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Sample records for fast-pyrolysis bio-oil ash

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

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

    2017-04-06

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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

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

    2012-05-01

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

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

    Science.gov (United States)

    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...

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

    Energy Technology Data Exchange (ETDEWEB)

    Huber, George W.; 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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Huber, George W.; 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

  11. FAST PYROLYSIS – EFFECT OF WOOD DRYING ON THE YIELD AND PROPERTIES OF BIO-OIL

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    Eriks Samulis

    2007-11-01

    Full Text Available The composition and properties of the products of fast pyrolysis of hardwood, obtained in a two-chamber (drying and pyrolytic ablation type reactor in the temperature range 450-600ºС, were investigated. It has been found that, upon the additional drying of wood at 200ºС and subsequent pyrolysis, the quality of bio-oil is improved owing to the decrease in the amount of water and acids. It has been shown that the increase of the drying temperature to 240ºС decreases the yield of the main product. Optimum parameters of the drying conditions and the temperature of the pyrolysis of wood, at which the bio-oil yield exceeds 60% and its calorific value makes up 17-20 МJ/kg, have been determined.

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

    Energy Technology Data Exchange (ETDEWEB)

    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. Bio-oil production from dry sewage sludge by fast pyrolysis in an electrically-heated fluidized bed reactor

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    Renato O. Arazo

    2017-01-01

    Full Text Available The optimization of bio-oil produced from sewage sludge using fast pyrolysis in a fluidized bed reactor was investigated. Effects of temperature, sludge particle size and vapor residence time on bio-oil properties, such as yield, high heating value (HHV and moisture content were evaluated through experimental and statistical analyses. Characterization of the pyrolysis products (bio-oil and biogas was also done. Optimum conditions produced a bio-oil product with an HHV that is nearly twice as much as lignocellulosic-derived bio-oil, and with properties comparable to heavy fuel oil. Contrary to generally acidic bio-oil, the sludge-derived bio-oil has almost neutral pH which could minimize the pipeline and engine corrosions. The Fourier Transform Infrared and gas-chromatography and mass spectrometry analyses of bio-oil showed a dominant presence of gasoline-like compounds. These results demonstrate that fast pyrolysis of sewage sludge from domestic wastewater treatment plant is a favorable technology to produce biofuels for various applications.

  14. Combining asphalt-rubber (AR) and fast-pyrolysis bio-oil to create a binder for flexible pavements

    OpenAIRE

    2013-01-01

    Best paper award of the conference The bio-oil from fast pyrolysis is mainly a product of the recycling of waste materials. This is a viscoelastic material, and after a heat treatment it has a viscosity similar to many types of asphalt used in the paving industry. Although bio-oil showed very good high temperature performance, the same was not verified at low temperatures. Therefore, GTR from cryogenic milling was used to modify the bio-oil. Then, a blend was produced by adding 20% (w/w) o...

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

    Science.gov (United States)

    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.

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

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    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.

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

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    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.

  18. Bio-Oil Production from Fast Pyrolysis of Corn Wastes and Eucalyptus Wood in a Fluidized Bed Reactor

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    M.A Ebrahimi-Nik

    2014-09-01

    Full Text Available Fast pyrolysis is an attractive technology for biomass conversion, from which bio-oil is the preferred product with a great potential for use in industry and transport. Corn wastes (cob and stover and eucalyptus wood are widely being produced throughout the world. In this study, fast pyrolysis of these two materials were examined under the temperature of 500 °C; career gas flow rate of 660 l h-1; particle size of 1-2 mm; 80 and 110 g h-1 of feed rate. The experiments were carried out in a continuous fluidized bed reactor. Pyrolysis vapor was condensed in 3 cooling traps (15, 0 and -40 °C plus an electrostatic one. Eucalyptus wood was pyrolyised to 12.4, 61.4, and 26.2 percent of bio-char, bio-oil and gas, respectively while these figures were as 20.15, 49.9, and 29.95 for corn wastes. In all experiments, the bio-oil obtained from electrostatic trap was a dark brown and highly viscose liquid.

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

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    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.

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

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    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.

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

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    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.

  2. Sulfur-Tolerant Molybdenum Carbide Catalysts Enabling Low-Temperature Stabilization of Fast Pyrolysis Bio-Oil

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    Li, Zhenglong; Choi, Jae Soon; Wang, Huamin; Lepore, Andrew W.; Connatser, Raynella M.; Lewis, Sam; Meyer, Harry; Santosa, Daniel M.; Zacher, Alan H.

    2017-08-18

    Low-temperature hydrogenation of carbonyl fractions can greatly improve the thermal stability of fast pyrolysis bio-oil which is crucial to achieve long-term operation of high-temperature upgrading reactors. The current state of the art, precious metals such as ruthenium, although highly effective in carbonyl hydrogenation, rapidly loses performance due to sulfur sensitivity. The present work showed that molybdenum carbides were active and sulfur-tolerant in low-temperature conversion carbonyl compounds. Furthermore, due to surface bifunctionality (presence of both metallic and acid sites), carbides catalyzed both C-O bond hydrogenation and C-C coupling reactions retaining most of carbon atoms in liquid products as more stable and higher molecular weight oligomeric compounds while consuming less hydrogen than ruthenium. The carbides proved to be resistant to other deactivation mechanisms including hydrothermal aging, oxidation, coking and leaching. These properties enabled carbides to achieve and maintain good catalytic performance in both aqueous-phase furfural conversion and real bio-oil stabilization with sulfur present. This finding strongly suggests that molybdenum carbides can provide a catalyst solution necessary for the development of commercially viable bio-oil stabilization technology.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  5. Production Cost Assessment of Palm Empty Fruit Bunch Conversion to Bio-Oil via Fast Pyrolysis

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    Yoga Peryoga

    2014-01-01

    Full Text Available Production cost assessment was based on palm oil mill of 30 metrics tons FFB/h capacity that produced EFB residue at app. 20 % wt of the initial FFB fed to the plant. The bio-oil plant will be located in the palm oil mill complex to eliminate the transportation cost of the EFB feedstock. The process included in this calculation is chopping, drying, grinding, pyrolysis, solid removal, bio oil recovery, and storage. The production cost is influenced by the amount of bio-oil production, material cost, operational cost including labor and utility cost. The sensitivity analysis shows that feedstock price drives the production cost. The result concludes that for the current condition, the bio-oil production cost from palm empty fruit bunch seems promising to be implemented in Indonesia. The best option is to have the bio-oil plant integrated with the palm oil mill, where in this case the EFB can be kept at no cost, off the market influence.

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

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    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.

  7. 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.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2012-12-01

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

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

    Science.gov (United States)

    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.

  10. Properties of Bio-oil from Fast Pyrolysis of Rice Husk%稻壳快速热裂解生物油的特性研究

    Institute of Scientific and Technical Information of China (English)

    郭秀娟; 王树荣; 王琦; 郭祚刚; 骆仲泱

    2011-01-01

    Physicochemical properties of bio-oil obtained from fast pyrolysis of rice husk were studied in the present work. Molecular distillation was used to separate the crude bio-oil into three fractions viz. light fraction, middle fraction and heavy fraction. Their chemical composition was analyzed by gas chromatograph and mass spectrometer (GC-MS). The thermal behavior, including evaporation and decomposition, was investigated using thermogravimetric analyzer coupled with Fourier transform infrared spectrometer (TG-FT1R). The product distribution was significantly affected by contents of cellulose, hemicellulose and lignin. The bio-oil yield was 46.36% (by mass) and the yield of gaseous products was 27% (by mass). The chemicals in the bio-oil included acids, aldehydes, ketones, alcohols, phenols, sugars, etc. The light fraction was mainly composed of acids and compounds with lower boiling point temperature, the middle and heavy fractions were consisted of phenols and levoglucosan. The thermal stability of the bio-oil was determined by the interactions and intersolubility of compounds. It was found that the thermal stability of bio-oil was better than the light fraction, but worse than the middle and heavy fractions.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  13. Hydrogen production via catalytic steam reforming of fast pyrolysis bio-oil in a two-stage fixed bed reactor system

    Energy Technology Data Exchange (ETDEWEB)

    Wu, C.; Huang, Q.; Sui, M.; Yan, Y.; Wang, F. [Research Center for Biomass Energy, State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai 200237 (China)

    2008-12-15

    Hydrogen production was prepared via catalytic steam reforming of fast pyrolysis bio-oil in a two-stage fixed bed reactor system. Low-cost catalyst dolomite was chosen for the primary steam reforming of bio-oil in consideration of the unavoidable deactivation caused by direct contact of metal catalyst and bio-oil itself. Nickel-based catalyst Ni/MgO was used in the second stage to increase the purity and the yield of desirable gas product further. Influential parameters such as temperature, steam to carbon ratio (S/C, S/CH{sub 4}), and material space velocity (W{sub B}HSV, GHSV) both for the first and the second reaction stages on gas product yield, carbon selectivity of gas product, CH{sub 4} conversion as well as purity of desirable gas product were investigated. High temperature (> 850 C) and high S/C (> 12) are necessary for efficient conversion of bio-oil to desirable gas product in the first steam reforming stage. Low W{sub B}HSV favors the increase of any gas product yield at any selected temperature and the overall conversion of bio-oil to gas product increases accordingly. Nickel-based catalyst Ni/MgO is effective in purification stage and 100% conversion of CH{sub 4} can be obtained under the conditions of S/CH{sub 4} no less than 2 and temperature no less than 800 C. Low GHSV favors the CH{sub 4} conversion and the maximum CH{sub 4} conversion 100%, desirable gas product purity 100%, and potential hydrogen yield 81.1% can be obtained at 800 C provided that GHSV is no more than 3600 h{sup -} {sup 1}. Carbon deposition behaviors in one-stage reactor prove that the steam reforming of crude bio-oil in a two-stage fixed bed reaction system is necessary and significant. (author)

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. Effect of operating parameters on production of bio-oil from fast pyrolysis of maize stalk in bubbling fluidized bed reactor

    Directory of Open Access Journals (Sweden)

    Ali Najaf

    2016-09-01

    Full Text Available The yield and composition of pyrolysis products depend on the characteristics of feed stock and process operating parameters. Effect of particle size, reaction temperature and carrier gas flow rate on the yield of bio-oil from fast pyrolysis of Pakistani maize stalk was investigated. Pyrolysis experiments were performed at temperature range of 360-540°C, feed particle size of 1-2 mm and carrier gas fl ow rate of 7.0-13.0 m3/h (0.61.1 m/s superficial velocity. Bio-oil yield increased with the increase of temperature followed by a decreasing trend. The maximum yield of bio-oil obtained was 42 wt% at a temperature of 490°C with the particle size of around 1.0 mm and carrier gas flow rate of 11.0 m3/h (0.9 m/s superficial velocity. High temperatures resulted in the higher ratios of char and non-condensable gas.

  17. Effect of biomass ash in catalytic fast pyrolysis of pine wood

    NARCIS (Netherlands)

    Yildiz, G.; Ronsse, F.; Venderbosch, R.H.; Duren, van R.; Kersten, S.R.A.; Prins, W.

    2015-01-01

    Fast pyrolysis experiments of pine wood have been performed in a continuously operated mechanically stirred bed reactor at 500 °C. The effects of the pine wood ash were studied by comparing non-catalytic and catalytic experiments (using a ZSM-5 based catalyst) with their ash-added counterparts. To s

  18. Influence of reaction conditions and the char separation system on the production of bio-oil from radiata pine sawdust by fast pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyun Ju; Park, Young-Kwon; Kim, Joo Sik [Faculty of Environmental Engineering, University of Seoul, 90 Jeonnong-Dong, Dondaemun-Gu, Seoul 130-743 (Korea)

    2008-08-15

    Radiata pine sawdust was pyrolyzed in a bubbling fluidized bed equipped with a char separation system. The influence of the reaction conditions on the production of bio-oil was investigated through the establishment of mass balance, and the examination of the products' chemical and physical characteristics. The optimal reaction temperature for the production of bio-oil was between 673 and 723 K, and the yield was above 50 wt.% of the product. An optimal feed size also existed. In a particle with a size that was less than 0.3 mm, the bio-oil yield decreased due to overheating, which led to gas formation. A higher flow rate and feeding rate were found to be more effective for the production of bio-oil, but did not significantly affect it. The main compounds of bio-oil were phenolics, including cresol, guaiacol, eugenol, benzendiol and their derivatives, ketones, and aldehydes. In addition, high-quality bio-oils, which contained less than 0.005 wt.% of solid, no ash and low concentrations of alkali and alkaline earth metals, were produced due to the char removal system. (author)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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%.

  1. A Comparison of Lignin, Macroalgae, Wood and Straw Fast Pyrolysis

    DEFF Research Database (Denmark)

    Trinh, Ngoc Trung; Jensen, Peter Arendt; Dam-Johansen, Kim

    2013-01-01

    with respect to carbon and oxygen contents, HHV, thermal behaviors and mean molecular weight. The HHV of wood, straw, lignin and algae oils were 24.0, 23.7, 29.7 and 25.7 MJ/kg db, respectively. The distributions of metals, Cl and S in char and bio-oil were investigated for the biomasses. Almost all the metals......A fast pyrolysis study on lignin and macroalgae (non-conventional biomass) and wood and straw (conventional biomass) were carried out in a pyrolysis centrifugal reactor at pyrolysis temperature of 550 ºC. The product distributions and energy recoveries were measured and compared among...... these biomasses. The fast pyrolysis of macroalgae showed a promising result with a bio-oil yield of 65 wt% dry ash free basis (daf) and 76 % energy recovery in the bio-oil while the lignin fast pyrolysis provides a bio-oil yield of 47 wt% daf and energy recovery in bio-oil of 45 %. The physiochemical properties...

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

    Science.gov (United States)

    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.

  3. Upgrading of bio-oil from the pyrolysis of biomass over the rice husk ash catalysts

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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

    Energy Technology Data Exchange (ETDEWEB)

    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. 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"

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Catalytic fast pyrolysis of lignocellulosic biomass

    Energy Technology Data Exchange (ETDEWEB)

    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.

  9. Avaliação de biocombustível derivado do bio-óleo obtido por pirólise rápida de biomassa lignocelulósica como aditivo para gasolina Evaluation of biofuel derived from lignocellulosic biomass fast pyrolysis bio-oil for use as gasoline addictive

    Directory of Open Access Journals (Sweden)

    Carmen Luisa Barbosa Guedes

    2010-01-01

    Full Text Available A biofuel was prepared from acid aqueous fraction (pH = 2 of bio-oil produced by fast pyrolysis (Bioware Technology of lignocellulosic biomass (sugar cane residue and tested in blends (2, 5, 10 e 20% v/v with gasoline type C (common marketed in Brazil. The specification tests made in the Refinery President Getúlio Vargas (PETROBRAS showed increasing in the octane number (MON and antiknock index (AKI with reduction in the residue generation during the combustion. The physicochemical characteristics of the biofuel were similar that combustible alcohol allowing its use as gasoline additive.

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

    Science.gov (United States)

    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.

  11. 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

    Energy Technology Data Exchange (ETDEWEB)

    Bhatt, Arpit [National Renewable Energy Lab. (NREL), Golden, CO (United States). Strategic Energy Analysis Center. Technology Systems and Sustainability Analysis Group; Zhang, Yimin [National Renewable Energy Lab. (NREL), Golden, CO (United States). Strategic Energy Analysis Center. Technology Systems and Sustainability Analysis Group; Heath, Garvin [National Renewable Energy Lab. (NREL), Golden, CO (United States). Strategic Energy Analysis Center. Technology Systems and Sustainability Analysis Group; Thomas, Mae [Eastern Research Group, Research Triangle Park, NC (United States); Renzaglia, Jason [Eastern Research Group, Research Triangle Park, NC (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    Trevor James Morgan

    Full Text Available 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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

    Directory of Open Access Journals (Sweden)

    Trevor James Morgan

    Full Text Available 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

  18. Biofuel from fast pyrolysis and catalytic hydrodeoxygenation.

    Energy Technology Data Exchange (ETDEWEB)

    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.

  19. Physiochemical properties of bio-oil produced at various temperatures from pine wood using an auger reactor.

    Science.gov (United States)

    Thangalazhy-Gopakumar, Suchithra; Adhikari, Sushil; Ravindran, Harideepan; Gupta, Ram B; Fasina, Oladiran; Tu, Maobing; Fernando, Sandun D

    2010-11-01

    A fast pyrolysis process produces a high yield of liquid (a.k.a. bio-oil) and has gained a lot of interest among various stakeholders. Nonetheless, some of the properties inherent by the bio-oil create significant challenges for its wider applications. Quality of the bio-oil and its yield are highly dependent on process parameters, such as temperature, feedstock, moisture content and residence time. In this study, the effect of temperature on bio-oil quality and its yield were examined using pine wood, an abundant biomass source in the southeastern part of the United States. Physical properties of bio-oil such as pH, water content, higher heating value, solid content and ash were analyzed and compared with a recently published ASTM standard. Bio-oil produced from pine wood using an auger reactor met specifications suggested by the ASTM standard. Thirty-two chemical compounds were analyzed. The study found that the concentration of phenol and its derivatives increased with the increase in pyrolysis temperature whereas the concentration of guaiacol and its derivatives decreased as the temperature increased. Concentration of acetic and other acids remained almost constant or increased with the increase in temperature although the pH value of the bio-oil decreased with the increase in temperature.

  20. Fast Pyrolysis of Biomass in a Spout-fluidized Bed Reactor--Analysis of Composition and Combustion Characteristics of Liquid Product from Biomass

    Institute of Scientific and Technical Information of China (English)

    陈明强; 王君; 王新运; 张学才; 张素平; 任铮伟; 颜涌捷

    2006-01-01

    In order to gain insight into the fast pyrolysis mechanism of biomass and the relationship between bio-oil composition and pyrolysis reaction conditions, to assess the possibility for the raw bio-oil to be used as fuel, and to evaluate the concept of spout-fluidized bed reactor as the reactor for fast pyrolysis of biomass to prepare fuel oil, the composition and combustion characteristics of bio-oil prepared in a spout-fluidized bed reactor with a designed maximum capacity 5 kg/h of sawdust as feeding material, were investigated by GC-MS and thermogravimetry. 14 aromatic series chemicals were identified. The thermogravimetric analysis indicated that the bio-oil was liable to combustion, the combustion temperature increased with the heating rate, and only minute ash was generated when it burned. The kinetics of the combustion reaction was studied and the kinetic parameters were calculated by both Ozawa-Flynn-Wall and Popsecu methods. The results agree well with each other. The most probable combustion mechanism functions determined by Popescu method are f(α)=k(1-α)2(400~406 ℃), f(α)=1/2k(1-α)3 (406~416 ℃) and f( α)=2k(1-α)3/2 (416~430 ℃) respectively.

  1. Fast pyrolysis of lignin, macroalgae and sewage sludge

    DEFF Research Database (Denmark)

    Trinh, Ngoc Trung

    In the last twenty years, the fast pyrolysis process has been explored to produce bio-oil from biomass. Fast pyrolysis is a thermal conversion technology that is performed at a temperatures of 450 - 600 ºC, high biomass heating ratess (100 - 2000 K/s), a short gas residence time (less than 2 s......) with no presence of oxygen. Fast pyrolysis can convert a large fraction of the biomass to bio-oil, and smaller fractions of char and gas. The pyrolysis centrifuge reactor (PCR) has been developed at the CHEC center at DTU Department of Chemical Engineering. The reactor is a compact design that uses a low flow rate...... constructed as a mobile unit of a tractor-propelled vehicle that is used on straw fields. A lot of work on PCR straw and wood pyrolysis with respect to pyrolysis conditions, moisture feedstock content, bio-oil properties, and PCR modelling is done before this PhD project. The bio-oil yields of approximately...

