F.; Fago, F.

    2007-01-01

    A series of isothermal hydrous pyrolysis experiments was performed on immature sedimentary rocks and peats of different lithology and organic source input to explore the generation of diamondoids during the thermal maturation of sediments. Oil generation curves indicate that peak oil yields occur between 340 and 360 ??C, followed by intense oil cracking in different samples. The biomarker maturity parameters appear to be insensitive to thermal maturation as most of the isomerization ratios of molecular biomarkers in the pyrolysates have reached their equilibrium values. Diamondoids are absent from immature peat extracts, but exist in immature sedimentary rocks in various amounts. This implies that they are not products of biosynthesis and that they may be generated during diagenesis, not just catagenesis and cracking. Most importantly, the concentrations of diamondoids are observed to increase with thermal stress, suggesting that they can be used as a molecular proxy for thermal maturity of source rocks and crude oils. Their abundance is most sensitive to thermal exposure above temperatures of 360-370 ??C (R0 = 1.3-1.5%) for the studied samples, which corresponds to the onset of intense cracking of other less stable components. Below these temperatures, diamondoids increase gradually due to competing processes of generation and dilution. Calibrations were developed between their concentrations and measured vitrinite reflectance through hydrous pyrolysis maturation of different types of rocks and peats. The geochemical models obtained from these methods may provide an alterative approach for determining thermal maturity of source rocks and crude oils, particularly in mature to highly mature Paleozoic carbonates. In addition, the extent of oil cracking was quantified using the concentrations of diamondoids in hydrous pyrolysates of rocks and peats, verifying that these hydrocarbons are valuable indicators of oil cracking in nature. ?? 2006 Elsevier Ltd. All rights

  1. 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.

  2. Enhancement of biofuels production by means of co-pyrolysis of Posidonia oceanica (L.) and frying oil wastes: Experimental study and process modeling.

    PubMed

    Zaafouri, Kaouther; Ben Hassen Trabelsi, Aida; Krichah, Samah; Ouerghi, Aymen; Aydi, Abdelkarim; Claumann, Carlos Alberto; André Wüst, Zibetti; Naoui, Silm; Bergaoui, Latifa; Hamdi, Moktar

    2016-05-01

    Energy recovery from lignocellulosic solid marine wastes, Posidonia oceanica wastes (POW) with slow pyrolysis responds to the growing trend of alternative energies as well as waste management. Physicochemical, thermogravimetric (TG/DTG) and spectroscopic (FTIR) characterizations of POW were performed. POW were first converted by pyrolysis at different temperatures (450°C, 500°C, 550°C and 600°C) using a fixed-bed reactor. The obtained products (bio-oil, syngas and bio char) were analyzed. Since the bio-oil yield obtained from POW pyrolysis is low (2wt.%), waste frying oil (WFO) was added as a co-substrate in order to improve of biofuels production. The co-pyrolysis gave a better yield of liquid organic fraction (37wt.%) as well as syngas (CH4,H2…) with a calorific value around 20MJ/kg. The stoichiometric models of both pyrolysis and co-pyrolysis reactions were performed according to the biomass formula: CαHβOγNδSε. The thermal kinetic decomposition of solids was validated through linearized Arrhenius model. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. 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.

  4. 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.

  5. 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.

  6. Formate-assisted pyrolysis

    DOEpatents

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

    2015-03-17

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

  7. Bio-oil and bio-char from low temperature pyrolysis of spent grains using activated alumina.

    PubMed

    Sanna, Aimaro; Li, Sujing; Linforth, Rob; Smart, Katherine A; Andrésen, John M

    2011-11-01

    The pyrolysis of wheat and barley spent grains resulting from bio-ethanol and beer production respectively was investigated at temperatures between 460 and 540 °C using an activated alumina bed. The results showed that the bio-oil yield and quality depend principally on the applied temperature where pyrolysis at 460 °C leaves a bio-oil with lower nitrogen content in comparison with the original spent grains and low oxygen content. The viscosity profile of the spent grains indicated that activated alumina could promote liquefaction and prevent charring of the structure between 400 and 460 °C. The biochar contains about 10-12% of original carbon and 13-20% of starting nitrogen resulting very attractive as a soil amendment and for carbon sequestration. Overall, value can be added to the spent grains opening a new market in bio-fuel production without the needs of external energy. The bio-oil from spent grains could meet about 9% of the renewable obligation in the UK.