  2. 农作物秸秆快速热解生物油主要成分分析%Analysis of Main Components in Fast Pyrolysis Bio-oil from Crop Straws

    Institute of Scientific and Technical Information of China (English)

    胡文静; 郑冰漪; 何亮; 李瑞

    2012-01-01

    The platform of self-developed vacuum fast pyrolysis system was used for fast pryrolysis reaction of corn straw, rice straws and cotton straws. GC-MS was used to analyze the products of three different kinds of feedstock. The results show that the content of phenol in cotton stalk, corn straw and straw stem are 24.34 %, 21.21% and 17.22 %, and the content of acid are 14.78 % , 13.95 % and 16.69 % , respectively. The hio-oils from different kinds of straw have certain differences in compounds and contents, but main components are base on phenols, aldehydes, ketones and organic acids etc. The content is similar, and especially the differences between corn straw and cotton stalk are the smallest. Therefore, the different types of materials which have similar components can be mixed in practical product.%采用自行研发的真空快速热解反应平台对棉秆、玉米秸秆和稻草秆进行了快速热解,并用气质联用(GC-MS)分析法分别对3种秸秆快速热解液相产物的化学组分进行了测定。实验结果表明:棉秆、玉米秸秆和稻草秆3种热解油中酚类GC含量分别为24.34%、21.21%和17.22%,酸类GC含量分别为14.78%、13.95%和16.69%;不同种类秸秆其热解液化产物在组分及含量上存在一定差别,但其成分均以苯酚类、醛类、酮类、有机酸类等化合物为主,且含量差异不大,其中玉米秸秆和棉秆各类化合物含量差异相对较小,因此,生产中可以将成分类似却不同种类的原料混合热解。

  3. 精制生物油和柴油混合燃料的柴油机性能%Performance of diesel engine running on diesel fuel and its blends with refined biomass fast pyrolysis bio-oil

    Institute of Scientific and Technical Information of China (English)

    麻剑; 谢阳; 罗麒元; 许沧粟

    2015-01-01

    Experimental tests were conducted to evaluate the engine performance and emission of a diesel engine with diesel fuel and simulated bio‐oil blends . The simulated bio‐oil was prepared based on the refined biomass fast pyrolysis bio‐oil with pure substances (analytically grade ) , and the fuel blends containing 10% and 20% by volume of simulated bio‐oil were named as B10 and B20 .Results indicate that the engine power for the B10 and B20 are about 3% and 7% lower than for the pure diesel fuel .The average drop of brake specific energy consumption for the B10 and B20 is about 7% at full‐load . The measured products of the imperfect combustion of fuel ,such as CO and HC ,were reduced notably for the B10 and B20 compared with the diesel fuel at medium and high loads ,which the NMHC emission decrease was about 75% at full‐load . Under full load conditions , the smoke emission characteristics of B10 and B20 were different with diesel fuel ,and the average reduction of smoke opacity was about 10% for B20 relative to B10 .%在柴油机上通过试验研究精制生物质热裂解油和柴油混合燃料的动力性、经济性和排放性等性能,其中试验用精制生物质热裂解油是根据其主要成分的比例由分析纯的单质配制的模型油。结果表明,在不改变柴油机参数的情况下,模型油代用部分柴油导致发动机外特性输出功率略有下降,模型油体积掺混比10%与20%的混合燃料(分别简称为B10和B20)降幅分别约为3%与7%;经济性略有改善,B10和B20的当量油耗率在外特性工况中相对纯柴油的平均降幅约为7%;在中高负荷工况中,混合燃料的不完全燃烧产物如CO、HC等排放下降明显,其中外特性下NM HC排放只有纯柴油的25%左右;外特性下B20的排气不透光度相对B10下降约10%。

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

    Science.gov (United States)

    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...

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

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Robert C. [Iowa State Univ., Ames, IA (United States). Biorenewables Research Lab.. Center for Sustainable Environmental Technologies. Bioeconomy Inst.; Jones, Samuel T. [Iowa State Univ., Ames, IA (United States). Biorenewables Research Lab.. Center for Sustainable Environmental Technologies. Bioeconomy Inst.

    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

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

    Science.gov (United States)

    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...

  7. Fast pyrolysis of oil palm shell (OPS)

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  9. 热过滤对流化床快速热解制取生物油产率和品质的影响%Effects of Hot Filtration on Yield and Quality of Bio-oil from Fast Pyrolysis of Chinese Fir in Fluidized Bed Reactor

    Institute of Scientific and Technical Information of China (English)

    朱沈嘉; 刘运权; 王夺; 叶跃元; 李水荣

    2015-01-01

    A hot filter was added to a 1 kg/h bench-scale continuous bubbling fluidized bed system for the fast pyrolysis of Chinese fir to get bio-oils. The effects of hot filter on the yield and stability of bio-oils were studied. The results indicated that both the yields of pyrolysis oil ( without hot filtration ) and filtered oil ( after hot filtration ) increased with the increase of pyrolysis temperature,and decreased after 475 ℃,at which the maximum yields were 58. 1% and 50. 7%,respectively. The addition of hot filter resulted in lower oil yield ( approximate 5% -10% decrease) ,which became worse when pyrolysis temperature increased. Compared to the pyrolysis-oilⅠ,the water content of filtered-oilⅠincreased from 13. 77% to 15. 83%,pH value increased from 2. 18 to 2. 23,and high-heating value decreased from 20. 47 MJ/kg to 19. 53 MJ/kg. However,it also showed significant reduction in solids contents,alkali and alkaline earth metals,and the overall decline was about 75%,which suppressed the happening of self-polymerization in bio-oils. During the aging tests,water content and kinematic viscosity of filtered-oilⅠincreased by 10. 2%and 57. 6%,but the fluctuation was less than that of pyrolysis-oilⅠ. GC/MS analysis of the bio-oils showed that less fluctuation in composition was observed in the filtered-oil Ⅰ. This indicated a positive impact of the hot filter on the quality of bio-oil.%在1 kg/h的小型鼓泡流化床热解反应装置中增设一热过滤装置,对杉木快速热解制取生物油进行了研究,考察了热过滤装置对生物油产率和品质的影响。结果表明:热解油(未经热过滤)和过滤油(经过热过滤)的产率随热解温度的升高先上升后下降,并都在475℃时达到最大值,分别为58.1%和50.7%。热过滤装置的引入降低了生物油的产率(下降5%~10%),且热解温度越高,过滤油产率下降越明显。相比于热解油Ⅰ,过滤油Ⅰ的含水率从13.77%增加到15.83%,pH值从2.18

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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...

  12. Catalytic fast pyrolysis of pine wood: Effect of successive catalyst regeneration

    NARCIS (Netherlands)

    Yildiz, Guray; Lathouwers, Tom; Toraman, Hilal Ezgi; Geem, van Kevin M.; Marin, Guy B.; Ronsse, Frederik; Duren, van Ruben; Kersten, Sascha R.A.; Prins, Wolter

    2014-01-01

    The main product of biomass fast pyrolysis is a liquid mixture of numerous organic molecules with water that is usually called pyrolysis oil or bio-oil. The research discussed in this paper was meant (1) to validate a new, semicontinuously operated pyrolysis setup and (2) to investigate the effect o

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

    Science.gov (United States)

    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. Fast pyrolysis of eucalyptus waste in a conical spouted bed reactor.

    Science.gov (United States)

    Amutio, Maider; Lopez, Gartzen; Alvarez, Jon; Olazar, Martin; Bilbao, Javier

    2015-10-01

    The fast pyrolysis of a forestry sector waste composed of Eucalyptus globulus wood, bark and leaves has been studied in a continuous bench-scale conical spouted bed reactor plant at 500°C. A high bio-oil yield of 75.4 wt.% has been obtained, which is explained by the suitable features of this reactor for biomass fast pyrolysis. Gas and bio-oil compositions have been determined by chromatographic techniques, and the char has also been characterized. The bio-oil has a water content of 35 wt.%, and phenols and ketones are the main organic compounds, with a concentration of 26 and 10 wt.%, respectively. In addition, a kinetic study has been carried out in thermobalance using a model of three independent and parallel reactions that allows quantifying this forestry waste's content of hemicellulose, cellulose and lignin.

  15. Distillation and isolation of commodity chemicals from Bio-oil made by tail-gas reactive prolysis

    Science.gov (United States)

    Owing to instabilities, very little has been accomplished with regards to simple cost-effective separations of fast-pyrolysis bio-oil. However, recent developments in the use of tail-gas reactive pyrolysis (TGRP) (Mullen and Boateng 2013) provide higher quality bio-oils that are thermally stable. We...

  16. Utilization of acetic acid-rich pyrolytic bio-oil by microalga Chlamydomonas reinhardtii: reducing bio-oil toxicity and enhancing algal toxicity tolerance.

    Science.gov (United States)

    Liang, Yi; Zhao, Xuefei; Chi, Zhanyou; Rover, Marjorie; Johnston, Patrick; Brown, Robert; Jarboe, Laura; Wen, Zhiyou

    2013-04-01

    This work was to utilize acetic acid contained in bio-oil for growth and lipid production of the microalga Chlamydomonas reinhardtii. The acetic acid-rich bio-oil fraction derived from fast pyrolysis of softwood contained 26% (w/w) acetic acid, formic acid, methanol, furfural, acetol, and phenolics as identified compounds, and 13% (w/w) unidentified compounds. Among those identified compounds, phenolics were most inhibitory to algal growth, followed by furfural and acetol. To enhance the fermentability of the bio-oil fraction, activated carbon was used to reduce the toxicity of the bio-oil, while metabolic evolution was used to enhance the toxicity tolerance of the microalgae. Combining activated carbon treatment and using evolved algal strain resulted in significant algal growth improvement. The results collectively showed that fast pyrolysis-fermentation process was a viable approach for converting biomass into fuels and chemicals. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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.

  18. Bio-Oil Separation and Stabilization by Near-Critical Propane Fractionation

    Energy Technology Data Exchange (ETDEWEB)

    Ginosar, Daniel M.; Petkovic, Lucia M.; Agblevor, Foster A.

    2016-08-01

    Bio-oils produced by thermal process are promising sources of sustainable, low greenhouse gas alternative fuels. These thermal processes are also well suited to decentralized energy production due to low capital and operating costs. Algae feedstocks for bio-oil production are of particular interest, due in part to their high-energy growth yields. Further, algae can be grown in non-arable areas in fresh, brackish, salt water, or even waste water. Unfortunately, bio-oils produced by thermal processes present significant stability challenges. These oils have complex chemical compositions, are viscous, reactive, and thermally unstable. Further, the components within the oils are difficult to separate by fractional distillation. By far, the most effective separation and stabilization method has been solvent extraction. However, liquid phase extraction processes pose two main obstacles to commercialization; they require a significant amount of energy to remove and recover the solvent from the product, and they have a propensity for the solvent to become contaminated with minerals from the char and ash present in the original bio-oil. Separation and fractionation of thermally produced bio-oils using supercritical fluids (SCF) offers the advantages of liquid solvent extraction while drastically reducing energy demands and the predisposition to carry over solids into the extracted phase. SCFs are dense fluids with liquid-like solvent properties and gas-like transport properties. Further, SCF density and solvent strength can be tuned with minor adjustments in pressure, co-solvent addition, or gas anti-solvent addition. Catalytic pyrolysis oils were produced from Scenedesmus dimorphus algae using a fluid catalytic cracking catalyst. Bio-oil produced from catalytic fast pyrolysis (CFP) was separated using critical fluids. Propane extraction was performed at 65 °C at a fluid reduced pressure of 2.0 (85 bar) using an eight to one solvent to feed ratio by weight. Extraction of

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

    OpenAIRE

    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 work...

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, S. B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Valkenburg, C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Walton, C. W. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Elliott, D. C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Holladay, J. E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stevens, D. J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kinchin, C. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Czernik, S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, S. B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Valkenburg, C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Walton, C. W. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Elliott, D. C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Holladay, J. E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stevens, D. J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kinchin, C. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Czernik, S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    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.

  2. An Optimization Model for Advanced Biofuel Production Based on Bio-oil Gasification

    OpenAIRE

    Li, Qi; Hu, Guiping

    2013-01-01

    Part 2: Sustainable Supply Chains; International audience; Biomass can be converted to transportation fuels through gasification. However, commercialization of biomass gasification has been hampered by its high capital and operating costs, in addition to the difficulties of transporting bulky solid biomass over a long distance. A novel approach is to convert biomass to bio-oil at widely distributed small-scale fast pyrolysis plants, transport the bio-oil to a centralized location, gasify the ...

  3. Stepwise Isothermal Fast Pyrolysis (SIFP of Biomass. Part III. SIFP of Olive Oil Industry Wastes

    Directory of Open Access Journals (Sweden)

    Nadia S. Luna

    2013-11-01

    Full Text Available Pyrolysis of olive oil industry wastes was carried out using stepwise isothermal fast pyrolysis (SIFP. SIFP consists of a succession of isothermal fast pyrolysis reactions in which the solid products obtained from the previous isothermal fast pyrolysis reaction become the substrates for subsequent reactions at higher temperatures. This article reports the results obtained from the SIFP of olive oil residue carried out between the temperatures of 300 and 500 °C using 100 °C intervals under reduced pressure (200 mm Hg. The maximum yield of liquid products occurred at 300 °C and consisted of around 35% bio-oil, which contained mainly phenols, furans, and fatty acid methyl esters (FAME. At 400 and 500 °C, FAME, which is derived from residual olive oil, was the major product.

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

    Science.gov (United States)

    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.

  5. Catalytic Fast Pyrolysis: A Review

    Directory of Open Access Journals (Sweden)

    Theodore Dickerson

    2013-01-01

    Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

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

    Science.gov (United States)

    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...

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

    Science.gov (United States)

    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.

  8. Large-scale biohydrogen production from bio-oil.

    Science.gov (United States)

    Sarkar, Susanjib; Kumar, Amit

    2010-10-01

    Large amount of hydrogen is consumed during the upgrading of bitumen into synthetic crude oil (SCO), and this hydrogen is exclusively produced from natural gas in Western Canada. Because of large amount of emission from natural gas, alternative sources for hydrogen fuel especially renewable feedstocks could significantly reduce CO(2) emissions. In this study, biomass is converted to bio-oil by fast pyrolysis. This bio-oil is steam reformed near bitumen upgrading plant for producing hydrogen fuel. A techno-economic model is developed to estimate the cost of hydrogen from biomass through the pathway of fast pyrolysis. Three different feedstocks including whole-tree biomass, forest residues (i.e. limbs, branches, and tops of tree produced during logging operations), and straw (mostly from wheat and barley crops) are considered for biohydrogen production. Delivered cost of biohydrogen from whole-tree-based biomass ($2.40/kg of H(2)) is lower than that of forest residues ($3.00/kg of H(2)) and agricultural residues ($4.55/kg of H(2)) at a plant capacity of 2000 dry tonnes/day. In this study, bio-oil is produced in the field/forest and transported to a distance of 500 km from the centralized remote bio-oil production plant to bitumen upgrading plant. Feedstock delivery cost and capital cost are the largest cost contributors to the bio-oil production cost, while more than 50% of the cost of biohydrogen production is contributed by bio-oil production and transportation. Carbon credits of $133, $214, and $356/tonne of CO(2) equivalent could make whole-tree, forest residues, and straw-based biohydrogen production competitive with natural gas-based H(2) for a natural gas price of $5/GJ, respectively.

  9. Mild Biomass Liquefaction Process for Economic Production of Stabilized Refinery-Ready Bio-oil

    Energy Technology Data Exchange (ETDEWEB)

    Gangwal, Santosh [Southern Research, Durham, NC (United States); Meng, Jiajia [Southern Research, Durham, NC (United States); McCabe, Kevin [Southern Research, Durham, NC (United States); Larson, Eric [Princeton Univ., NJ (United States). Princeton Environmental Inst.; Mastro, Kelly [Southern Research, Durham, NC (United States)

    2016-04-25

    Southern Research (SR) in cooperation with U.S. Department of Energy (DOE), Bioenergy Technology Office (BETO), investigated a biomass liquefaction process for economic production of stabilized refinery-ready bio-oil. The project was awarded by DOE under a Funding Opportunity Announcement (DE-FOA-0000686) for Bio-oil Stabilization and Commoditization that intended to evaluate the feasibility of using bio-oil as a potential feedstock in an existing petroleum refinery. SR investigated Topic Area 1 of the FOA at Technology Readiness Level 2-3 to develop thermochemical liquefaction technologies for producing a bio-oil feedstock from high-impact biomass that can be utilized within a petroleum refinery. Bio-oil obtained from fast pyrolysis of biomass is a green intermediate that can be further upgraded into a biofuel for blending in a petroleum refinery using a hydro-deoxygenation (HDO) route. Co-processing pyrolysis bio-oil in a petroleum refinery is an attractive approach to leverage the refinery’s existing capital. However, the petroleum industry is reluctant to accept pyrolysis bio-oil because of a lack of a standard definition for an acceptable bio-oil feedstock in existing refinery processes. Also per BETO’s multiyear program plan, fast pyrolysis-based bio-fuel is presently not cost competitive with petroleum-based transportation fuels. SR aims to develop and demonstrate a cost-effective low-severity thermal liquefaction and hydrodeoxygenation (HDO) process to convert woody biomass to stabilized bio-oils that can be directly blended with hydrotreater input streams in a petroleum refinery for production of gasoline and/or diesel range hydrocarbons. The specific project objectives are to demonstrate the processes at laboratory scale, characterize the bio-oil product and develop a plan in partnership with a refinery company to move the technology towards commercialization.

  10. Low-Severity Hydroprocessing to Stabilize Bio-oil: TechnoEconomic Assessment

    Energy Technology Data Exchange (ETDEWEB)

    Tews, Iva J.; Elliott, Douglas C.

    2014-08-31

    The impetus for this study was the suggestion that recent developments in fast pyrolysis (FP) bio-oil production had indicated instability of the bio-oil in storage which might lead to unacceptable viscosity increases. Commercial operation of FP in Finland began in 2014 and the distribution of the bio-oil to isolated users has been proposed as the long-term plan. Stability of the shipped bio-oil therefore became a concern. Experimental results at PNNL with low-severity hydroprocessing of bio-oil for stabilization has validated a process in which the stability of the bio-oil could be improved, as measured by viscosity increase following storage of the product at 80 °C for 24h. In the work reported here the assessed process configuration consists of fast pyrolysis followed by low temperature and pressure hydroprocessing to produce a stable fuel oil product. The product could then be stored for an extended period of time without significant viscosity increase. This work was carried out as part of a collaborative project between Technical Research Centre of Finland (VTT) and Pacific Northwest National Laboratory (PNNL). The public funding agents for the work were Tekes in Finland and the Bioenergy Technologies Office of the U.S. Department of Energy. The effort was proposed as an evaluation of the process developed in earlier collaboration and jointly invented by VTT and PNNL researchers.

  11. One-Dimensional Biomass Fast Pyrolysis Model with Reaction Kinetics Integrated in an Aspen Plus Biorefinery Process Model

    Energy Technology Data Exchange (ETDEWEB)

    Humbird, David; Trendewicz, Anna; Braun, Robert; Dutta, Abhijit

    2017-01-27

    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 gas losses caused by stripping of the bio-oil by the fluidizing gas in the simulated absorber/condenser. 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.

  12. STEPWISE ISOTHERMAL FAST PYROLYSIS (SIFP OF BIOMASS PART I. SIFP OF PINE SAWDUST

    Directory of Open Access Journals (Sweden)

    Patricia López Rivilli

    2011-05-01

    Full Text Available Pyrolysis of pine wood sawdust was carried out using stepwise isothermal fast pyrolysis (SIFP, focusing on the search of reaction conditions to obtain chemicals in good yields from biomass. SIFP consists of successive isothermal fast pyrolysis reactions, where solid products obtained in the previous isothermal fast pyrolysis become the substrate of the subsequent reaction at a higher temperature. This article reports results obtained by SIFP of pine sawdust between 200 and 600°C using 100°C intervals under vacuum (0.2 mm, using nitrogen as carrier gas. Both sets of reactions made it possible to obtain most of the compounds that have been previously described in conventional fast pyrolysis experiments; however this system produces a smaller number of chemical compounds in each isothermal FP, making it easier to obtain determined chemicals with industrial or research value. Maximum yield of liquid products occurred at 300°C, giving around 30% of bio-oil, which contained mainly phenols and furan derivatives. Liquid-Liquid extraction led to a rich mixture of phenol derivatives. Results showed that SIFP is an interesting technique to obtain enriched fractions of products derived from biomass pyrolysis.

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

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Logan C. [National; Ciesielski, Peter N. [National; Jarvis, Mark W. [National; Mukarakate, Calvin [National; Nimlos, Mark R. [National; Donohoe, Bryon S. [National

    2017-07-12

    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, 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.

  14. Characterization of biomass fast pyrolysis. Advantages and drawbacks of different possible criteria

    Energy Technology Data Exchange (ETDEWEB)

    Lede, Jacques [LRGP-CNRS-INPL, 1, rue Grandville, BP 20451, Nancy Cedex (France); Authier, Olivier [LRGP-CNRS-INPL, 1, rue Grandville, BP 20451, Nancy Cedex (France); EDF-R and D, Departement Mecanique des Fluides, Energies et Environnement, 6, quai Watier, BP 49, Chatou Cedex (France)

    2011-09-15

    The literature shows that different possible criteria are used for defining biomass fast pyrolysis. On the basis of a simplified modeling of a cellulose (biomass model compound) particle pyrolysis, the present paper points out that the most often considered parameters (i.e., temperature and heating rate) are inappropriate. They are very difficult to define and measure, and according to their definitions, important errors can be made (kinetic measurements and reactor scaling up). Other possible parameters are also examined such as particle initial size, available heat flux density, heat transfer coefficient, and products elimination efficiency. In order to be able to compare different experimental conditions on a similar basis, it is shown that at the biomass sample level, fast pyrolysis is favoured (enhancement of bio-oil fractions) if two necessary conditions are simultaneously fulfilled. They include high external heat transfer coefficient and efficient products removal. (orig.)

  15. Stabilization of Bio-Oil Fractions for Insertion into Petroleum Refineries

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Robert C. [Iowa State Univ., Ames, IA (United States); Smith, Ryan [Iowa State Univ., Ames, IA (United States); Wright, Mark [Iowa State Univ., Ames, IA (United States); Elliott, Douglas [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Resasco, Daniel [Univ. of Oklahoma, Norman, OK (United States); Crossley, Steven [Univ. of Oklahoma, Norman, OK (United States)

    2014-09-28

    This project is part of a collaboration effort between Iowa State University (ISU), University of Oklahoma (OK) and Pacific Northwest National Laboratory (PNNL). The purpose of this project is to stabilize bio-oil fractions and improve their suitability for insertion into petroleum refineries. Bio-oil from fast pyrolysis of biomass is a complex mixture of unstable organic compounds. These organic compounds react under standard room conditions resulting in increases in bio-oil viscosity and water content – both detrimental for bio-oil storage and transportation. This study employed fractionation and upgrading systems to improve the stability of bio-oil. The fractionation system consists of a series of condensers, and electrostatic precipitators designed to separate bio-oil into five fractions: soluble carbohydrates (SF1&2), clean phenolic oligomers (CPO) and middle fraction (SF3&4), light oxygenates (SF5). A two-stage upgrading process was designed to process bio-oil stage fractions into stable products that can be inserted into a refinery. In the upgrading system, heavy and middle bio-oil fractions were upgraded into stable oil via cracking and subsequent hydrodeoxygenation. The light oxygenate fraction was steam reformed to provide a portion of requisite hydrogen for hydroprocessing. Hydrotreating and hydrocracking employed hydrogen from natural gas, fuel gas and light oxygenates reforming. The finished products from this study consist of gasoline- and diesel-blend stock fuels.

  16. Bio-oil Stabilization by Hydrogenation over Reduced Metal Catalysts at Low Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Huamin; Lee, Suh-Jane; Olarte, Mariefel V.; Zacher, Alan H.

    2016-08-30

    Biomass fast pyrolysis integrated with bio-oil upgrading represents a very attractive approach for converting biomass to hydrocarbon transportation fuels. However, the thermal and chemical instability of bio-oils presents significant problems when they are being upgraded, and development of effective approaches for stabilizing bio-oils is critical to the success of the technology. Catalytic hydrogenation to remove reactive species in bio-oil has been considered as one of the most efficient ways to stabilize bio-oil. This paper provides a fundamental understanding of hydrogenation of actual bio-oils over a Ru/TiO2 catalyst under conditions relevant to practical bio-oil hydrotreating processes. Bio-oil feed stocks, bio-oils hydrogenated to different extents, and catalysts have been characterized to provide insights into the chemical and physical properties of these samples and to understand the correlation of the properties with the composition of the bio-oil and catalysts. The results indicated hydrogenation of various components of the bio-oil, including sugars, aldehydes, ketones, alkenes, aromatics, and carboxylic acids, over the Ru/TiO2 catalyst and 120 to 160oC. Hydrogenation of these species significantly changed the chemical and physical properties of the bio-oil and overall improved its thermal stability, especially by reducing the carbonyl content, which represented the content of the most reactive species (i.e., sugar, aldehydes, and ketones). The change of content of each component in response to increasing hydrogen additions suggests the following bio-oil hydrogenation reaction sequence: sugar conversion to sugar alcohols, followed by ketone and aldehyde conversion to alcohols, followed by alkene and aromatic hydrogenation, and then followed by carboxylic acid hydrogenation to alcohols. Hydrogenation of bio-oil samples with different sulfur contents or inorganic material contents suggested that sulfur poisoning of the reduced Ru metal catalysts was

  17. Effect of acid, steam explosion, and size reduction pretreatments on bio-oil production from sweetgum, switchgrass, and corn stover.

    Science.gov (United States)

    Wang, Hui; Srinivasan, Radhakrishnan; Yu, Fei; Steele, Philip; Li, Qi; Mitchell, Brian; Samala, Aditya

    2012-05-01

    Bio-oil produced from biomass by fast pyrolysis has the potential to be a valuable substitute for fossil fuels. In a recent work on pinewood, we found that pretreatment alters the structure and chemical composition of biomass, which influence fast pyrolysis. In this study, we evaluated dilute acid, steam explosion, and size reduction pretreatments on sweetgum, switchgrass, and corn stover feedstocks. Bio-oils were produced from untreated and pretreated feedstocks in an auger reactor at 450 °C. The bio-oil's physical properties of pH, water content, acid value, density, and viscosity were measured. The chemical characteristics of the bio-oils were determined by gas chromatography-mass spectrometry. The results showed that bio-oil yield and composition were influenced by the pretreatment method and feedstock type. Bio-oil yields of 52, 33, and 35 wt% were obtained from medium-sized (0.68-1.532 mm) untreated sweetgum, switchgrass, and corn stover, respectively, which were higher than the yields from other sizes. Bio-oil yields of 56, 46, and 51 wt% were obtained from 1% H(2)SO(4)-treated medium-sized sweetgum, switchgrass, and corn stover, respectively, which were higher than the yields from untreated and steam explosion treatments.

  18. Past, Present, and Future Production of Bio-oil

    Energy Technology Data Exchange (ETDEWEB)

    Steele, Philip; Yu, Fei; Gajjela, Sanjeev

    2009-04-01

    Bio-oil is a liquid product produced by fast pyrol-ysis of biomass. The fast pyrolysis is performed by heating the biomass rapidly (2 sec) at temperatures ranging from 350 to 650 oC. The vapors produced by this rapid heating are then condensed to produce a dark brown water-based emulsion composed of frag-ments of the original hemicellulose, cellulose and lignin molecules contained in the biomass. Yields range from 60 to 75% based on the feedstock type and the pyrolysis reactor employed. The bio-oil pro-duced by this process has a number of negative prop-erties that are produced mainly by the high oxygen content (40 to 50%) contributed by that contained in water (25 to 30% of total mass) and oxygenated compounds. Each bio-oil contains hundreds of chemi-cal compounds. The chemical composition of bio-oil renders it a very recalcitrant chemical compound. To date, the difficulties in utilizing bio-oil have limited its commercial development to the production of liq-uid smoke as food flavoring. Practitioners have at-tempted to utilize raw bio-oil as a fuel; they have also applied many techniques to upgrade bio-oil to a fuel. Attempts to utilize raw bio-oil as a combustion engine fuel have resulted in engine or turbine dam-age; however, Stirling engines have been shown to successfully combust raw bio-oil without damage. Utilization of raw bio-oil as a boiler fuel has met with more success and an ASTM standard has recently been released describing bio-oil characteristics in relation to assigned fuel grades. However, commercialization has been slow to follow and no reports of distribution of these bio-oil boiler fuels have been reported. Co-feeding raw bio-oil with coal has been successfully performed but no current power generation facilities are following this practice. Upgrading of bio-oils to hydrocarbons via hydroprocessing is being performed by several organizations. Currently, limited catalyst life is the obstacle to commercialization of this tech-nology. Researchers

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Emissions and properties of Bio-oil and Natural Gas Co-combustion in a Pilot Stabilised Swirl Burner

    Science.gov (United States)

    Kowalewski, Dylan

    Fast pyrolysis oil, or bio-oil, has been investigated to replace traditional fossil fuels in industrial burners. However, flame stability is a challenge due to its high water content. In order to address its instability, bio-oil was co-fired with natural gas in a lab scale 10kW swirl burner at energy ratios from 0% bio-oil to 80% bio-oil. To evaluate the combustion, flame shape, exhaust and particulate emissions, temperatures, as well as infrared emission were monitored. As the bio-oil energy fraction increased, NO emissions increased due to the nitrogen content of bio-oil. CO and particulate emissions increased likely due to carbonaceous residue exiting the combustion zone. Unburnt Hydrocarbon (UHC) emissions increased rapidly as combustion became poor at 60-80% bio-oil energy. The temperature and infrared output decreased with more bio-oil energy. The natural gas proved to be effective at anchoring the bio-oil flame to the nozzle, decreasing instances of extinction or blowout.

  1. Influence of the Pyrolysis Temperature on Sewage Sludge Product Distribution, Bio-Oil, and Char Properties

    DEFF Research Database (Denmark)

    Trinh, Ngoc Trung; Jensen, Peter Arendt; Dam-Johansen, Kim

    2013-01-01

    centrifugel reactor (PCR) at 475, 525, 575, and 625 °C. Maxima of both organic oil yield of 41 wt % on a dry ash free feedstock basis (daf) and a sludge oil energy recovery of 50% were obtained at 575 °C. The water-insoluble fraction, molecular-weight distribution, higher heating value (HHV), and thermal......Fast pyrolysis may be used for sewage sludge treatment with the advantages of a significant reduction of solid waste volume and production of a bio-oil that can be used as fuel. A study of the influence of the reaction temperature on sewage sludge pyrolysis has been carried out using a pyrolysis...... behaviors of sludge oils were found to be considerably influenced by the applied pyrolysis temperatures. The sludge oil properties obtained at the optimal temperature of 575 °C were a HHV of 25.5 MJ/kg, a water-insoluble fraction of 18.7 wt %, a viscosity of 43.6 mPa s at 40 °C, a mean molecular weight...

  2. A Systems Approach to Bio-Oil Stabilization - Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Robert C; Meyer, Terrence; Fox, Rodney; Submramaniam, Shankar; Shanks, Brent; Smith, Ryan G

    2011-12-23

    The objective of this project is to develop practical, cost effective methods for stabilizing biomass-derived fast pyrolysis oil for at least six months of storage under ambient conditions. The U.S. Department of Energy has targeted three strategies for stabilizing bio-oils: (1) reducing the oxygen content of the organic compounds comprising pyrolysis oil; (2) removal of carboxylic acid groups such that the total acid number (TAN) of the pyrolysis oil is dramatically reduced; and (3) reducing the charcoal content, which contains alkali metals known to catalyze reactions that increase the viscosity of bio-oil. Alkali and alkaline earth metals (AAEM), are known to catalyze decomposition reactions of biomass carbohydrates to produce light oxygenates that destabilize the resulting bio-oil. Methods envisioned to prevent the AAEM from reaction with the biomass carbohydrates include washing the AAEM out of the biomass with water or dilute acid or infusing an acid catalyst to passivate the AAEM. Infusion of acids into the feedstock to convert all of the AAEM to salts which are stable at pyrolysis temperatures proved to be a much more economically feasible process. Our results from pyrolyzing acid infused biomass showed increases in the yield of anhydrosugars by greater than 300% while greatly reducing the yield of light oxygenates that are known to destabilize bio-oil. Particulate matter can interfere with combustion or catalytic processing of either syngas or bio-oil. It also is thought to catalyze the polymerization of bio-oil, which increases the viscosity of bio-oil over time. High temperature bag houses, ceramic candle filters, and moving bed granular filters have been variously suggested for syngas cleaning at elevated temperatures. High temperature filtration of bio-oil vapors has also been suggested by the National Renewable Energy Laboratory although there remain technical challenges to this approach. The fast pyrolysis of biomass yields three main organic

  3. Effect of Fast Pyrolysis Conditions on Structural Transformation and Reactivity of Herbaceous Biomasses at High Temperatures

    DEFF Research Database (Denmark)

    Trubetskaya, Anna; Jensen, Anker D.; Jensen, Peter Arendt

    of organic and inorganic matter on the char structural transformations. The results indicate no influence of the free radicals on char reactivity and burnout. The formation of free radicals in fast pyrolysis is related to the differences in the ash composition, namely presence of K+ ions in the wheat straw...

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

    Energy Technology Data Exchange (ETDEWEB)

    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. Fast Pyrolysis of Lignin Using a Pyrolysis Centrifuge Reactor

    DEFF Research Database (Denmark)

    Trinh, Ngoc Trung; Jensen, Peter Arendt; Sárossy, Zsuzsa

    2013-01-01

    Fast pyrolysis of lignin from an ethanol plant was investigated on a lab scale pyrolysis centrifuge reactor (PCR) with respect to pyrolysis temperature, reactor gas residence time, and feed rate. A maximal organic oil yield of 34 wt % dry basis (db) (bio-oil yield of 43 wt % db) is obtained...... at temperatures of 500−550 °C, reactor gas residence time of 0.8 s, and feed rate of 5.6 g/min. Gas chromatography mass spectrometry and size-exclusion chromatography were used to characterize the Chemical properties of the lignin oils. Acetic acid, levoglucosan, guaiacol, syringols, and p-vinylguaiacol are found...... to be major chemical components in the lignin oil. The maximal yields of 0.62, 0.67, and 0.38 wt % db were obtained for syringol, p-vinylguaiacol, and guaiacol, respectively. The reactor temperature effect was investigated in a range of 450−600 °C and has a considerable effect on the observed chemical...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-02-25

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-02-28

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    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

  10. Fast pyrolysis of biomass at high temperatures

    DEFF Research Database (Denmark)

    Trubetskaya, Anna

    This Ph.D. thesis describes experimental and modeling investigations of fast high temperature pyrolysis of biomass. Suspension firing of biomass is widely used for power generation and has been considered as an important step in reduction of greenhouse gas emissions by using less fossil fuels. Fast...... pyrolysis at high temperatures plays a significant role in the overall combustion process since the biomass type, the reaction kinetics and heat transfer rates during pyrolysis influence the volatile gas release. The solid residue yield and its properties in suspension firing, including particle size...... and shape, composition, reactivity and burnout depend significantly on the operating conditions of the fast pyrolysis. Biomass fast pyrolysis experiments were performed in a laboratory-scale wire mesh reactor and bench scale atmospheric pressure drop tube / entrained flow reactors with the aim...

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

    Science.gov (United States)

    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.

  12. Characterization of Hydrotreated Fast Pyrolysis Liquids

    NARCIS (Netherlands)

    Oasmaa, A.; Kuoppala, E.; Ardiyanti, A.; Venderbosch, R. H.; Heeres, H. J.

    2010-01-01

    This paper focuses on analytical methods to determine the composition of hydrotreated fast pyrolysis liquids. With this information, it is possible to gain insights in the chemical transformations taking place during catalytic hydrotreatment (hydrogenation and/or hydrodeoxygenation, H DO) of pyrolys

  13. Exploratory studies on fast pyrolysis oil upgrading

    NARCIS (Netherlands)

    Mahfud, Farchad Husein

    2007-01-01

    Pyrolysis oil is a dark brown liquid which can be produced in high yield from different kind of biomass sources by means of fast pyrolysis. Pyrolysis oil is considered as a promising second generation energy carrier and may play an important role in the future of "biobased economies". The energy

  14. Exploratory studies on fast pyrolysis oil upgrading

    NARCIS (Netherlands)

    Mahfud, Farchad Husein

    2007-01-01

    Pyrolysis oil is a dark brown liquid which can be produced in high yield from different kind of biomass sources by means of fast pyrolysis. Pyrolysis oil is considered as a promising second generation energy carrier and may play an important role in the future of "biobased economies". The energy con

  15. Synthesis and Characterization of Bio-Oil Phenol Formaldehyde Resin Used to Fabricate Phenolic Based Materials.

    Science.gov (United States)

    Cui, Yong; Hou, Xiaopeng; Wang, Wenliang; Chang, Jianmin

    2017-06-18

    In this study, bio-oil from the fast pyrolysis of renewable biomass was used as the raw material to synthesize bio-oil phenol formaldehyde (BPF) resin-a desirable resin for fabricating phenolic-based material. During the synthesis process, paraformaldehyde was used to achieve the requirement of high solid content and low viscosity. The properties of BPF resins were tested. Results indicated that BPF resin with the bio-oil addition of 20% had good performance on oxygen index and bending strength, indicating that adding bio-oil could modify the fire resistance and brittleness of PF resin. The thermal curing behavior and heat resistance of BPF resins were investigated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Results showed that adding bio-oil had an impact on curing characteristics and thermal degradation process of PF resin, but the influence was insignificant when the addition was relatively low. The chemical structure and surface characteristics of BPF resins were determined by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The analysis demonstrated that adding bio-oil in the amount of 20% was able to improve the crosslinking degree and form more hydrocarbon chains in PF resin.

  16. Compatibility Assessment of Fuel System Elastomers with Bio-oil and Diesel Fuel

    Energy Technology Data Exchange (ETDEWEB)

    Kass, Michael D.; Janke, Christopher J.; Connatser, Raynella M.; Lewis, Samuel A.; Keiser, James R.; Gaston, Katherine

    2016-08-18

    Bio-oil derived via fast pyrolysis is being developed as a renewable fuel option for petroleum distillates. The compatibility of neat bio-oil with six elastomer types was evaluated against the elastomer performance in neat diesel fuel, which served as the baseline. The elastomers included two fluorocarbons, six acrylonitrile butadiene rubbers (NBRs), and one type each of fluorosilicone, silicone, styrene butadiene rubber (SBR), polyurethane, and neoprene. Specimens of each material were exposed to the liquid and gaseous phases of the test fuels for 4 weeks at 60 degrees C, and properties in the wetted and dried states were measured. Exposure to bio-oil produced significant volume expansion in the fluorocarbons, NBRs, and fluorosilicone; however, excessive swelling (over 80%) was only observed for the two fluorocarbons and two NBR grades. The polyurethane specimens were completely degraded by the bio-oil. In contrast, both silicone and SBR exhibited lower swelling levels in bio-oil compared to neat diesel fuel. The implication is that, while polyurethane and fluorocarbon may not be acceptable seal materials for bio-oils, silicone may offer a lower cost alternative.

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

    Energy Technology Data Exchange (ETDEWEB)

    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. Preparation of Hydrogen through Catalytic Steam Reforming of Bio-oil

    Institute of Scientific and Technical Information of China (English)

    吴层; 颜涌捷; 李庭琛; 亓伟

    2007-01-01

    Hydrogen was prepared via catalytic steam reforming of bio-oil which was obtained from fast pyrolysis of biomass in a fluidized bed reactor. Influential factors including temperature, weight hourly space velocity (WHSV) of bio-oil, mass ratio of steam to bio-oil (S/B) as well as catalyst type on hydrogen selectivity and other desirable gas products were investigated. Based on hydrogen in stoichiometric potential and carbon balance in gaseous phase and feed, hydrogen yield and carbon selectivity were examined. The experimental results show that higher temperature favors the hydrogen selectivity by H2 mole fraction in gaseous products stream and it plays an important role in hydrogen yield and carbon selectivity. Higher hydrogen selectivity and yield, and carbon selectivity were obtained at lower bio-oil WHSV. In catalytic steam reforming system a maximum steam concentration value exists, at which hydrogen selectivity and yield, and carbon selectivity keep constant. Through experiments, preferential operation conditions were obtained as follows: temperature 800~850℃, bio-oil WHSV below 3.0 h-1, and mass ratio of steam to bio-oil 10~12. The performance tests indicate that Ni-based catalysts are optional, especially Ni/a-Al2O3 effective in the steam reforming process.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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).

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

    Energy Technology Data Exchange (ETDEWEB)

    Adom, Felix K. [Argonne National Lab. (ANL), Argonne, IL (United States); Cai, Hao [Argonne National Lab. (ANL), Argonne, IL (United States); Dunn, Jennifer B. [Argonne National Lab. (ANL), Argonne, IL (United States); Hartley, Damon [Idaho National Lab. (INL), Idaho Falls, ID (United States); Searcy, Erin [Idaho National Lab. (INL), Idaho Falls, ID (United States); Tan, Eric [National Renewable Energy Lab. (NREL), Golden, CO (United States); Jones, Sue [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Snowden-Swan, Lesley [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2016-03-01

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

  2. Influence of fast pyrolysis temperature on biochar labile fraction and short-term carbon loss in a loamy soil

    DEFF Research Database (Denmark)

    Bruun, Esben; Hauggaard-Nielsen, Henrik; Ibrahim, Norazana;

    2011-01-01

    Production of bio-oil, gas and biochar from pyrolysis of biomass is considered a promising technology for combined production of bioenergy and recalcitrant carbon (C) suitable for sequestration in soil. Using a fast pyrolysis centrifuge reactor (PCR) the present study investigated the relation......, emphasizing the importance of knowing the biochar labile fraction when evaluating a specific biochars C sequestration potential. The pyrolysis temperature influenced the outputs of biochar, bio-oil and syngas significantly, as well as the stability of the biochar produced. Contrary to slow pyrolysis a fast...... in soil. As these labile carbohydrates are rapidly mineralized, their presence lowers the biochar-C sequestration potential. By raising the pyrolysis temperature, biochar with none or low contents of these fractions can be produced, but this will be on the expense of the biochar quantity. The yield of CO2...