  8. In-depth investigation on quantitative characterization of pyrolysis oil by 31P NMR

    SciTech Connect

    Ben, Haoxi; Ferrell, III, Jack R.

    2016-01-29

    The characterization of different heteroatom functional groups by employing 31P NMR has been developed for almost 30 years. In this study, an in-depth investigation of this commonly used method has been accomplished for the analysis of pyrolysis oil. Several commonly used internal standards for 31P NMR have been examined by in situ monitoring. The results indicated that endo-N-hydroxy-5-norbornene-2,3-dicarboximide (NHND) is not stable after a long period of storage or experiment (>12 hours), but both cyclohexanol and triphenylphosphine oxide (TPPO) can be used as internal standards if a long experiment or storage is required. The pyrolysis oil has also been investigated by both short time (16 hours) in situ monitoring and long time (14 days) ex situ monitoring. The results showed that aliphatic OH, carboxylic acids and water contents are not very stable after 2 hours, and thus a short time of preparation, storage, and experiment need to be considered to ensure a precise quantitative measurement. The decomposition products are still unclear, but some preliminary investigations for different acids, (e.g. formic acid) have been accomplished. The results indicated that the aromatic carboxylic acids (benzoic acid and vanillic acid) are more stable than formic acid and acetic acid. Interestingly, the formic acid will even decompose to some other compounds at the very beginning of the in situ monitoring test. Further characterization found that water is one of the major products for the decomposition of formic acid in the 31P NMR solution. Finally, as far as we know, this is the first report on such time-dependent changes when using 31P NMR to analyze the pyrolysis oil, and these results show that proper application of this method is essential to achieve reliable quantitative data.

  9. Detailed compositional characterization of plastic waste pyrolysis oil by comprehensive two-dimensional gas-chromatography coupled to multiple detectors.

    PubMed

    Toraman, Hilal E; Dijkmans, Thomas; Djokic, Marko R; Van Geem, Kevin M; Marin, Guy B

    2014-09-12

    The detailed compositional characterization of plastic waste pyrolysis oil was performed with comprehensive two-dimensional GC (GC×GC) coupled to four different detectors: a flame ionization detector (FID), a sulfur chemiluminescence detector (SCD), a nitrogen chemiluminescence detector (NCD) and a time of flight mass spectrometer (TOF-MS). The performances of different column combinations were assessed in normal i.e. apolar/mid-polar and reversed configurations for the GC×GC-NCD and GC×GC-SCD analyses. The information obtained from the four detectors and the use of internal standards, i.e. 3-chlorothiophene for the FID and the SCD and 2-chloropyridine for the NCD analysis, enabled the identification and quantification of the pyrolysis oil in terms of both group type and carbon number: hydrocarbon groups (n-paraffins, iso-paraffins, olefins and naphthenes, monoaromatics, naphthenoaromatics, diaromatics, naphthenodiaromatics, triaromatics, naphthenotriaromatics and tetra-aromatics), nitrogen (nitriles, pyridines, quinolines, indole, caprolactam, etc.), sulfur (thiols/sulfides, thiophenes/disulfides, benzothiophenes, dibenzothiophenes, etc.) and oxygen containing compounds (ketones, phenols, aldehydes, ethers, etc.). Quantification of trace impurities is illustrated for indole and caprolactam. The analyzed pyrolysis oil included a significant amount of nitrogen containing compounds (6.4wt%) and to a lesser extent sulfur containing compounds (0.6wt%). These nitrogen and sulfur containing compounds described approximately 80% of the total peak volume for respectively the NCD and SCD analysis. TOF-MS indicated the presence of the oxygen containing compounds. However only a part of the oxygen containing compounds (2.5wt%) was identified because of their low concentrations and possible overlap with the complex hydrocarbon matrix as no selective detector or preparative separation for oxygen compounds was used.