  3. Structural and Compositional Transformations of Biomass Chars during Fast Pyrolysis

    DEFF Research Database (Denmark)

    Trubetskaya, Anna; Steibel, Markus; Spliethoff, Hartmut

    In this work the physical and chemical transformations of biomass chars during fast pyrolysis, considered as a 2nd stage of combustion, has been investigated. Seven biomasses containing different amount of ash and organic components were reacted at up to 1673 K with high heating rates in a wire......-mesh reactor and the resulting chars were retrieved. In order to obtain information on the structural and compositional transformations of the biomass chars, samples were subjected to elemental analysis, scanning electron microcopy with EDX and Raman spectrometry. The results show that there are significant...... changes in both the organic and inorganic constituents of the chars.Under high heating rates (> 100 K/s) char particles underwent different types of melting and pores of different size were developed in dependency on the temperature and biomass composition. The Si-rich rice husks char did not show any...

  4. Online upgrading of organic vapors from the fast pyrolysis of biomass

    Institute of Scientific and Technical Information of China (English)

    LI Hong-yu; YAN Yong-jie; REN Zheng-wei

    2008-01-01

    The online upgrading process that combined the fast pyrolysis of biomass and catalytic cracking of bio-oil was developed to produce a high quality liquid product from the biomass. The installation consisted of a fluidized bed reactor for pyrolysis and a packed bed reactor for upgrading. The proper pyrolysis processing conditions with a temperature of 500℃ and a flow rate of 4m3·h-1 were determined in advance. Under such conditions, the effects of temperature and weight hourly space velocity (WHSV) on both the liquid yields and the oil qualities of the online catalytic cracking process were investigated. The results showed that such a combined process had the superiority of increasing the liquid yield and improving the product quality over the separate processes. Furthermore, when the temperature was 500℃, with a WHSV of 3h-1, the liquid yield reached the maximum and the oxygenic compounds also decreased obviously.

  5. Catalytic Conversion of Bio-oil to Fuel for Transportation

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard

    The incitement for decreasing the modern society's dependency on fossil based fuel and energy is both environmentally and politically driven. Development of biofuels could be part of the future solution. The combination of ash pyrolysis and catalytic upgrading of the produced bio-oil has been ide...

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

    Energy Technology Data Exchange (ETDEWEB)

    Czernik, S.; Wang, D.; Chornet, E. [National Renewable Energy Lab., Golden, CO (United States). Center for Renewable Chemical Technologies and Materials

    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.

  7. Effect of Fast Pyrolysis Conditions on Structural Transformation and Reactivity of Herbaceous Biomasses at High Temperatures

    DEFF Research Database (Denmark)

    Trubetskaya, Anna; Jensen, Anker D.; Jensen, Peter Arendt

    Fast pyrolysis of wheat straw and rice husks was carried out in an entrained-flow reactor (EFR) and compared with the results from the wire-mesh reactor (WMR) in terms of the char yield at high-temperatures (1000-1500°C) to study the effect of heating rate, final temperature, ash content and part......Fast pyrolysis of wheat straw and rice husks was carried out in an entrained-flow reactor (EFR) and compared with the results from the wire-mesh reactor (WMR) in terms of the char yield at high-temperatures (1000-1500°C) to study the effect of heating rate, final temperature, ash content...... and particle size on the char yield. X-ray diffractometry (XRD), N-adsorption (BET), scanning electron microscopy (SEM), particle size analysis (CAMSIZER XT), nuclear magnetic resonance spectroscopy (29Si NMR; 13C NMR) and electron spinning resonance spectroscopy (ESR) were conducted to investigate the effect...... of organic and inorganic matter on the char structural transformations. The results indicate no influence of the free radicals on char reactivity and burnout. The formation of free radicals in fast pyrolysis is related to the differences in the ash composition, namely presence of K+ ions in the wheat straw...

  8. Thermogravimetric analysis and fast pyrolysis of Milkweed.

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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).

  10. Gasification of bio-oil: Effects of equivalence ratio and gasifying agents on product distribution and gasification efficiency.

    Science.gov (United States)

    Zheng, Ji-Lu; Zhu, Ming-Qiang; Wen, Jia-Long; Sun, Run-Cang

    2016-07-01

    Bio-oil derived from fast pyrolysis of rice husk was gasified for producing gas. The effectiveness of equivalence ratio and gasifying agents on the gas composition, ratio of H2/CO, tar amount, low heating value, degree of oxidation and cold gas efficiency of the gas were comprehensively investigated. Under different equivalence ratios and gasifying agents, the gases can be used as synthesis gas for Fischer-Tropsch synthesis, fuel gas for gas turbines in a power plant and reducing gas for ore reduction, respectively. The H2 concentration, CO level and cold gas efficiency of the resulted gas derived from gasification of bio-oil were significantly higher, while tar content was remarkably lower than those derived from gasification of solid biomass using the same equivalent ratio value and gasifying agent. In short, bio-oil gasification is economically feasible for large scale production of fuels and chemicals.

  11. Bio-oil fractionation and condensation

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Robert C.; Jones, Samuel T.; Pollard, Anthony

    2017-04-04

    The present invention relates to a method of fractionating bio-oil vapors which involves providing bio-oil vapors comprising bio-oil constituents. The bio-oil vapors are cooled in a first stage which comprises a condenser having passages for the bio-oil separated by a heat conducting wall from passages for a coolant. The coolant in the condenser of the first stage is maintained at a substantially constant temperature, set at a temperature in the range of 75 to 100.degree. C., to condense a first liquid fraction of liquefied bio-oil constituents in the condenser of the first stage. The first liquid fraction of liquified bio-oil constituents from the condenser in the first stage is collected. Also disclosed are steps for subsequently recovering further liquid fractions of liquefied bio-oil constituents. Particular compositions of bio-oil condensation products are also described.

  12. Bio-oil fractionation and condensation

    Science.gov (United States)

    Brown, Robert C; Jones, Samuel T; Pollard, Anthony

    2013-07-02

    A method of fractionating bio-oil vapors which involves providing bio-oil vapors comprising bio-oil constituents is described. The bio-oil vapors are cooled in a first stage which comprises a condenser having passages for the bio-oil separated by a heat conducting wall from passages for a coolant. The coolant in the condenser of the first stage is maintained at a substantially constant temperature, set at a temperature in the range of 75 to 100.degree. C., to condense a first liquid fraction of liquefied bio-oil constituents in the condenser of the first stage. The first liquid fraction of liquified bio-oil constituents from the condenser in the first stage is collected. Also described are steps for subsequently recovering further liquid fractions of liquefied bio-oil constituents. Particular compositions of bio-oil condensation products are also described.

  13. Catalytic Fast Pyrolysis of Wild Reed Over Nanoporous SBA-15 Catalysts.

    Science.gov (United States)

    Park, Y K; Yoo, Myung Lang; Park, Sung Hoon

    2016-05-01

    Wild reed was pyrolyzed over two nanoporous SBA-15 catalysts with different acid characteristics: Si-SBA-15 and Al-SBA-15. Al was grafted on Si-SBA-15 to increase the acidity and enhance the catalytic activity. Fast pyrolysis was carried out using a pyrolysis-gas chromatography/mass spectrometry system at 550 degrees C for real-time analysis of the products. Significant improvement of the product bio-oil quality was attained by catalytic reforming over nanoporous Al-SBA-15. The fraction of total oxygenates was reduced because of the decrease in. the fraction of ketones, aldehydes, and carboxylates, which deteriorate the fuel quality of bio-oil. On the other hand, the fractions of furans and aromatics, which are the chemicals with high value-added, were increased by the catalytic reforming. The catalytic activity of Al-SBA-15 was considerably higher than that of Si-SBA-15 because the incorporation of Al increased the catalyst acidity.

  14. Bio-oil production of softwood and hardwood forest industry residues through fast and intermediate pyrolysis and its chromatographic characterization.

    Science.gov (United States)

    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.

  15. Techno-economic analysis of advanced biofuel production based on bio-oil gasification.

    Science.gov (United States)

    Li, Qi; Zhang, Yanan; Hu, Guiping

    2015-09-01

    This paper evaluates the economic feasibility of an integrated production pathway combining fast pyrolysis and bio-oil gasification. The conversion process is simulated with Aspen Plus® for a 2000 metric ton per day facility. Techno-economic analysis of this integrated pathway has been conducted. A total capital investment of $510 million has been estimated and the minimum fuel selling price (MSP) is $5.59 per gallon of gasoline equivalent. The sensitivity analysis shows that the MSP is most sensitive to internal rate of return, fuel yield, biomass feedstock cost, and fixed capital investment. Monte-Carlo simulation shows that MSP for bio-oil gasification would be more than $6/gal with a probability of 0.24, which indicates this pathway is still at high risk with current economic and technical situation.

  16. Study on condensation of biomass pyrolysis gas by spray bio-oil droplets

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Kun; Cheng, Wen-Long [University of Science and Technology of China (China)], email: wlcheng@ustc.edu.cn; Chen, Jing [Anhui Electric Power Design Institute (China); Shi, Wen-Jing [Anhui Heli Co., Ltd (China)

    2011-07-01

    This is a study of bio-oil generated by fast pyrolysis; a biomass feedstock is heated to pyrolyze at a rapid rate, the gas pyrolyzed is then condensed rapidly. The interesting result is a potential alternative fuel oil. An analysis was made of the effects of the initial pyrolysis gas temperatures, the initial bio-oil droplets temperatures and diameters, and the flow ratio of the gas and the liquid droplets on the heat and mass transfer between the gas and the liquid droplets. A few criterion equations were achieved with respect to the spray condenser. This paper established the gas-liquid phase equilibrium of an aqueous multi-composition system and the spray condensation model coupling heat and mass transfer. Model calculation and analysis showed that: spray condensation can effectively cool the high-temperature pyrolysis gas quickly; with gas liquid flowing, mass transfer rate reduces; and the relationship of gas and liquid flow ratio can achieve good accuracy.

  17. Catalyst studies on the hydrotreatment of fast pyrolysis oil

    NARCIS (Netherlands)

    Wildschut, J.; Melian-Cabrera, I.; Heeres, H. J.

    2010-01-01

    Catalytic hydrotreatment is considered an attractive technology for fast pyrolysis oil upgrading to liquid transportation fuels. We here report an experimental study to gain insights in catalyst stability when using Ru/C catalysts for the hydrotreatment of fast pyrolysis oil (350 degrees C and 200 b

  18. Catalyst studies on the hydrotreatment of fast pyrolysis oil

    NARCIS (Netherlands)

    Wildschut, J.; Melian-Cabrera, I.; Heeres, H. J.

    2010-01-01

    Catalytic hydrotreatment is considered an attractive technology for fast pyrolysis oil upgrading to liquid transportation fuels. We here report an experimental study to gain insights in catalyst stability when using Ru/C catalysts for the hydrotreatment of fast pyrolysis oil (350 degrees C and 200 b

  19. Process modeling and supply chain design for advanced biofuel production based on bio-oil gasification

    Science.gov (United States)

    Li, Qi

    As a potential substitute for petroleum-based fuel, second generation biofuels are playing an increasingly important role due to their economic, environmental, and social benefits. With the rapid development of biofuel industry, there has been an increasing literature on the techno-economic analysis and supply chain design for biofuel production based on a variety of production pathways. A recently proposed production pathway of advanced biofuel is to convert biomass to bio-oil at widely distributed small-scale fast pyrolysis plants, then gasify the bio-oil to syngas and upgrade the syngas to transportation fuels in centralized biorefinery. This thesis aims to investigate two types of assessments on this bio-oil gasification pathway: techno-economic analysis based on process modeling and literature data; supply chain design with a focus on optimal decisions for number of facilities to build, facility capacities and logistic decisions considering uncertainties. A detailed process modeling with corn stover as feedstock and liquid fuels as the final products is presented. Techno-economic analysis of the bio-oil gasification pathway is also discussed to assess the economic feasibility. Some preliminary results show a capital investment of 438 million dollar and minimum fuel selling price (MSP) of $5.6 per gallon of gasoline equivalent. The sensitivity analysis finds that MSP is most sensitive to internal rate of return (IRR), biomass feedstock cost, and fixed capital cost. A two-stage stochastic programming is formulated to solve the supply chain design problem considering uncertainties in biomass availability, technology advancement, and biofuel price. The first-stage makes the capital investment decisions including the locations and capacities of the decentralized fast pyrolysis plants and the centralized biorefinery while the second-stage determines the biomass and biofuel flows. The numerical results and case study illustrate that considering uncertainties can be

  20. A Systems Approach to Bio-Oil Stabilization - Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Brown, Robert C; Meyer, Terrence; Fox, Rodney; Submramaniam, Shankar; Shanks, Brent; Smith, Ryan G

    2011-12-23

    The objective of this project is to develop practical, cost effective methods for stabilizing biomass-derived fast pyrolysis oil for at least six months of storage under ambient conditions. The U.S. Department of Energy has targeted three strategies for stabilizing bio-oils: (1) reducing the oxygen content of the organic compounds comprising pyrolysis oil; (2) removal of carboxylic acid groups such that the total acid number (TAN) of the pyrolysis oil is dramatically reduced; and (3) reducing the charcoal content, which contains alkali metals known to catalyze reactions that increase the viscosity of bio-oil. Alkali and alkaline earth metals (AAEM), are known to catalyze decomposition reactions of biomass carbohydrates to produce light oxygenates that destabilize the resulting bio-oil. Methods envisioned to prevent the AAEM from reaction with the biomass carbohydrates include washing the AAEM out of the biomass with water or dilute acid or infusing an acid catalyst to passivate the AAEM. Infusion of acids into the feedstock to convert all of the AAEM to salts which are stable at pyrolysis temperatures proved to be a much more economically feasible process. Our results from pyrolyzing acid infused biomass showed increases in the yield of anhydrosugars by greater than 300% while greatly reducing the yield of light oxygenates that are known to destabilize bio-oil. Particulate matter can interfere with combustion or catalytic processing of either syngas or bio-oil. It also is thought to catalyze the polymerization of bio-oil, which increases the viscosity of bio-oil over time. High temperature bag houses, ceramic candle filters, and moving bed granular filters have been variously suggested for syngas cleaning at elevated temperatures. High temperature filtration of bio-oil vapors has also been suggested by the National Renewable Energy Laboratory although there remain technical challenges to this approach. The fast pyrolysis of biomass yields three main organic

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

    Science.gov (United States)

    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. Fabrication of Glass Fiber Reinforced Composites Based on Bio-Oil Phenol Formaldehyde Resin

    Directory of Open Access Journals (Sweden)

    Yong Cui

    2016-11-01

    Full Text Available In this study, bio-oil from fast pyrolysis of renewable biomass was added by the mass of phenol to synthesize bio-oil phenol formaldehyde (BPF resins, which were used to fabricate glass fiber (GF reinforced BPF resin (GF/BPF composites. The properties of the BPF resin and the GF/BPF composites prepared were tested. The functional groups and thermal property of BPF resin were thoroughly investigated by Fourier transform infrared (FTIR spectra and dynamic thermomechanical analysis (DMA. Results indicated that the addition of 20% bio-oil exhibited favorable adaptability for enhancing the stiffness and heat resistance of phenol formaldehyde (PF resin. Besides, high-performance GF/BPF composites could be successfully prepared with the BPF resin based on hand lay-up process. The interface characteristics of GF/BPF composites were determined by the analysis of dynamic wettability (DW and scanning electron microscopy (SEM. It exhibited that GF could be well wetted and embedded in the BPF resin with the bio-oil addition of 20%.

  3. Catalytic Hydrodeoxygenation of Bio-oil Model Compounds over Pt/HY Catalyst

    Science.gov (United States)

    Lee, Heejin; Kim, Hannah; Yu, Mi Jin; Ko, Chang Hyun; Jeon, Jong-Ki; Jae, Jungho; Park, Sung Hoon; Jung, Sang-Chul; Park, Young-Kwon

    2016-06-01

    The hydrodeoxygenation of a model compound of lignin-derived bio-oil, guaiacol, which can be obtained from the pyrolysis of biomass to bio-oil, has attracted considerable research attention because of its huge potential as a substitute for conventional fuels. In this study, platinum-loaded HY zeolites (Pt/HY) with different Si/Al molar ratios were used as catalysts for the hydrodeoxygenation of guaiacol, anisole, veratrole, and phenol to a range of hydrocarbons, such as cyclohexane. The cyclohexane (major product) yield increased with increasing number of acid sites. To produce bio-oil with the maximum level of cyclohexane and alkylated cyclohexanes, which would be suitable as a substitute for conventional transportation fuels, the Si/Al molar ratio should be optimized to balance the Pt particle-induced hydrogenation with acid site-induced methyl group transfer. The fuel properties of real bio-oil derived from the fast pyrolysis of cork oak was improved using the Pt/HY catalyst.

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

    Energy Technology Data Exchange (ETDEWEB)

    Solak, Agnieszka; Rutkowski, Piotr, E-mail: piotr.rutkowski@pwr.wroc.pl

    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.

  5. Quantitative analysis of crude and stabilized bio-oils by comprehensive two-dimensional gas-chromatography.

    Science.gov (United States)

    Djokic, Marko R; Dijkmans, Thomas; Yildiz, Guray; Prins, Wolter; Van Geem, Kevin M

    2012-09-28

    Bio-oils produced by fast pyrolysis of lignocellulosic biomass have proven to be a promising, clean, and renewable energy source. To better assess the potential of using bio-oils for the production of chemicals and fuels a new comprehensive characterization method is developed. The combination of the analyical power of GC×GC-FID and GC×GC-TOF-MS allows to obtain an unseen level of detail for both crude and hydrotreated bio-oils originated from pine wood biomass. The use of GC×GC proves to be essential to capture the compositional differences between crude and stabilized bio-oils. Our method uses a flame ionization detector to quantify the composition, while GC×GC-TOF-MS is used for the qualitative analysis. This method allows quantification of around 150 tentatively identified compounds, describing approximately 80% of total peak volume. The number of quantified compounds in bio-oils is increased with a factor five compared to the present state-of-the-arte. The necessity of using multiple internal standards (dibutyl ether and fluoranthene) and a cold-on column injector is also verified. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve; Evans, Tabitha; Starace, Anne K.; ten Dam, Jeroen; Watson, Michael J.; Magrini, Kim

    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 present in this stream. This 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). 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.

  7. Mass spectrometric studies of fast pyrolysis of cellulose

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. A Short Historical Review of Fast Pyrolysis of Biomass Une brève revue historique de la pyrolyse rapide de la biomasse

    Directory of Open Access Journals (Sweden)

    Radlein D.

    2013-10-01

    Full Text Available In this short review, we survey the historical progress of fast pyrolysis technologies for thermochemical liquefaction of biomass to produce so-called "bio-oil". Our focus is on the potential applications of bio-oil as a liquid fuel for heat and power generation. We point out some of the inherent properties of bio-oil that create difficulties standing in the way of these applications. Finally, we take a brief look at some processes that aim to valorize bio-oil by conversion to higher value liquid fuel products. Dans cette revue nous nous proposons de dresser un rappel historique des progrès relatifs aux technologies de liquéfaction thermochimiques par pyrolyse rapide, encore appelée pyrolyse flash, de la biomasse pour produire ce que l’on appelle communément une "bio-huile". Nous insisterons sur ses applications comme combustible liquide pour la production de chaleur et d’électricité. Nous ferons ressortir quelques propriétés spécifiques aux bio-huiles qui peuvent créer des difficultés d’usage. Nous terminerons par un bref aperçu de quelques procédés permettant de valoriser la bio-huile en carburants liquides de plus forte valeur ajoutée.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  12. Bio-oil from Flash Pyrolysis of Agricultural Residues

    DEFF Research Database (Denmark)

    Ibrahim, Norazana

    -oil was around 525 °C to 550 °C for all straw moisture contents. It was investigated how differences in biomass composition influence pyrolysis products yields and the composition of char and bio-oils. Details about this investigation are explained in Paper II (Chapter 3). The used pine wood had a low ash...... at reactor temperatures ranging from 475 to 575 oC. It was observed that the formation of char and gas is affected by the biomass alkali content. Increasing biomass alkali content caused an increased feedstock conversion at low temperature, a lower maximum liquid organic yield temperature and a lower maximum......This thesis describes the production of bio-oils from flash pyrolysis of agricultural residues, using a pyrolysis centrifugal reactor (PCR). By thermal degradation of agricultural residues in the PCR, a liquid oil, char and non-condensable gases are produced. The yield of each fraction...

  13. Fast pyrolysis of wheat straw combined with SI-MCM-41 catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Ates, Funda; Putun, Ayse Eren [Anadolu University, Department of Chemical Engineering, Faculty of Engineering and Architecture (Turkey)], e-mail: fdivrikl@anadolu.edu.tr, email: aeputun@anadolu.edu.tr; Tophanecioglu, Sibel [Erkurt Holding (Turkey)], email: sibel8888@gmail.com

    2011-07-01

    The purpose of this paper is to give the results of an experiment in which the respective results from fast pyrolysis of wheat straw catalyzed with Si-MCM-4, and in the non-catalytic condition were compared. This experiment was carried out in a well-swept fixed-bed reactor with a heating rate of 300 degree C/min and in a nitrogen atmosphere after which, the main characteristics of pyrolyzed feedstock were determined by proximate, ultimate and component analysis. As the results of this experiment show, the maximum oil yield was 31.9% in a non-catalytic pyrolysis procedure and this gas yield increased in the pyrolysis experiment with catalyst, although the bio-oil yield decreased. On the other hand, the use of catalyst had the benefit of reducing the percentage of oxygen, the presence of which in the fuel is not desirable. Through testing pyrolysis oils, it was established that the use of a catalyst in the pyrolysis can improve fuel quality and produce valuable chemicals.

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

    Science.gov (United States)

    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.

  15. Life cycle assessment of the production of hydrogen and transportation fuels from corn stover via fast pyrolysis

    Science.gov (United States)

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

    Science.gov (United States)

    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.

  17. Preparation and characterization of bio-oils from internally circulating fluidized-bed pyrolyses of municipal, livestock, and wood waste.

    Science.gov (United States)

    Cao, Jing-Pei; Xiao, Xian-Bin; Zhang, Shou-Yu; Zhao, Xiao-Yan; Sato, Kazuyoshi; Ogawa, Yukiko; Wei, Xian-Yong; Takarada, Takayuki

    2011-01-01

    Fast pyrolyses of sewage sludge (SS), pig compost (PC), and wood chip (WC) were investigated in an internally circulating fluidized-bed to evaluate bio-oil production. The pyrolyses were performed at 500 °C and the bio-oil yields from SS, PC, and WC were 45.2%, 44.4%, and 39.7% (dried and ash-free basis), respectively. The bio-oils were analyzed with an elemental analyzer, Karl-Fischer moisture titrator, bomb calorimeter, Fourier transformation infrared spectrometer, gel permeation chromatograph, and gas chromatography/mass spectrometry. The results show that the bio-oil from SS is rich in aliphatic and organonitrogen species, while the bio-oil from PC exhibits higher caloric value due to its higher carbon content and lower oxygen content in comparison with that from SS. The bio-oils from SS and PC have similar chemical composition of organonitrogen species. Most of the compounds detected in the bio-oil from WC are organooxygen species. Because of its high oxygen content, low H/C ratio, and caloric value, the bio-oil from WC is unfeasible for use as fuel feedstock, but possible for use as chemical feedstock.

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

    Science.gov (United States)

    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

  19. Effect of Fast Pyrolysis Conditions on the Biomass Solid Residues at High Temperatures (1000-1400°C)

    DEFF Research Database (Denmark)

    Trubetskaya, Anna; Jensen, Anker D.; Jensen, Peter Arendt

    Fast pyrolysis of wood and straw was conducted in a drop tube furnace (DTF) and compared with the experimental work on the wire-mesh reactor (WMR) to study the influence of temperature (1000-1400°C), biomass origin (softwood, hardwood, grass) and heating rate (1000°C/s, 10^4 °C/s) on the char yield...... to the parental fuel, whereas alfalfa straw char particle size remained unaltered with the higher temperatures. In this study, the retained shape of beechwood and herbaceous biomass samples is related to the presence of extractives and formation of silicates. Soot yield from herbaceous fuels occurs lower than...... and morphology. Scanning electron microscopy (SEM/EDS), elementary analysis, CAMSIZER XT, ash compositional analysis were applied to characterize the effect of operational conditions on the solid and gas products. Char yield from fast pyrolysis in the DFT setup was 2 to 6 % (daf) lower than in the WMR apparatus...

  20. Fast pyrolysis of biomass thermally pretreated by torrefaction

    Science.gov (United States)

    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 ...

  1. In-Situ Catalytic Fast Pyrolysis Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. Ex-Situ Catalytic Fast Pyrolysis Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    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.

  3. Cellulose-Lignin interactions during slow and fast pyrolysis

    NARCIS (Netherlands)

    Hilbers, T.J.; Wang, Z.; Pecha, B.; Westerhof, R.J.M.; Kersten, S.R.A.; Pelaez-Samaniego, M.R.; Garcia-Perez, M.

    2015-01-01

    The interactions between lignin and cellulose during the slow pyrolysis of their blends were studied by means of Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). Fast pyrolysis was studied using Pyrolysis-Gas Chromatography/Mass Spectroscopy (Py–GC/MS). Crystalline cellulose

  4. Impact of harvest time and cultivar on conversion of switchgrass to bio-oils via fast pyrolysis

    Science.gov (United States)

    The study of the effects of harvest time on switchgrass (Panicum virgatum L.) biomass and bioenergy production reported herein is the final part complementing two prior studies reporting on the harvest of six switchgrass cultivars grown at three northern United States locations over three years, har...

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

    Science.gov (United States)

    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.

  6. Palladium catalyzed hydrogenation of bio-oils and organic compounds

    Science.gov (United States)

    Elliott, Douglas C.; Hu, Jianli; Hart, Todd R.; Neuenschwander, Gary G.

    2008-09-16

    The invention provides palladium-catalyzed hydrogenations of bio-oils and certain organic compounds. Experimental results have shown unexpected and superior results for palladium-catalyzed hydrogenations of organic compounds typically found in bio-oils.

  7. Pyrolysis of waste animal fats in a fixed-bed reactor: Production and characterization of bio-oil and bio-char

    Energy Technology Data Exchange (ETDEWEB)

    Ben Hassen-Trabelsi, A., E-mail: aidabenhassen@yahoo.fr [Centre de Recherche et de Technologies de l’Energie (CRTEn), Technopôle Borj-Cédria, B.P 95, 2050, Hammam Lif (Tunisia); Kraiem, T. [Centre de Recherche et de Technologies de l’Energie (CRTEn), Technopôle Borj-Cédria, B.P 95, 2050, Hammam Lif (Tunisia); Département de Géologie, Université de Tunis, 2092, Tunis (Tunisia); Naoui, S. [Centre de Recherche et de Technologies de l’Energie (CRTEn), Technopôle Borj-Cédria, B.P 95, 2050, Hammam Lif (Tunisia); Belayouni, H. [Département de Géologie, Université de Tunis, 2092, Tunis (Tunisia)

    2014-01-15

    Highlights: • Produced bio-fuels (bio-oil and bio-char) from some animal fatty wastes. • Investigated the effects of main parameters on pyrolysis products distribution. • Determined the suitable conditions for the production of the maximum of bio-oil. • Characterized bio-oils and bio-chars obtained from several animal fatty wastes. - Abstract: Several animal (lamb, poultry and swine) fatty wastes were pyrolyzed under nitrogen, in a laboratory scale fixed-bed reactor and the main products (liquid bio-oil, solid bio-char and syngas) were obtained. The purpose of this study is to produce and characterize bio-oil and bio-char obtained from pyrolysis of animal fatty wastes. The maximum production of bio-oil was achieved at a pyrolysis temperature of 500 °C and a heating rate of 5 °C/min. The chemical (GC–MS analyses) and spectroscopic analyses (FTIR analyses) of bio-oil showed that it is a complex mixture consisting of different classes of organic compounds, i.e., hydrocarbons (alkanes, alkenes, cyclic compounds…etc.), carboxylic acids, aldehydes, ketones, esters,…etc. According to fuel properties, produced bio-oils showed good properties, suitable for its use as an engine fuel or as a potential source for synthetic fuels and chemical feedstock. Obtained bio-chars had low carbon content and high ash content which make them unattractive for as renewable source energy.

  8. 97e Intermediate Temperature Catalytic Reforming of Bio-Oil for Distributed Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    Marda, J. R.; Dean, A. M.; Czernik, S.; Evans, R. J.; French, R.; Ratcliff, M.

    2008-01-01

    With the world's energy demands rapidly increasing, it is necessary to look to sources other than fossil fuels, preferably those that minimize greenhouse emissions. One such renewable source of energy is biomass, which has the added advantage of being a near-term source of hydrogen. While there are several potential routes to produce hydrogen from biomass thermally, given the near-term technical barriers to hydrogen storage and delivery, distributed technologies such that hydrogen is produced at or near the point of use are attractive. One such route is to first produce bio-oil via fast pyrolysis of biomass close to its source to create a higher energy-density product, then ship this bio-oil to its point of use where it can be reformed to hydrogen and carbon dioxide. This route is especially well suited for smaller-scale reforming plants located at hydrogen distribution sites such as filling stations. There is also the potential for automated operation of the conversion system. A system has been developed for volatilizing bio-oil with manageable carbon deposits using ultrasonic atomization and by modifying bio-oil properties, such as viscosity, by blending or reacting bio-oil with methanol. Non-catalytic partial oxidation of bio-oil is then used to achieve significant conversion to CO with minimal aromatic hydrocarbon formation by keeping the temperature at 650 C or less and oxygen levels low. The non-catalytic reactions occur primarily in the gas phase. However, some nonvolatile components of bio-oil present as aerosols may react heterogeneously. The product gas is passed over a packed bed of precious metal catalyst where further reforming as well as water gas shift reactions are accomplished completing the conversion to hydrogen. The approach described above requires significantly lower catalyst loadings than conventional catalytic steam reforming due to the significant conversion in the non-catalytic step. The goal is to reform and selectively oxidize the

  9. A new approach to study fast pyrolysis of pulverized coal

    Energy Technology Data Exchange (ETDEWEB)

    Wang, J.; Yao, J.; Lin, W. [Chinese Academy of Sciences, Institute of Chemical Metallurgy Fast Reactions Laboratory, Beijing, BJ (China)

    2002-07-01

    An experimental study of the effects of varying bed temperature and coal particle size on the fast pyrolysis of pulverized coal in a downer reactor is described. A Datong bituminous coal (particle size 0.5 and 0.34 mm) was studied at temperatures ranging from 592{sup o} C to 720{sup o} C. The experiments were conducted in a batch apparatus. An on-line gas analyzer was used to measure carbon dioxide release curves. The experimental data were used to develop a pyrolysis model that quantifies the fast heating of fine coal particles. 14 refs., 4 figs., 2 tabs.

  10. Research on biomass fast pyrolysis for liquid fuel

    Energy Technology Data Exchange (ETDEWEB)

    Luo Zhongyang; Wang Shurong; Liao Yanfen; Zhou Jinsong; Gu Yueling; Cen Kefa

    2004-05-01

    A fluidized bed reactor with 3 kg h{sup -1} throughput operating at an atmospheric pressure with an inert atmosphere at 773 K has been used to produce bio-oils from the wood feedstocks such as Pterocarpus indicus, Cunninghamia lanceolata, and Fraxinus mandshurica, as well as from rice straw. The best oil-producing characteristics were for P. indicus and the worst were with rice straw. These data were used to design a larger scale unit of 20 kg h{sup -1} throughput, and to estimate the production costs at an industrial scale. The quality of the bio-oil produced remains poor, and a combination of high value products and energy applications are needed for profitability.

  11. Research on biomass fast pyrolysis for liquid fuel

    Energy Technology Data Exchange (ETDEWEB)

    Zhongyang Luo; Shurong Wang; Yanfen Liao; Jinsong Zhou; Yueling Gu; Kefa Cen [Zhejiang Univ., Clean Energy and Environment Engineering Key Lab. of Ministry of Education, Hangzhou (China)

    2004-05-01

    A fluidized bed reactor with 3 kg h{sup -1} throughput operating at an atmospheric pressure with an inert atmosphere at 773 K has been used to produce bio-oils from the wood feedstocks such as Pterocarpus indicus, Cunninghamia lanceolata, and Fraxinus mandshurica, as well as from rice straw. The best oil-producing characteristics were for P. indicus and the worst were with rice straw. These data were used to design a larger scale unit of 20 kg h{sup -1} throughput, and to estimate the production costs at an industrial scale. The quality of the bio-oil produced remains poor, and a combination of high value products and energy applications are needed for profitability. (Author)

  12. Catalytic steam reforming of bio-oil

    DEFF Research Database (Denmark)

    Trane, R.; Dahl, S.; Skjøth-Rasmussen, M.S.;

    2012-01-01

    in an early stage of development and far from industrial application mainly due the short lifetime of the catalysts, but there are also other aspects of the process which need clarification. Future investigations in SR of bio-oil could be to find a sulfur tolerant and stable catalyst, or to investigate...

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

    Energy Technology Data Exchange (ETDEWEB)

    Chornet, E.; Wang, D.; Montane, D. [National Renewable Energy Lab., Golden, CO (United States)] [and others

    1995-09-01

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

  14. Co-production of furfural and acetic acid from corncob using ZnCl2 through fast pyrolysis in a fluidized bed reactor.

    Science.gov (United States)

    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. Biomass fast pyrolysis in fluidized bed : product cleaning by in-situ filtration

    NARCIS (Netherlands)

    Wang, Xiaoquan

    2006-01-01

    This thesis is dedicated to the subject of fast pyrolysis in a fluid bed reactor. A large part of the work is related to reactor design aspects of fast pyrolysis, a subject that has not been considered sufficiently. Past research efforts were focussed mainly on the kinetics of wood pyrolysis and the

  16. Combustion characteristics and kinetics of bio-oil

    Institute of Scientific and Technical Information of China (English)

    Ruixia ZHANG; Zhaoping ZHONG; Yaji HUANG

    2009-01-01

    The combustion characteristics of bio-oils derived from rice husk and corn were studied by thermogravimetry analysis. According to the thermo-gravimetry (TG), differential thermogravimetry (DTG) and differential thermal analysis (DTA) curves of bio-oils in air and nitrogen atmosphere, we analyzed the combustion characteristics of different kinds of bio-oils in different atmospheres and worked out the combustion kinetics parameters of the bio-oil, providing reliable base data for the burning of bio-oil. The thermogravimetry indicated that the combustion process of bio-oil was divided into three stages. At the same time, the combustion process can be described by different order reaction models, and with the method of Coats-Redfern, the activation energy and frequency factor of different kinds of bio-oils were obtained.

  17. Production of bio-oil from fixed bed pyrolysis of bagasse

    Energy Technology Data Exchange (ETDEWEB)

    M. Asadullah; M.A. Rahman; M.M. Ali; M.S. Rahman; M.A. Motin; M.B. Sultan; M.R. Alam [University of Rajshahi, Rajshahi (Bangladesh). Department of Applied Chemistry and Chemical Technology

    2007-11-15

    The objective of this work was to produce renewable liquid fuel (bio-oil) from locally produced bagasse by pyrolysis in a batch feeding and fixed bed reactor. The experiments were performed at different temperatures ranging from 300 to 600{sup o}C. The bio-oil was collected from two condensers of different temperatures and defined as oil-1 and oil-2. The maximum total yield of bio-oil was found to be 66.0 wt% based on bagasse. The carbon based non-condensable gases were CO, CO{sub 2}, methane, ethane, ethene, propane and propene. The density and viscosity of oil-1 were found to be 1130 kg/m{sup 3} and 19.32 centipoise and that were 1050 kg/m{sup 3} and 4.25 centipoise for oil-2, respectively. The higher heating values (HHV) of them were 17.25 and 19.91 MJ/kg, respectively. The pH of the bio-oils was found to be around 3.5 and 4.5 for oil-1 and oil-2, respectively. The water, solid and ash contents of oil-1 and oil-2 were determined and found to be around 15, 0.02 and 0.03 wt% and 11, 0.01 and 0.02 wt%, respectively based on bagasse. 22 refs., 2 figs., 4 tabs.

  18. In-Situ Catalytic Fast Pyrolysis Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    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.

  19. Ex-Situ Catalytic Fast Pyrolysis Technology Pathway

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Specialists' workshop on fast pyrolysis of biomass

    Energy Technology Data Exchange (ETDEWEB)

    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)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-01-01

    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.

  2. Upgrading of bio-oil via acid-catalyzed reactions in alcohols : a mini review

    NARCIS (Netherlands)

    Hu, X.; Gunawan, R.; Mourant, D.; Mahmudul Hasan, M.D.; Wu, L.; Song, Y.; Lievens, C.; Li, C.Z.

    2017-01-01

    Bio-oil is a condensable liquid produced from the pyrolysis of biomass, which can be upgraded to biofuels. Bio-oil is corrosive as it contains significant amounts of carboxylic acids, creating difficulties in handling of bio-oil and applications of bio-oil. Acid-treatment of bio-oil in alcohols is

  3. Effect of glycerol as co-solvent on yields of bio-oil from rice straw through hydrothermal liquefaction.

    Science.gov (United States)

    Cao, Leichang; Zhang, Cheng; Hao, Shilai; Luo, Gang; Zhang, Shicheng; Chen, Jianmin

    2016-11-01

    This study examined the effect of glycerol used as a co-solvent on yields of bio-oil derived from rice straw through hydrothermal liquefaction (HTL). The reaction was conducted in a high-pressure batch reactor with different volume ratios of glycerol to water. The quality of the derived bio-oil was analyzed in terms of its elemental composition, heating value, water content, ash content, and acid number. Fourier transform infrared spectroscopy and gas chromatography-mass spectrometry were conducted to analyze the chemical composition of the derived bio-oils. The following optimal conditions were obtained: 1:1 vol ratio of glycerol to water with 5wt% of Na2CO3 at 260°C for 1h. Under these conditions, 50.31wt% of bio-oil and 26.65wt% of solid residue were produced. Therefore, glycerol can be used as a co-solvent in HTL of rice straw at moderate temperatures to obtain bio-oil with high yield and quality.

  4. Effects of preparation method on the performance of Ni/Al(2)O(3) catalysts for hydrogen production by bio-oil steam reforming.

    Science.gov (United States)

    Li, Xinbao; Wang, Shurong; Cai, Qinjie; Zhu, Lingjun; Yin, Qianqian; Luo, Zhongyang

    2012-09-01

    Steam reforming of bio-oil derived from the fast pyrolysis of biomass is an economic and renewable process for hydrogen production. The main objective of the present work has been to investigate the effects of the preparation method of Ni/Al(2)O(3) catalysts on their performance in hydrogen production by bio-oil steam reforming. The Ni/Al(2)O(3) catalysts were prepared by impregnation, co-precipitation, and sol-gel methods. XRD, XPS, H(2)-TPR, SEM, TEM, TG, and N(2) physisorption measurements were performed to characterize the texture and structure of the catalysts obtained after calcination and after their subsequent use. Ethanol and bio-oil model compound were selected for steam reforming to evaluate the catalyst performance. The catalyst prepared by the co-precipitation method was found to display better performance than the other two. Under the optimized reaction conditions, an ethanol conversion of 99% and a H(2) yield of 88% were obtained.

  5. Ultra-Low Carbon Emissions from Coal-Fired Power Plants through Bio-Oil Co-Firing and Biochar Sequestration.

    Science.gov (United States)

    Dang, Qi; Mba Wright, Mark; Brown, Robert C

    2015-12-15

    This study investigates a novel strategy of reducing carbon emissions from coal-fired power plants through co-firing bio-oil and sequestering biochar in agricultural lands. The heavy end fraction of bio-oil recovered from corn stover fast pyrolysis is blended and co-fired with bituminous coal to form a bio-oil co-firing fuel (BCF). Life-cycle greenhouse gas (GHG) emissions per kWh electricity produced vary from 1.02 to 0.26 kg CO2-eq among different cases, with BCF heavy end fractions ranging from 10% to 60%, which corresponds to a GHG emissions reduction of 2.9% to 74.9% compared with that from traditional bituminous coal power plants. We found a heavy end fraction between 34.8% and 37.3% is required to meet the Clean Power Plan's emission regulation for new coal-fired power plants. The minimum electricity selling prices are predicted to increase from 8.8 to 14.9 cents/kWh, with heavy end fractions ranging from 30% to 60%. A minimum carbon price of $67.4 ± 13 per metric ton of CO2-eq was estimated to make BCF power commercially viable for the base case. These results suggest that BCF co-firing is an attractive pathway for clean power generation in existing power plants with a potential for significant reductions in carbon emissions.