  10. 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.

  11. Influence of zinc chloride addition on the chemical structure of bio-oil obtained during co-pyrolysis of wood/synthetic polymer blends.

    PubMed

    Rutkowski, Piotr

    2009-12-01

    The chemical structure of liquid products of the pinewood sawdust (W) co-pyrolysis with polystyrene (PS) and polypropylene (PP) with and without the zinc chloride as an additive was investigated. The pyrolysis process was carried out at 450 degrees C with the heating rate of 5 degrees C/min. The yield of liquid products of pyrolysis was in the range of 37-91 wt% and their form was liquid or semi-solid depending on the composition of the wood/polymer blend. The zinc chloride addition to wood/polymer blends has influenced the range of samples decomposition as well as the chemical structure of resulted bio-oils. All bio-oils from wood/polypropylene blends were two-phase (liquid and solid). Contrarily, all bio-oils obtained from biopolymer/polypropylene blends with zinc chloride added were yellow liquids. All analyses proved that the structure and the quality of bio-oil strongly depend on both the composition of the blend and the presence of ZnCl(2) as an additive. The FT-IR analyses of oils showed that oxygen-containing groups and hydrocarbons content highly depend on the composition of biomass/synthetic polymer mixture. The fractionation of bio-oils by column chromatography with four different solvents was followed by GC-MS analysis. Results confirmed the significant removal and/or transformation of oxygen-containing organic compounds due to the zinc chloride presence during pyrolysis process.

  12. New insights on timing of oil and gas generation in the central Gulf Coast interior zone based on hydrous-pyrolysis kinetic parameters

    USGS Publications Warehouse

    Lewan, Michael D.; Dutton, Shirley P.; Ruppel, Stephen C.; Hentz, Tucker F.

    2002-01-01

    Timing of oil and gas generation from Turonian and Smackover source rocks in the central Gulf CoastInterior Zone was determined in one-dimensional burial-history curves (BHCs) using hydrous-pyrolysis kinetic parameters. The results predict that basal Smackover source-rock intervals with Type-IIS kerogen completed oil generation between 121 and 99 Ma, and Turonian source-rocks with Type-II kerogen remain immature over most of the same area. The only exception to the latter occurs in the northwestern part of the Mississippi salt basin, where initial stages of oil generation have started as a result of higher thermal gradients. This maturity difference between Turonian and Smackover source rocks is predicted with present-day thermal gradients. Predicted oil generation prior to the Sabine and Monroe uplifts suggests that a significant amount of the oil emplaced in Cretaceous reservoirs of these uplifts would have been lost during periods of erosion. Hydrous-pyrolysis kineticparameters predict that cracking of Smackover oil to gas started 52 Ma, which postdates major uplift and erosional events of the Sabine and Monroe uplifts. This generated gas would accumulate and persist in these uplift areas as currently observed. The predicted timing of oil and gas generation with hydrous-pyrolysis kinetic parameters is in accordance with the observed scarcity of oil from Turonian source rocks, predominance of gas accumulations on the Sabine and Monroe uplifts, and predominance of oil accumulations along the northern rim of the Interior Zone.

  13. Determination of Carbonyl Groups in Pyrolysis Bio-oils Using Potentiometric Titration: Review and Comparison of Methods

    DOE PAGES

    Black, Stuart; Ferrell, Jack R.