  6. Catalytic Conversion of Bio-Oil to Oxygen-Containing Fuels by Acid-Catalyzed Reaction with Olefins and Alcohols over Silica Sulfuric Acid

    Directory of Open Access Journals (Sweden)

    Qingwen Wang

    2013-09-01

    Full Text Available Crude bio-oil from pine chip fast pyrolysis was upgraded with olefins (1-octene, cyclohexene, 1,7-octadiene, and 2,4,4-trimethylpentene plus 1-butanol (iso-butanol, t-butanol and ethanol at 120 °C using a silica sulfuric acid (SSA catalyst that possesses a good catalytic activity and stability. Gas chromatography-mass spectrometry (GC-MS, Fourier transform infrared spectroscopy (FT-IR and proton nuclear magnetic resonance (1H-NMR analysis showed that upgrading sharply increased ester content and decreased the amounts of levoglucosan, phenols, polyhydric alcohols and carboxylic acids. Upgrading lowered acidity (pH value rose from 2.5 to >3.5, removed the unpleasant odor and increased hydrocarbon solubility. Water content dramatically decreased from 37.2% to about 7.0% and the heating value increased from 12.6 MJ·kg−1 to about 31.9 MJ·kg−1. This work has proved that bio-oil upgrading with a primary olefin plus 1-butanol is a feasible route where all the original heating value of the bio-oil plus the added olefin and alcohol are present in the resulting fuel.

  7. Summary of Fast Pyrolysis and Upgrading GHG Analyses

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. Catalytic Upgrading of bio-oil using 1-octene and 1-butanol over sulfonic acid resin catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhijun; Wang, Qingwen; Tripathi, Prabhat; Pittman, Charles U.

    2011-02-04

    Raw bio-oil from fast pyrolysis of biomass must be refined before it can be used as a transporation fuel, a petroleum refinery feed or for many other fuel uses. Raw bio-oil was upgraded with the neat model olefin, 1-octene, and with 1-octene/1-butanol mixtures over sulfonic acid resin catalysts frin 80 to 150 degrees celisus in order to simultaneously lower water content and acidity and to increase hydrophobicity and heating value. Phase separation and coke formation were key factors limiting the reaction rate during upgrading with neat 1-octene although octanols were formed by 1-octene hydration along with small amounts of octyl acetates and ethers. GC-MS analysis confirmed that olefin hydration, carboxylic acid esterification, acetal formation from aldehydes and ketones and O- and C-alkylations of phenolic compounds occurred simultaneously during upgrading with 1-octene/1-butanol mixtures. Addition of 1-butanol increased olefin conversion dramatically be reducing mass transfer restraints and serving as a cosolvent or emulsifying agent. It also reacted with carboxylic acids and aldehydes/ketones to form esters, and acetals, respectively, while also serving to stabilize bio-oil during heating. 1-Butanol addition also protected the catalysts, increasing catalyst lifetime and reducing or eliminationg coking. Upgrading sharply increased ester content and decreased the amounts of levoglucosan, polyhydric alcohols and organic acids. Upgrading lowered acidity (pH value rise from 2.5 to >3.0), removed the uppleasant ordor and increased hydrocarbon solubility. Water content decreased from 37.2% to < 7.5% dramatically and calorific value increased from 12.6 MJ kg to about 30.0 MJ kg.

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

    DEFF Research Database (Denmark)

    Hoff, Thomas C.; Gardner, David W.; Thilakaratne, Rajeeva

    2016-01-01

    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 represent...

  10. On-line catalytic upgrading of biomass fast pyrolysis products

    Institute of Scientific and Technical Information of China (English)

    LU Qiang; ZHU XiFeng; LI WenZhi; ZHANG Ying; CHEN DengYu

    2009-01-01

    Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was employed to achieve fast pyrolysis of biomass and on-line analysis of the pyrolysis vapors. Four biomass materials (poplar wood, fir wood, cotton straw and rice husk) were pyrolyzed to reveal the difference among their products. Moreover, catalytic cracking of the pyrolysis vapors from cotton straw was performed by using five catalysts, including two microporous zeolites (HZSM-5 and HY) and three mesoporous catalysts (ZrO2&TiO2, SBA-15 and AI/SBA-15). The results showed that the distribution of the pyrolytic products from the four materials differed a little from each other, while catalytic cracking could significantly alter the pyrolytic products. Those important primary pyrolytic products such as levoglucosen, hydroxyacetaldehyde and 1-hydroxy-2-propanone were decreased greatly after catalysis. The two microporous zeolites were ef-fective to generate high yields of hydrocarbons, while the three mesoporous materials favored the formation of furan, furfural and other furan compounds, as well as acetic acid.

  11. Application of fast pyrolysis biochar to a loamy soil - Effects on carbon and nitrogen dynamics and potential for carbon sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Bruun, E.W.

    2011-05-15

    Thermal decomposition of biomass in an oxygen-free environment (pyrolysis) produces bio-oil, syngas, and char. All three products can be used to generate energy, but an emerging new use of the recalcitrant carbon-rich char (biochar) is to apply it to the soil in order to enhance soil fertility and at the same time mitigate climate change by sequestering carbon in the soil. In general, the inherent physicochemical characteristics of biochars make these materials attractive agronomic soil conditioners. However, different pyrolysis technologies exist, i.e. slow pyrolysis, fast pyrolysis, and full gasification systems, and each of these influence the biochar quality differently. As of yet, there is only limited knowledge on the effect of applying fast pyrolysis biochar (FP-biochar) to soil. This PhD project provides new insights into the short-term impacts of adding FP-biochar to soil on the greenhouse gas (GHG) emissions and on soil carbon and nitrogen dynamics. The FP-biochars investigated in the thesis were generated at different reactor temperatures by fast pyrolysis of wheat straw employing a Pyrolysis Centrifuge Reactor (PCR). The carbohydrate content ranged from more than 35 % in FP-biochars made at a low reactor temperature (475 deg. C) down to 3 % in FP-biochars made at high temperatures (575 deg. C). The relative amount of carbohydrates in the FP-biochar was found to be correlated to the short-term degradation rates of the FP-biochars when applied to soil. Fast and slow pyrolysis of wheat straw resulted in two different biochar types with each their distinct physical structures and porosities, carbohydrate contents, particle sizes, pH values, BET surface areas, and elemental compositions. These different physicochemical properties obviously have different impacts on soil processes, which underscores that results obtained from soil studies using slow pyrolysis biochars (SP-biochar) are not necessarily applicable for FP-biochars. For example, the incorporation

  12. Hydraulic Systems with Tap Water versus Bio-oils

    DEFF Research Database (Denmark)

    Conrad, Finn

    1997-01-01

    Deals with the advantages of using pure tap water hydraulics versus bio-oils for suiteable applications. Focus is in particular on food processing industry.......Deals with the advantages of using pure tap water hydraulics versus bio-oils for suiteable applications. Focus is in particular on food processing industry....

  13. Green bio-oil extraction for oil crops

    Science.gov (United States)

    Zainab, H.; Nurfatirah, N.; Norfaezah, A.; Othman, H.

    2016-06-01

    The move towards a green bio-oil extraction technique is highlighted in this paper. The commonly practised organic solvent oil extraction technique could be replaced with a modified microwave extraction. Jatropha seeds (Jatropha curcas) were used to extract bio-oil. Clean samples were heated in an oven at 110 ° C for 24 hours to remove moisture content and ground to obtain particle size smaller than 500μm. Extraction was carried out at different extraction times 15 min, 30 min, 45 min, 60 min and 120 min to determine oil yield. The biooil yield obtained from microwave assisted extraction system at 90 minutes was 36% while that from soxhlet extraction for 6 hours was 42%. Bio-oil extracted using the microwave assisted extraction (MAE) system could enhance yield of bio-oil compared to soxhlet extraction. The MAE extraction system is rapid using only water as solvent which is a nonhazardous, environment-friendly technique compared to soxhlet extraction (SE) method using hexane as solvent. Thus, this is a green technique of bio-oil extraction using only water as extractant. Bio-oil extraction from the pyrolysis of empty fruit bunch (EFB), a biomass waste from oil palm crop, was enhanced using a biocatalyst derived from seashell waste. Oil yield for non-catalytic extraction was 43.8% while addition of seashell based biocatalyst was 44.6%. Oil yield for non-catalytic extraction was 43.8% while with addition of seashell-based biocatalyst was 44.6%. The pH of bio-oil increased from 3.5 to 4.3. The viscosity of bio-oil obtained by catalytic means increased from 20.5 to 37.8 cP. A rapid and environment friendly extraction technique is preferable to enhance bio-oil yield. The microwave assisted approach is a green, rapid and environmental friendly extraction technique for the production of bio-oil bearing crops.

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

    Science.gov (United States)

    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.

  15. Compositional analysis of bio-oil from pyrolysis of algae%海藻热解生物油的成分分析

    Institute of Scientific and Technical Information of China (English)

    王爽; 王谦; 徐姗楠; 姜秀民; 吉恒松; 何志霞

    2013-01-01

      为了明确海藻热解生物油的主要成分及热解工况对成分的影响,对海藻生物质(条浒苔、马尾藻)不同工况下热解制得的生物油进行气相色谱质谱联用分析。海藻类生物油成分除了含氮化合物外,主要是一些烃类、酮类、醛类、醇类和酚类化合物,以及较大分子量的羧酸及其衍生物,并包含了少量呋喃、吡喃、吡啶等衍生物的杂环化合物。条浒苔油中羧酸及其衍生物(37.85%)和烃类物质(16.61%)较多,而马尾藻生物油中甾族(30.16%)和醇类化合物(24.81%)较多,也检测出油酸、棕榈酸酯和花生酸。不同工况下产生的生物油在组成成分上非常相似,只是相对含量有所不同。热解温度对海藻油组分分布起了重要作用,而载气流量对热解海藻油组分分布的影响不明显。试验结果还表明海藻油中含氮化合物的形成主要与蛋白质的分解有关。海藻生物油相对于陆上植物热解生物油优点为高含烃量,低含氧量。海藻热解制油工艺中温度应控制在500~600℃之间,能达到较佳产油率和油品。%Though the work of pyrolysis of biomass for bio-oil has attained many achievements, the research on seaweed for bio-oil has been proceeding slowly. In this paper, fast pyrolysis experiments of algae biomass (Enteromorpha clathrata and Sargassum natans) were studied. Two kinds of algal bio-oil (Enteromorpha clathrata and Sargassum natans) obtained under different work conditions (400, 500, 600℃ and carried gas) were analyzed by using GC-MS analysis. Besides nitrogen-containing compounds, the major constituents of algal bio-oil were hydrocarbon, alcohols, ketones, aldehydes, and phenolic compounds, as well as large molecular weight carboxylic acids and their derivatives. The algal bio-oil also included a small amount of heterocyclic compounds (derivatives of furan, pyridine, pyran, etc.). It was seen from the

  16. Fast pyrolysis of biomass in fluidized bed reactor UNICAMP, Brazil: problems, causes and solutions; Pirolise rapida de biomassa em reator de leito fluidizado UNICAMP-Brasil: problemas, causas e solucoes

    Energy Technology Data Exchange (ETDEWEB)

    Mesa Perez, Juan Miguel; Marin Mesa, Henry Ramon [Bioware Tecnologia, Campinas, SP (Brazil); Rocha, Jose Dilcio; Olivares Gomez, Edgardo [Universidade Estadual de Campinas (NIPE/UNICAMP), SP (Brazil). Nucleo Interdisciplinar de Planejamento Energetico; Cortez, Luis Augusto Barbosa; Shimabukuro, Fabio Rodrigo; Vallin, Marco Jim Gui [Universidade Estadual de Campinas (FEAGRI/UNICAMP), SP (Brazil). Fac. de Engenharia Agricola

    2006-07-01

    The fluidized bed reactor developed by the researchers of the UNICAMP in the installations of the Sugar Cane Technology Center (CTC), in Piracicaba-SP, is the first reactor of biomass fast pyrolysis in Brazil to produce bio-oil. In this work the problems of operation with the reactor in functioning are presented as the emptying of gases produced in the pyrolysis by means of the biomass feeding system, the block of the thread of biomass feeding, the inert material sintering in the bed, etc. The possible causes are described. Thus it, the first ones could be solved, either by the reduction of the height of the inert bed, or by the increase of the wadding percentage of the thread, among others. These results of the exploratory tests make possible the steady work of the plant, greater knowledge of the phenomena that occur during the fast pyrolysis in flutizide bed, as well as the establishment of adjusted levels for the identified independent factors during the remaining experimental works. (author)

  17. The Fate of Trace Elements in Yanshan Coal during Fast Pyrolysis

    Directory of Open Access Journals (Sweden)

    Jiatao Dang

    2016-04-01

    Full Text Available In this study, a high-sulfur and high-ash yield coal sample obtained from the Yanshan coalfield in Yunnan, China was analyzed. A series of char samples was obtained by pyrolysis at various temperatures (300, 400, 500, 600, 700, 800, and 900 °C and at a fast heating rate (1000 °C/min. A comprehensive investigation using inductively coupled plasma mass spectrometry (ICP-MS, a mercury analyzer, ion-selective electrode (ISE measurements, X-ray diffraction (XRD analysis, and Fourier transform infrared (FTIR spectroscopy was performed to reveal the effects of the pyrolysis temperature on the transformation behavior of trace elements (TEs and the change in the mineralogical characteristics and functional groups in the samples. The results show that the TE concentrations in the raw coal are higher than the average contents of Chinese coal. The concentrations of Be, Li, and U in the char samples are higher than those in raw coal, while the opposite was observed for As, Ga, Hg, and Rb. The F and Se concentrations are initially higher but decrease with pyrolysis temperature, which is likely caused by associated fracturing with fluoride and selenide minerals. Uranium shows the highest enrichment degree, and Hg shows the highest volatilization degree compared to the other studied TEs. As the temperature increases, the number of OH groups decreases, and the mineral composition changes; for example, pyrite decomposes, while oldhamite and hematite occur in the chars. It is suggested that the behavior and fate of TEs in coal during fast pyrolysis are synergistically influenced by self-characteristic modes of occurrence and mineralogical characteristics.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yimin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Goldberg, Marshall [MRG and Associates, Nevada City, CA (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Abdullah, Zia [Battelle Memorial Inst., Columbus, OH (United States); Chadwell, Brad [Battelle Memorial Inst., Columbus, OH (United States); Taha, Rachid [Battelle Memorial Inst., Columbus, OH (United States); Hindin, Barry [Battelle Memorial Inst., Columbus, OH (United States); Ralston, Kevin [Battelle Memorial Inst., Columbus, OH (United States)

    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.

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

    Science.gov (United States)

    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.

  2. Biomass Fast Pyrolysis Reactors: A Review of a Few Scientific Challenges and of Related Recommended Research Topics Réacteur de pyrolyse rapide de la biomasse : une revue de quelques verrous scientifiques et d’actions de recherches recommandées

    Directory of Open Access Journals (Sweden)

    Lédé J.

    2013-06-01

    Full Text Available The use of biomass as an alternative energy resource requires its prior processing. Many options are possible. The present paper focuses on thermochemical routes and more specifically on fast pyrolysis carried out for the preparation of so called bio-oils. The optimization and scaling up of fast pyrolysis processes for improving bio oils yields and properties come up against several difficulties. The aim of the paper is to show that some of them are related to the lack of several basic scientific knowledges, more specifically at the level of the high temperature fast pyrolysis reactor. The analysis of these challenges (biomass sample thermal decomposition, biomass-reactor interactions, secondary reactions suggests the development of several research topics. L’utilisation de la biomasse en tant que ressource énergétique de substitution nécessite sa transformation préalable. De nombreuses options sont possibles. Cet article s’intéresse aux voies thermochimiques et plus spécifiquement à la pyrolyse rapide mise en oeuvre pour la préparation d’huiles de pyrolyse. L’optimisation et l’extrapolation des procédés de pyrolyse rapide pour améliorer les rendements et propriétés des huiles de pyrolyse se heurtent à plusieurs difficultés. Le but de cet article est de montrer que certaines sont liées au manque de certaines connaissances scientifiques de base, plus précisément au niveau du réacteur haute température. L’analyse de ces verrous (décomposition thermique d’un grain de biomasse, interactions biomasse-réacteur, réactions secondaires suggère le développement de plusieurs axes de recherche.

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

    Science.gov (United States)

    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.

  4. Bio-oil from Flash Pyrolysis of Agricultural Residues

    DEFF Research Database (Denmark)

    Ibrahim, Norazana

    bio-oils. Mainly the influence of feedstock type (wheat straw, rice husk and pine wood), feedstock water content and reactor temperature on the yield of char, bio-oil and gas were investigated. The storage stability of bio-oils with respect to changes in viscosity, water content and pH were...... liquid organics yield. In addition, the chemical compositions of the bio-oils and the chars of the investigated feedstocks were also analyzed. The utilization of the pyrolysis oil in static combustion equipments such as boilers and turbine have shown that the suitability of the pyrolysis oil...... to substitute fossil fuel. However, several limitations still arise due to the instability of the pyrolysis oil that may cause problems with transport and storage. Pyrolysis oil contains more than hundred of chemical compounds and has a wide range of volatility (different boiling points). The stability...

  5. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Ji-Lu, E-mail: triace@163.com; Zhu, Ming-Qiang; Wu, Hai-tang

    2015-09-15

    Highlights: • Swine carcasses can be converted to bio-oil by alkaline hydrothermal liquefaction. • It seems that the use of the bio-oil for heat or CHP is technically suitable. • Some valuable chemicals were found in the bio-oils. • The bio-oil and the solid residue constituted an energy efficiency of 93.63% for the feedstock. • The solid residue can be used as a soil amendment, to sequester C and for preparing activated carbon. - Abstract: It is imperative that swine carcasses are disposed of safely, practically and economically. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil was performed. Firstly, the effects of temperature, reaction time and pH value on the yield of each liquefaction product were determined. Secondly, liquefaction products, including bio-oil and solid residue, were characterized. Finally, the energy recovery ratio (ERR), which was defined as the energy of the resultant products compared to the energy input of the material, was investigated. Our experiment shows that reaction time had certain influence on the yield of liquefaction products, but temperature and pH value had bigger influence on the yield of liquefaction products. Yields of 62.2 wt% bio-oil, having a high heating value of 32.35 MJ/kg and a viscosity of 305cp, and 22 wt% solid residue were realized at a liquefaction temperature of 250 °C, a reaction time of 60 min and a pH value of 9.0. The bio-oil contained up to hundreds of different chemical components that may be classified according to functional groups. Typical compound classes in the bio-oil were hydrocarbons, organic acids, esters, ketones and heterocyclics. The energy recovery ratio (ERR) reached 93.63%. The bio-oil is expected to contribute to fossil fuel replacement in stationary applications, including boilers and furnaces, and upgrading processes for the bio-oil may be used to obtain liquid transport fuels.

  6. Effect of fast pyrolysis conditions on biomass solid residues at high temperatures

    DEFF Research Database (Denmark)

    Trubetskaya, Anna; Jensen, Peter Arendt; Jensen, Anker Degn

    2016-01-01

    Fast pyrolysis of wood and straw was conducted in a drop tube furnace (DTF) and compared with corresponding data from a wire mesh reactor (WMR) to study the influence of temperature (1000-1400)°C, biomass origin (pinewood, beechwood, wheat straw, alfalfa straw), and heating rate (103 °C/s, 104 °C...... in its half-width with respect to the parental fuel, whereas the alfalfa straw char particle size remained unaltered at higher temperatures. Soot particles in a range from 60 to 300 nm were obtained during fast pyrolysis. The soot yield from herbaceous fuels was lower than from wood samples, possibly due...

  7. CHARACTERIZATION OF BIO-OIL FROM PALM KERNEL SHELL PYROLYSIS

    Directory of Open Access Journals (Sweden)

    R. Ahmad

    2014-12-01

    Full Text Available Pyrolysis of palm kernel shell in a fixed-bed reactor was studied in this paper. The objectives were to investigate the effect of pyrolysis temperature and particle size on the products yield and to characterize the bio-oil product. In order to get the optimum pyrolysis parameters on bio-oil yield, temperatures of 350, 400, 450, 500 and 550 °C and particle sizes of 212–300 µm, 300–600 µm, 600µm–1.18 mm and 1.18–2.36 mm under a heating rate of 50 °C min-1 were investigated. The maximum bio-oil yield was 38.40% at 450 °C with a heating rate of 50 °C min-1 and a nitrogen sweep gas flow rate of 50 ml min-1. The bio-oil products were analysed by Fourier transform infra-red spectroscopy (FTIR and gas chromatography–mass spectroscopy (GCMS. The FTIR analysis showed that the bio-oil was dominated by oxygenated species. The phenol, phenol, 2-methoxy- and furfural that were identified by GCMS analysis are highly suitable for extraction from the bio-oil as value-added chemicals. The highly oxygenated oils need to be upgraded in order to be used in other applications such as transportation fuels.

  8. Hydrothermal liquefaction of aquatic plants to bio-oils

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, D.; Zhang, L.; Zhang, S.; Fu, H.; Chen, J. [Fudan Univ., Shanghai (China). Dept. of Environmental Science and Engineering

    2010-07-01

    This study investigated the feasibility of producing bio-oils from aquatic plants by hydrothermal liquefaction using 2 typical aquatic plants as feedstocks, notably Enteromorpha prolifera and water hyacinth which are typical aquatic plants found in seawater and freshwater. Bio-oil production from these 2 feedstocks was studied in a batch reactor at controlled temperatures under an initial partial pressure of 2.0 MPa N2. The effects of temperature and reaction time on the liquefaction products yields were also studied. GC-MS and elemental analysis were carried out to analyze the composition of bio-oils. The bio-oil produced from Enteromorpha prolifera contained mainly fatty acids, esters and quite a few heterocyclic compounds. Phenols and their derivatives were found to be the main compounds in bio-oils produced from water hyacinth. An elemental analysis revealed that bio-oils produced from the 2 aquatic plants have higher energy density. It was concluded that the use of aquatic plants as feedstock for liquid fuel can contribute to environmental protection and sustainable energy development by reducing greenhouse gas emissions associated with the burning of fossil fuels. 9 refs., 3 tabs.

  9. Demineralization of Sargassum spp. macroalgae biomass: selective hydrothermal liquefaction process for bio-oil production

    Directory of Open Access Journals (Sweden)

    Liz M Díaz-Vázquez

    2015-02-01

    Full Text Available Algae biomasses are considered a viable option for the production of biofuel because of their high yields of oil produced per dry weight. Brown macroalgae Sargassum spp. are one of the most abundant species of algae in the shores of Puerto Rico. Its availability in large quantity presents a great opportunity for use as a source of renewable energy. However, high ash content of macroalgae affects the conversion processes and the quality of resulting fuel products. This research studied the effect of different demineralization treatments of Sargassum spp. biomass, subsequent hydrothermal liquefaction (HTL and bio-oil characterization. Demineralization constituted five different treatments: nanopure water, nitric acid, citric acid, sulfuric acid, and acetic acid. Performance of demineralization was evaluated by analyzing both demineralized biomass and HTL products by the following analyses: total carbohydrates, proteins, lipids, ash content, caloric content, metals analysis, Fourier Transform Infrared - Attenuated Total Reflectance (FTIR-ATR Spectroscopy, Energy Dispersive Spectroscopy (EDS, Scanning Electron Microscopy (SEM, and GCMS analysis. HTL of Sargassum spp. before and after citric acid treatment, was performed in a 1.8 L batch reactor system at 350°C with a holding time of 60 min and high pressures (5-21 MPa. Demineralization treatment with nitric acid was found the most effective in reducing the ash content of the macroalgae biomass from 27.46% to 0.99% followed by citric acid treatment that could reduce the ash content to 7%. Citric acid did not show significant leaching of organic components such as carbohydrates and proteins, and represented a less toxic and hazardous option for demineralization. HTL of untreated and citric acid treated Sargassum spp. resulted in bio-oil yields of 18.4±0.1 % and 22.2±0.1 % (ash free dry basis, respectively.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    Qiangu Yan; Hossein Toghiani; Zhiyong Cai; Jilei Zhang

    2014-01-01

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

  12. Effect of temperature in fluidized bed fast pyrolysis of biomass: oil quality assessment in test units

    NARCIS (Netherlands)

    Westerhof, Roel Johannes Maria; Brilman, Derk Willem Frederik; van Swaaij, Willibrordus Petrus Maria; Kersten, Sascha R.A.

    2010-01-01

    Pine wood was pyrolyzed in a 1 kg/h fluidized bed fast pyrolysis reactor that allows a residence time of pine wood particles up to 25 min. The reactor temperature was varied between 330 and 580 °C to study the effect on product yields and oil composition. Apart from the physical−chemical analysis, a

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

    Science.gov (United States)

    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...

  14. Fast pyrolysis in a novel wire-mesh reactor: decomposition of pine wood and model compounds

    NARCIS (Netherlands)

    Hoekstra, E.; Swaaij, van W.P.M.; Kersten, S.R.A.; Hogendoorn, J.A.

    2012-01-01

    In fast pyrolysis, biomass decomposition processes are followed by vapor phase reactions. Experimental results were obtained in a unique wire-mesh reactor using pine wood, KCl impregnated pine wood and several model compounds (cellulose, xylan, lignin, levoglucosan, glucose). The wire-mesh reactor w

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, S. B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Valkenburg, C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Walkton, C. W. [Dept. of Energy (DOE), Washington DC (United States); Elliott, D. C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Holladay, J. E. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Stevens, D. J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kinchin, C. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Czernik, S. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    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.

  16. Influence of Crystal Allomorph and Crystallinity on the Products and Behavior of Cellulose during Fast Pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-09-06

    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.

  17. Catalytic Hydrotreatment of Fast Pyrolysis Oil : Model Studies on Reaction Pathways for the Carbohydrate Fraction

    NARCIS (Netherlands)

    Wildschut, J.; Arentz, J.; Rasrendra, C. B.; Venderbosch, R. H.; Heeres, H. J.

    2009-01-01

    Fast pyrolysis oil can be upgraded by a catalytic hydrotreatment (250-400 degrees C, 100-200 bar) using heterogeneous catalysts such as Ru/C to hydrocarbon-like products that can serve as liquid transportation fuels. Insight into the complex reaction pathways of the various component fractions durin

  18. Fast pyrolysis of biomass : an experimental study on mechanisms influencing yield and composition of the products

    NARCIS (Netherlands)

    Hoekstra, Elly

    2011-01-01

    Pyrolysis oil originating from biomass has the potential to replace ‘crude fossil oil’ and to produce fuels and chemicals in a more sustainable way. The favorable perspective of fast pyrolysis as biomass pre-treatment step is directly related to the production of a liquid as main product and the sig

  19. Hydrotreatment of Fast Pyrolysis Oil Using Heterogeneous Noble-Metal Catalysts

    NARCIS (Netherlands)

    Wildschut, Jelle; Mahfud, Farchad H.; Venderbosch, Robbie H.; Heeres, Hero J.

    2009-01-01

    Fast pyrolysis oils from lignocellulosic biomass are promising second-generation biofuels. Unfortunately, the application range for such oils is limited because of the high acidity (pH similar to 2.5) and the presence of oxygen in a variety of chemical functionalities, and upgrading of the oils is r

  20. Effect of Temperature in Fluidized Bed Fast Pyrolysis of Biomass: Oil Quality Assessment in Test Units

    NARCIS (Netherlands)

    Westerhof, R.J.M.; Brilman, D.W.F.; Swaaij, van W.P.M.; Kersten, S.R.A.

    2010-01-01

    Pine wood was pyrolyzed in a 1 kg/h fluidized bed fast pyrolysis reactor that allows a residence time of pine wood particles up to 25 min. The reactor temperature was varied between 330 and 580 °C to study the effect on product yields and oil composition. Apart from the physical−chemical analysis, a

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

    Science.gov (United States)

    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...

  2. Insights in the hydrotreatment of fast pyrolysis oil using a ruthenium on carbon catalyst

    NARCIS (Netherlands)

    Wildschut, Jelle; Iqbal, Muhammad; Mahfud, Farchad H.; Melian-Cabrera, Ignacio; Venderbosch, Robbie H.; Heeres, Hero J.

    2010-01-01

    The use of Ru/C (5%-wt.) as a catalyst for the hydrogenation of fast pyrolysis oil was explored at 350 degrees C and 200 bar pressure in a batch reactor set-up with the main objective to determine the effect of the reaction time on the oil yield and elemental compositions of the product phases. High

  3. Pyrolysis of waste animal fats in a fixed-bed reactor: production and characterization of bio-oil and bio-char.

    Science.gov (United States)

    Ben Hassen-Trabelsi, A; Kraiem, T; Naoui, S; Belayouni, H

    2014-01-01

    Several animal (lamb, poultry and swine) fatty wastes were pyrolyzed under nitrogen, in a laboratory scale fixed-bed reactor and the main products (liquid bio-oil, solid bio-char and syngas) were obtained. The purpose of this study is to produce and characterize bio-oil and bio-char obtained from pyrolysis of animal fatty wastes. The maximum production of bio-oil was achieved at a pyrolysis temperature of 500 °C and a heating rate of 5 °C/min. The chemical (GC-MS analyses) and spectroscopic analyses (FTIR analyses) of bio-oil showed that it is a complex mixture consisting of different classes of organic compounds, i.e., hydrocarbons (alkanes, alkenes, cyclic compounds...etc.), carboxylic acids, aldehydes, ketones, esters,...etc. According to fuel properties, produced bio-oils showed good properties, suitable for its use as an engine fuel or as a potential source for synthetic fuels and chemical feedstock. Obtained bio-chars had low carbon content and high ash content which make them unattractive for as renewable source energy. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Thermogravimetric investigation on the degradation properties and combustion performance of bio-oils.

    Science.gov (United States)

    Ren, Xueyong; Meng, Jiajia; Moore, Andrew M; Chang, Jianmin; Gou, Jinsheng; Park, Sunkyu

    2014-01-01

    The degradation properties and combustion performance of raw bio-oil, aged bio-oil, and bio-oil from torrefied wood were investigated through thermogravimetric analysis. A three-stage process was observed for the degradation of bio-oils, including devolatilization of the aqueous fraction and light compounds, transition of the heavy faction to solid, and combustion of carbonaceous residues. Pyrolysis kinetics parameters were calculated via the reaction order model and 3D-diffusion model, and combustion indexes were used to qualitatively evaluate the thermal profiles of tested bio-oils for comparison with commercial oils such as fuel oils. It was found that aged bio-oil was more thermally instable and produced more combustion-detrimental carbonaceous solid. Raw bio-oil and bio-oil from torrefied wood had comparable combustion performance to fuel oils. It was considered that bio-oil has a potential to be mixed with or totally replace the fuel oils in boilers.

  5. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil.

    Science.gov (United States)

    Zheng, Ji-Lu; Zhu, Ming-Qiang; Wu, Hai-tang

    2015-09-01

    It is imperative that swine carcasses are disposed of safely, practically and economically. Alkaline hydrothermal liquefaction of swine carcasses to bio-oil was performed. Firstly, the effects of temperature, reaction time and pH value on the yield of each liquefaction product were determined. Secondly, liquefaction products, including bio-oil and solid residue, were characterized. Finally, the energy recovery ratio (ERR), which was defined as the energy of the resultant products compared to the energy input of the material, was investigated. Our experiment shows that reaction time had certain influence on the yield of liquefaction products, but temperature and pH value had bigger influence on the yield of liquefaction products. Yields of 62.2wt% bio-oil, having a high heating value of 32.35MJ/kg and a viscosity of 305cp, and 22wt% solid residue were realized at a liquefaction temperature of 250°C, a reaction time of 60min and a pH value of 9.0. The bio-oil contained up to hundreds of different chemical components that may be classified according to functional groups. Typical compound classes in the bio-oil were hydrocarbons, organic acids, esters, ketones and heterocyclics. The energy recovery ratio (ERR) reached 93.63%. The bio-oil is expected to contribute to fossil fuel replacement in stationary applications, including boilers and furnaces, and upgrading processes for the bio-oil may be used to obtain liquid transport fuels. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. VISCOSITY ANALYSIS OF EMPTY FRUIT BUNCH (EFB BIO-OIL

    Directory of Open Access Journals (Sweden)

    Z.S. Nazirah

    2013-12-01

    Full Text Available Empty fruit bunches (EFB are one of the solid wastes produced by the palm oil industry, which is increasing rapidly. The aim of this paper is to analyse the viscosity of empty fruit bunch (EFB bio-oil that can be extracted from all solid waste EFB as a sample, and a few processes were executed. The samples underwent two processes, which were pre-treatment and pyrolysis. The pre-treatment involved three processes, namely, cutting, shredding and sieving, which were necessary in order to prepare EFB into a particle size suitable for the reactor. After that, the samples were fed into the feedback reactor as feedstock for the pyrolysis process to produce bio-oil. Once the bio-oil was produced, its viscosity was tested using the Brookfield Viscometer in two conditions: before and after the chemical reaction. The bio-oil was treated by adding 10 ml and 20 ml of acetone respectively through the chemical reaction. The viscosity test was carried out at different temperatures, which were 25°C, 30°C, 35°C, 40°C, 45°C and 50°C respectively. The observed viscosity of the EFB bio-oil varied and was higher as the temperature decreased. In addition, the viscosity of the EFB bio-oil was higher when it reacted chemically with the acetone added. Therefore, the results showed that the chemical reaction with acetone has the potential to increase the viscosity of EFB bio-oil.

  7. 生物质快速热裂解主要参数对产物产率及其分布的影响%Effects of biomass fast pyrolysis key parameters on yields and distributions of products

    Institute of Scientific and Technical Information of China (English)

    刘荣厚; 牛卫生; 于晓芳; 李天舒; 张春梅; 李金洋

    2003-01-01

    Sawdust fast pyrolysis experiments were conducted in a fluidized bed reactor at a biomass feed rate of 0.80~2.00 kg*h-1. The effects of process conditions, like fluidized bed reactor temperature, feed size and vapor residence time on the product yields were studied. When reactor temperatures were varied from 450℃ to 600℃, a maximum bio-oil yield of 53.33%wt was achieved at 500℃ with a char and gaseous yields of 8.97 %wt and 37.70%wt respectively. The particle size of sawdust varied in the range of 0~0.90 mm. The yield of bio-oil was maximum (58.23%wt of biomass feed) for the particle size of 0.45~0.60 mm with a char yield of 8.23%wt. Vapor residence times were ranged from 0.80 to 1.50 s at temperature of 500℃ with a particle size less than 0.20 mm. A maximum bio-oil yield of 62.60%wt was achieved at 500℃ when the vapor residence time was held constant at 0.80 s. However, at the longer residence time(1.50 s), bio-oil yield was slightly lower. Bio-oil is a miscible mixture of polar organics with water. The results showed the potential of sawdust fast pyrolysis for liquid hydrocarbon fuels production.%在生物质喂入率为0.8~2.0 kg*h-1的流化床上以木屑为原料进行了快速热裂解试验,系统研究了木屑热裂解过程中的流化床反应器温度、生物质粒径和气相滞留期三个主要参数对热裂解产物产率的影响.结果表明,当反应器温度在450~600℃之间变化时,在500℃条件下,生物油产率最高,其值为53.33%,而木炭及不可冷凝气体产率分别为8.97%和37.70%.当温度为500℃,木屑粒径在0.90 mm以下时,粒径在0.45~0.60 mm范围内的生物油产率最大,达到58.23%,这时木炭产率为8.23%.对粒径小于0.20 mm的木屑在温度500℃,气相滞留期0.80, 1.20, 1.50 s三个量级上的热裂解表明,气相滞留期为0.80 s时,生物油产率达到最大值为62.60%.但是,当气相滞留期较长时(1.50 s),生物油产率稍有下降.生物油是极性有机物

  8. Catalytic Hydrogenation of Bio-Oil for Chemicals and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, Douglas C.

    2006-02-14

    The scope of work includes optimizing processing conditions and demonstrating catalyst lifetime for catalyst formulations that are readily scaleable to commercial operations. We use a bench-scale, continuous-flow, packed-bed, catalytic, tubular reactor, which can be operated in the range of 100-400 mL/hr., from 50-400 C and up to 20MPa (see Figure 1). With this unit we produce upgraded bio-oil from whole bio-oil or useful bio-oil fractions, specifically pyrolytic lignin. The product oils are fractionated, for example by distillation, for recovery of chemical product streams. Other products from our tests have been used in further testing in petroleum refining technology at UOP and fractionation for product recovery in our own lab. Further scale-up of the technology is envisioned and we will carry out or support process design efforts with industrial partners, such as UOP.

  9. Combustion Characterization of Individual Bio-oil Droplets

    DEFF Research Database (Denmark)

    Hansen, Brian Brun; Jensen, Peter Arendt

    2015-01-01

    was tested in a single particle reactor at conditions relevant for suspension firing (A: 1200 °C, 5.5 % O2; B: 1200 °C, 2.9 % O2 and C: 990 °C, 5.5 % O2). The slurries were tested to optimize the bio-oil composition for use as an alternative power plant start-up fuel. Pyrolysis times for 5 mg bio-oil samples...... and thereby decreased flame stability. Most promising were oil or diesel (not palm oil) containing slurries (1 and 5) with heating values in the range of 15 MJ/kg.......Single droplet combustion characteristics has been investigated for bio-oil slurries, containing biomass residue, and compared to conventional fuels for pulverized burners, such as fuel oil (start up) and wood chips (solid biomass fuel). The investigated fuels ignition delays and pyrolysis behavior...

  10. Characterization of Deactivated Bio-oil Hydrotreating Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Huamin; Wang, Yong

    2015-10-06

    Deactivation of bio-oil hydrotreating catalysts remains a significant challenge because of the poor quality of pyrolysis bio-oil input for hydrotreating and understanding their deactivation mode is critical to developing improved catalysts and processes. In this research, we developed an understanding of the deactivation of two-step bio-oil hydrotreating catalysts (sulfided Ru/C and sulfided CoMo/C) through detailed characterization of the catalysts using various complimentary analytical techniques. Severe fouling of both catalysts by carbonaceous species was the major form of deactivation, which is consistent with the significant loss of surface area and pore volume of both deactivated catalysts and the significant increase of the bulk density. Further analysis of the carbonaceous species by thermogravimetric analysis and x-ray photoelectron spectroscopy indicated that the carbonaceous species was formed by condensation reaction of active species such as sugars and sugar derivatives (aldehydes and ketones) in bio-oil feedstock during bio-oil hydrotreating under the conditions and catalysts used. Microscopy results did not show metal sintering of the Ru/C catalyst. However, X-ray diffraction indicated a probable transformation of the highly-active CoMoS phase in the sulfided CoMo/C catalyst to Co8S9 and MoS2 phase with low activity. Loss of the active site by transport of inorganic elements from the bio-oil and the reactor construction material onto the catalyst surface also might be a cause of deactivation as indicated by elemental analysis of spent catalysts.

  11. Entrained flow gasification of coal/bio-oil slurries

    DEFF Research Database (Denmark)

    Feng, Ping; Lin, Weigang; Jensen, Peter Arendt;

    2016-01-01

    Coal/bio-oil slurry (CBS) is a new partial green fuel for bio-oil utilization. CBS reacts with gasification agents at high temperatures and converts into hydrogen and carbon monoxide. This paper provides a feasibility study for the gasification of CBS in an atmospheric entrained flow reactor...... for syngas production. Experiments have shown that CBS can be successfully processed and gasified in the entrained flow reactor to produce syngas with almost no tar content and low residual carbon formation. High reactor temperature and steam/carbon ratio is favourable for H2 production. At 1400 °C...

  12. Atmospheric Hydrodeoxygenation of Biomass Fast Pyrolysis Vapor by MoO3

    DEFF Research Database (Denmark)

    Zhou, Guofeng; Jensen, Peter Arendt; Le, Duy Michael

    2016-01-01

    MoO3 has been tested as a catalyst in hydrodeoxygenation (HDO) of both model compounds (acetone and guaiacol) and real biomass pyrolysis vapors under atmospheric pressure. The pyrolysis vapor was obtained by fast pyrolysis of wood or lignin in a continuous fast pyrolysis reactor at a fixed...... temperature of 500 °C, and it subsequently passed through a downstream, close coupled, fixed bed reactor containing the MoO3 catalyst. The influences of the catalyst temperature and the concentration of H2 on the HDO of the pyrolysis vapors were investigated. The level of HDO of the biomass pyrolysis vapors...... was not significant at temperatures below 400 °C. At 450 °C catalyst temperature and 93 vol % H2 concentration, the wood pyrolysis vapor was more active toward cracking forming gas species instead of performing the desired HDO forming hydrocarbons. The lignin pyrolysis vapor was more resistant to cracking and yielded...