    2016-01-06

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here in this study, we present a modification of the traditional carbonyl oximation procedures that results inmore » less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. Some compounds such as carbohydrates are not measured by the traditional method (modified Nicolaides method), resulting in low estimations of the carbonyl content. Furthermore, we have shown that reaction completion for the traditional method can take up to 300 hours. The new method presented here (the modified Faix method) reduces the reaction time to 2 hours, uses triethanolamine (TEA) in the place of pyridine, and requires a smaller sample size for the analysis. Carbonyl contents determined using this new method are consistently higher than when using the traditional titration methods.« less

  14. Determination of Carbonyl Groups in Pyrolysis Bio-oils Using Potentiometric Titration: Review and Comparison of Methods

    SciTech Connect

    Black, Stuart; Ferrell, Jack R.

    2016-01-06

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here in this study, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. Some compounds such as carbohydrates are not measured by the traditional method (modified Nicolaides method), resulting in low estimations of the carbonyl content. Furthermore, we have shown that reaction completion for the traditional method can take up to 300 hours. The new method presented here (the modified Faix method) reduces the reaction time to 2 hours, uses triethanolamine (TEA) in the place of pyridine, and requires a smaller sample size for the analysis. Carbonyl contents determined using this new method are consistently higher than when using the traditional titration methods.

  15. [Fast discrimination of edible vegetable oil based on Raman spectroscopy].

    PubMed

    Zhou, Xiu-Jun; Dai, Lian-Kui; Li, Sheng

    2012-07-01

    A novel method to fast discriminate edible vegetable oils by Raman spectroscopy is presented. The training set is composed of different edible vegetable oils with known classes. Based on their original Raman spectra, baseline correction and normalization were applied to obtain standard spectra. Two characteristic peaks describing the unsaturated degree of vegetable oil were selected as feature vectors; then the centers of all classes were calculated. For an edible vegetable oil with unknown class, the same pretreatment and feature extraction methods were used. The Euclidian distances between the feature vector of the unknown sample and the center of each class were calculated, and the class of the unknown sample was finally determined by the minimum distance. For 43 edible vegetable oil samples from seven different classes, experimental results show that the clustering effect of each class was more obvious and the class distance was much larger with the new feature extraction method compared with PCA. The above classification model can be applied to discriminate unknown edible vegetable oils rapidly and accurately.

  16. Improvement of bio-oil yield and quality in co-pyrolysis of corncobs and high density polyethylene in a fixed bed reactor at low heating rate

    NASA Astrophysics Data System (ADS)

    Supramono, D.; Lusiani, S.

    2016-11-01

    Over the past few decades, interest in developing biomass-derived fuel has been increasing rapidly due to the decrease in fossil fuel reserves. Bio-oil produced by biomass pyrolysis however contains high oxygen compounds resulting in low calorific-value fuel and therefore requiring upgrading. In co-pyrolysis of the feed blend of plastics of High Density Polyethylene (HDPE) and biomass of com cob particles, at some compositions free radicals from plastic decomposition containing more hydrogen radicals are able to bond oxygen radicals originating from biomass to reduce oxygenate compounds in the bio-oil thus increasing bio-oil quality. This phenomenon is usually called synergetic effect. In addition to that, the pattern of heating of the feed blend in the pyrolysis reactor is predicted to affect biooil quality and yield. In a batch reactor, co-pyrolysis of corncobs and HDPE requires low heating rate to reach a peak temperature at temperature rise period followed by heating for some time at peak temperature called holding time at constant temperature period. No research has been carried out to investigate how long holding time is set in co-pyrolysis of plastic and biomass to obtain high yield of bio-oil. Holding time may affect either crosslinking of free radicals in gas phase, which increases char product, or secondary pyrolysis in the gas phase, which increases non-condensable gas in the gas phase of pyrolysis reactor, both of which reduce bio-oil yield. Therefore, holding time of co-pyrolysis affects the mass rate of bio-oil formation as the pyrolysis proceeds and quality of the bio-oil. In the present work, effects of holding time on the yield and quality of bio-oil have been investigated using horizontal fixed bed of the feed blends at heating rate of 5°C, peak temperature of 500°C and N2 flow rate of