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

    Science.gov (United States)

    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.

  14. Chemicals derived from pyrolysis bio-oils as antioxidants in fuels and lubricants

    Science.gov (United States)

    Softwood and hardwood lignins and hardwood were pyrolyzed to produce bio-oils to produce lignin-derived bio-oils of which phenols were the major component. These bio-oils were extracted with alkali to yield a range of lignin-related phenols having molecular weights (MWs) from 110 to 344. When tested...

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

    OpenAIRE

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

    2016-01-01

    Background 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 th...

  16. Techno-economic assessment of fast pyrolysis for the valorization of short rotation coppice cultivated for phytoextraction

    OpenAIRE

    Kuppens, Tom; VAN DAEL, Miet; Vanreppelen, Kenny; Thewys, Theo; Yperman, Jan; Carleer, Robert; SCHREURS, Sonja; Van Passel, Steven

    2014-01-01

    The main barrier in the commercialization of phytoextraction as a sustainable alternative for remediating metal contaminated soils is its long time period, which can be countered by biomass valorization. From an environmental point of view, fast pyrolysis of the biomass is promising because its lower process temperature prevents metal volatilization. The remaining question is whether fast pyrolysis is also preferred from an economic point of view. Therefore, a techno-economic ass...

  17. EXPERIMENTAL STUDY ON BIO-OIL PYROLYSIS/GASIFICATION

    Directory of Open Access Journals (Sweden)

    Mou Zhang

    2010-02-01

    Full Text Available This study aims to understand the mechanism of bio-oil gasification and the influence of operating parameters on the properties of the gas products. Firstly, the pyrolysis/gasification of bio-oil was performed using a thermogravimetric analyzer (TGA. The evaporation of gas products from bio-oil were measured on-line with coupled Fourier Transform Infrared Spectroscopy (FTIR. The main gas products were CO, CO2, CH4, H2O, and light hydrocarbons, etc. Organics mainly evolved out at lower temperature (100-200°C, while the cracking of heavy hydrocarbon components took place at higher temperature (>200°C. Simultaneously, the gasification behavior of bio-oil was investigated in a fixed bed gasification reactor under different temperature and residence time. The gas product evolving was checked using micro-gas chromatography. It was observed that the yield of CO and H2 increased with increasing gasification temperature above 600°C, and the maximum value was obtained at 800°C. Prolonging the residence time was not favorable for the upgrading of syngas quality.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Susanne B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Snowden-Swan, Lesley J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Meyer, Pimphan A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Zacher, Alan H. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Olarte, Mariefel V. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Wang, Huamin [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Drennan, Corinne [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    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.

  19. Phosphorus recovery from sewage sludge char ash

    NARCIS (Netherlands)

    Atienza-Martinez, M.; Gea, G.; Arauzo, J.; Kersten, S.R.A.; Kootstra, A.M.J.

    2014-01-01

    Phosphorus was recovered from the ash obtained after combustion at different temperatures (600 °C, 750 °C and 900 °C) and after gasification (at 820 °C using a mixture of air and steam as fluidising agent) of char from sewage sludge fast pyrolysis carried out at 530 °C. Depending on the leaching con

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

    Energy Technology Data Exchange (ETDEWEB)

    Chornet, E.; Wang, D.; Czernik, S. [National Renewable Energy Lab., Golden, CO (United States)] [and others

    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.

  1. Bio-oil fueled diesel power plant; Biooeljyllae toimiva dieselvoimala

    Energy Technology Data Exchange (ETDEWEB)

    Vuorinen, A. [Modigen Oy, Helsinki (Finland)

    1995-12-31

    The project mission is to develop a diesel power plant which is capable of using liquid bio-oils as the main fuel of the power plant. The applicable bio-oils are rape seed oils and pyrolysis oils. The project was started in 1994 by installing a 1.5 MW Vasa 4L32 engine in VTT Energy laboratory in Otaniemi. During 1995 the first tests with the rape seed oils were made. The tests show that the rape seed oil can be used in Vasa 32 engines without difficulties. In the second phase of the project during 1996 and 1997 pyrolysis oil made of wood will be tested. Finally a diesel power plant concept with integrated pyrolysis oil, electricity and heat production will be developed

  2. Bio-oil fuelled diesel power plant; Biooeljyllae toimiva dieselvoimala

    Energy Technology Data Exchange (ETDEWEB)

    Vuorinen, A. [Modigen Oy, Helsinki (Finland)

    1997-12-01

    The project mission is to develop a diesel power plant which is capable of using liquid bio-oils as the main fuel of the power plant. The applicable bio-oils are rape seed oils and pyrolysis oils. The project was started in 1994 by installing a 1.5 MW Vasa 4L32 engine in VTT Energy laboratory in Otaniemi. During 1995 the first tests with the rape seed oils were made. The tests show that the rape seed oil can be used in Vasa 32 engines without difficulties. In the second phase of the project during 1996 pyrolysis oil made of wood was tested. Finally a diesel power plant concept with integrated pyrolysis oil, electricity and heat production will be developed

  3. 生物质快速热裂解炭的分析及活化研究%Characterization and Activation of Pyrolytic Char from Fast Pyrolysis

    Institute of Scientific and Technical Information of China (English)

    尹倩倩; 王树荣

    2013-01-01

    采用化学(KOH)方法对两种具有代表性的生物质原料(花梨木和稻壳)的快速热裂解固体产物-热解炭进行了活化,并采用氮吸附、X射线衍射(XRD)、傅里叶红外光谱分析(FTIR)和扫描电镜(SEM)技术测试了热解炭的结构特性、表面特性以及物理化学性质.结果表明,这两种热解炭经过活化后可以获得许多优良的性质,固定碳含量增加,灰分含量减少.同时,活化后BET比表面积迅速增大,超过1100m2/g,而且热解炭的石墨化程度都有所加深.热解炭通过活化过程可以实现其高品质利用,有利于生物质热裂解技术的工业化发展.%The pyrolytic chars from fast pyrolysis of rosewood and rice husk have been activated with KOH solvent. The texture and structure, surface properties and physico-chemical properties of the pyrolytic chars have been characterized by N2 physisorption, X-ray diffraction (XRD), Fourier transform infrared spectroscopy ( FTIR) and Scanning electron microscope ( SEM). Compared with the original pyrolytic chars, the activated chars had higher fixed carbon content and lower ash content. The BET surface area increased beyond 1100m /g after activation. Moreover,the activated chars had higher graphitization degree. Through this activation process, high grade utilization of pyrolytic char will be achieved, as will benefit the industrialization of biomass fast pyrolysis technology.

  4. Simultaneous fast pyrolysis and catalytic upgrading of lignin to obtain a marine diesel fuel

    DEFF Research Database (Denmark)

    Zhou, Guofeng

    The topic of this Ph.D. project is to convert lignin, a by-product from a 2nd generation bio-ethanol plant, into a marine diesel fuel by fast pyrolysis followed with catalytic upgrading of the pyrolysis vapor. Lignin, a major component of lignocellulosic biomass, is underutilized in the 2nd...... generation bio-ethanol plants. Shipping industry on the other hand is looking for clean alternative fuels in order to meet stricter fuel quality and emission standards. To convert lignin into a renewable marine diesel fuel will both accelerate the development of modern bio-refinery and transfer the marine...

  5. Upgrading of crude algal bio-oil in supercritical water.

    Science.gov (United States)

    Duan, Peigao; Savage, Phillip E

    2011-01-01

    We determined the influence of a Pt/C catalyst, high-pressure H2, and pH on the upgrading of a crude algal bio-oil in supercritical water (SCW). The SCW treatment led to a product oil with a higher heating value (∼42 MJ/kg) and lower acid number than the crude bio-oil. The product oil was also lower in O and N and essentially free of sulfur. Including the Pt/C catalyst in the reactor led to a freely flowing liquid product oil with a high abundance of hydrocarbons. Overall, many of the properties of the upgraded oil obtained from catalytic treatment in SCW are similar to those of hydrocarbon fuels derived from fossil fuel resources. Thus, this work shows that the crude bio-oil from hydrothermal liquefaction of a microalga can be effectively upgraded in supercritical water in the presence of a Pt/C catalyst. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-01-18

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

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

    Science.gov (United States)

    Sanna, Aimaro; Andrésen, John M

    2012-10-01

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

  9. Pyrolysis of Parinari polyandra Benth fruit shell for bio-oil production

    Directory of Open Access Journals (Sweden)

    Temitope E. Odetoye

    2014-09-01

    Full Text Available Non-conventional agricultural residues such as Parinari polyandra Benth fruit shell (PPBFS are potential sources of biomass feedstock that have not been investigated for bio oil production. In this study, PPBFS was pyrolyzed via an intermediate pyrolysis process for the production of bio oil. The bio oils were obtained using a fixed bed reactor within a temperature range of 375–550 oC and were characterized to determine their physicochemical properties. The most abundant organic compounds present were acetic acid, toluene, 2-cyclopenten-1-one, 2-furanmethanol, phenol, guaiacol and 2,6-dimethoxyphenol. The bio-oil produced at 550 oC possessed a higher quantity of desirable compounds than those produced at lower temperatures. The presence of acetic acids in the bio-oil suggested the need to upgrade the bio-oil before utilization as a fuel source.

  10. Production of hydrogen, liquid fuels, and chemicals from catalytic processing of bio-oils

    Science.gov (United States)

    Huber, George W; Vispute, Tushar P; Routray, Kamalakanta

    2014-06-03

    Disclosed herein is a method of generating hydrogen from a bio-oil, comprising hydrogenating a water-soluble fraction of the bio-oil with hydrogen in the presence of a hydrogenation catalyst, and reforming the water-soluble fraction by aqueous-phase reforming in the presence of a reforming catalyst, wherein hydrogen is generated by the reforming, and the amount of hydrogen generated is greater than that consumed by the hydrogenating. The method can further comprise hydrocracking or hydrotreating a lignin fraction of the bio-oil with hydrogen in the presence of a hydrocracking catalyst wherein the lignin fraction of bio-oil is obtained as a water-insoluble fraction from aqueous extraction of bio-oil. The hydrogen used in the hydrogenating and in the hydrocracking or hydrotreating can be generated by reforming the water-soluble fraction of bio-oil.

  11. Fast Pyrolysis of Four Lignins from Different Isolation Processes Using Py-GC/MS

    Directory of Open Access Journals (Sweden)

    Xiaona Lin

    2015-06-01

    Full Text Available Pyrolysis is a promising approach that is being investigated to convert lignin into higher value products including biofuels and phenolic chemicals. In this study, fast pyrolysis of four types of lignin, including milled Amur linden wood lignin (MWL, enzymatic hydrolysis corn stover lignin (EHL, wheat straw alkali lignin (AL and wheat straw sulfonate lignin (SL, were performed using pyrolysis gas-chromatography/mass spectrometry (Py-GC/MS. Thermogravimetric analysis (TGA showed that the four lignins exhibited widely different thermolysis behaviors. The four lignins had similar functional groups according to the FTIR analysis. Syringyl, guaiacyl and p-hydroxyphenylpropane structural units were broken down during pyrolysis. Fast pyrolysis product distributions from the four lignins depended strongly on the lignin origin and isolation process. Phenols were the most abundant pyrolysis products from MWL, EHL and AL. However, SL produced a large number of furan compounds and sulfur compounds originating from kraft pulping. The effects of pyrolysis temperature and time on the product distributions from corn stover EHL were also studied. At 350 °C, EHL pyrolysis mainly produced acids and alcohols, while phenols became the main products at higher temperature. No obvious influence of pyrolysis time was observed on EHL pyrolysis product distributions.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  13. Bio-oil based biorefinery strategy for the production of succinic acid

    DEFF Research Database (Denmark)

    Wang, Caixia; Thygesen, Anders; Liu, Yilan

    2013-01-01

    /L by addition of 20 v/v% AP-bio-oil. When enzymatic hydrolysate of corn stover was used as carbon source, 10.3 g/L succinic acid was produced. The obtained succinic acid concentration increased to 11.5 g/L when 12.5 v/v% AP-bio-oil was added. However, it decreased to 8 g/L when 50 v/v% AP-bio-oil was added. GC...

  14. Bio-oil based biorefinery strategy for the production of succinic acid

    Science.gov (United States)

    2013-01-01

    Background Succinic acid is one of the key platform chemicals which can be produced via biotechnology process instead of petrochemical process. Biomass derived bio-oil have been investigated intensively as an alternative of diesel and gasoline fuels. Bio-oil could be fractionized into organic phase and aqueous phase parts. The organic phase bio-oil can be easily upgraded to transport fuel. The aqueous phase bio-oil (AP-bio-oil) is of low value. There is no report for its usage or upgrading via biological methods. In this paper, the use of AP-bio-oil for the production of succinic acid was investigated. Results The transgenic E. coli strain could grow in modified M9 medium containing 20 v/v% AP-bio-oil with an increase in OD from 0.25 to 1.09. And 0.38 g/L succinic acid was produced. With the presence of 4 g/L glucose in the medium, succinic acid concentration increased from 1.4 to 2.4 g/L by addition of 20 v/v% AP-bio-oil. When enzymatic hydrolysate of corn stover was used as carbon source, 10.3 g/L succinic acid was produced. The obtained succinic acid concentration increased to 11.5 g/L when 12.5 v/v% AP-bio-oil was added. However, it decreased to 8 g/L when 50 v/v% AP-bio-oil was added. GC-MS analysis revealed that some low molecular carbon compounds in the AP-bio-oil were utilized by E. coli. Conclusions The results indicate that AP-bio-oil can be used by E. coli for cell growth and succinic acid production. PMID:23657107

  15. Characterization of Japanese cedar bio-oil produced using a bench-scale auger pyrolyzer

    OpenAIRE

    2016-01-01

    A bench-scale auger reactor was designed for use as a laboratory-scale fast pyrolyzer for producing bio-oil from Japanese cedar. An analytical pyrolysis method was performed simultaneously to determine the distribution of pyrolysis products. The pyrolysis temperature was found to have the greatest influence on the bio-oil characteristics; bio-oil yields increased as the pyrolysis temperature increased from 450 to 550 °C. The concentration of levoglucosan in the bio-oil, however, decreased sig...

  16. Bio-oils from acidic, neutral and alkaline hydrothermal liquefaction of cellulose: a comparative study

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Sudong [Department of Mechanical and Manufacturing Engineering, Centre for Environmental Engineering Research and Education, Schulich School of Engineering, University of Calgary (Canada); Liu, Fang; Tan, Zhongchao [Department of Mechanical and Mechatronics Engineering, University of Waterloo (Canada)

    2011-07-01

    Hydrothermal liquefaction (HTL) is a popular technology for the conversion of biomass to bio-oil. Although alkaline and neutral HTL have been widely studied in the literature so far, there are almost no data available in the literature on acidic HTL of biomass to bio-oil and on the differences between acidic and neutral/alkaline HTL of biomass to bio-oil. The purpose of this study was therefore to investigate and compare acidic, neutral and alkaline HTL of cellulose to bio-oil, with respect to bio-oil compositions and yields in specific conditions. As the result found was that acidic, neutral and alkaline conditions clearly impact the HTL bio-oil compositions. There is a similar trend for high temperatures and long residence time to have negative effects on HTL bio-oil yields for acidic, neutral and alkaline HTL. However, the reaction mechanisms behind them are various. This study presents the highly different underlying chemistries and the HTL bio-oil compositions that were investigated. Further classification of HTL of biomass to bio-oil is therefore necessary.

  17. Catalytic hydrotreatment of fast-pyrolysis oil using non-sulfided bimetallic Ni-Cu catalysts on a delta-Al2O3 support

    NARCIS (Netherlands)

    Ardiyanti, A. R.; Khromova, S. A.; Venderbosch, R. H.; Yakovlev, V. A.; Heeres, H. J.

    2012-01-01

    Fast pyrolysis oil from lignocellulosic biomass is an attractive energy carrier. However, to improve the product characteristics such as a reduced polarity and higher thermal stability, upgrading is required. We here report activities on the catalytic hydrotreatment of fast pyrolysis oil using bimet

  18. Production of Liquid Fuel by Fast Pyrolysis of Lignocellulose and Its Upgrading by Hydrotreating%木质纤维素快速热裂解及加氢提质制备液体燃料的研究进展

    Institute of Scientific and Technical Information of China (English)

    王玉军; 毛贵涛; 骆广生

    2012-01-01

    以秸秆、草和木材等农林废弃物中的木质纤维素为原料的第二代生物燃料生产技术是未来可再生能源的重要发展趋势,该技术的关键是如何去除生物质中的氧,加氢脱氧提质是重要的手段之一.综述了近年来国内外以木质纤维素为原料,通过快速热裂解工艺先制备生物油,并进一步加氢提质以获得氧含量很低的生物液体燃料的应用基础研究及工业化进展.由快速热裂解和加氢脱氧相结合的工艺制备得到的产物只含碳、氢元素以及少量的氧元素,可以与当前的石油炼制工艺很好地结合,因此该组合工艺具有广阔的应用前景.%With the depletion of crude oil, the renewable energy sources has caught much more attention, and the first generation biofuel technology has got much complaint because of the competition with human food, thus, the second generation biomass conversion technology using straw, grass, wood as raw materials has become a more important trend. The challenge of the second generation technologies is how to remove the oxygen element from the bio-oil, and the hydrodeoxygenation is one of the most important solutions. In this paper, we review the production of bio-oil through the fast pyrolysis of lignocellulose, and the fundamental research and industrial development of bio-oil's upgrading technology by the hydrotreating to produce biofuels with a low oxygen content. The products produced by the combination of fast pyrolysis and the hydrodeoxygenation only contain carbon, hydrogen and little oxygen, and has a very good compatibility with the refinery process of fossil oil, therefore, the combination process has the broad prospect of application.

  19. Volatile compounds and antioxidant capacity of the bio-oil obtained by pyrolysis of Japanese red pine (pinus densiflora siebold and zucc.).

    Science.gov (United States)

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

    2015-03-02

    In the present study, sawdust bio-oil (SBO) manufactured by fast pyrolysis of Japanese red pine (Pinus densiflora Siebold and Zucc.) sawdust was analyzed for its volatile chemical compound composition and evaluated for its free radical scavenging potential, inhibition of lipid peroxidation and reducing power. Gas chromatography and mass spectroscopy revealed 29 volatile compounds, comprising 97.6% of the total volatile compounds in SBO. The antioxidant potential of SBO in terms of IC50 values was 48.44 µg/mL for hydroxyl radical scavenging, 89.52 µg/mL for 1,1-diphenyl-2-picrylhydraxyl radical scavenging, 94.23 µg/mL for 2,2'-azino-bis[3-ethylbenzothiazoline-6-sulphonic acid] radical scavenging, and 136.06 µg/mL for superoxide radical scavenging activity. The total phenol content in SBO was 5.7% gallic acid equivalent. Based on the composition of its volatile compounds, high free radical scavenging potential and antioxidant properties, SBO could be used as a source of antioxidant compounds, flavoring agents and nutraceuticals in the food, pharmaceutical, and cosmetic industries.

  20. Volatile Compounds and Antioxidant Capacity of the Bio-Oil Obtained by Pyrolysis of Japanese Red Pine (Pinus Densiflora Siebold and Zucc.

    Directory of Open Access Journals (Sweden)

    Jayanta Kumar Patra

    2015-03-01

    Full Text Available In the present study, sawdust bio-oil (SBO manufactured by fast pyrolysis of Japanese red pine (Pinus densiflora Siebold and Zucc. sawdust was analyzed for its volatile chemical compound composition and evaluated for its free radical scavenging potential, inhibition of lipid peroxidation and reducing power. Gas chromatography and mass spectroscopy revealed 29 volatile compounds, comprising 97.6% of the total volatile compounds in SBO. The antioxidant potential of SBO in terms of IC50 values was 48.44 µg/mL for hydroxyl radical scavenging, 89.52 µg/mL for 1,1-diphenyl-2-picrylhydraxyl radical scavenging, 94.23 µg/mL for 2,2'-azino-bis[3-ethylbenzothiazoline-6-sulphonic acid] radical scavenging, and 136.06 µg/mL for superoxide radical scavenging activity. The total phenol content in SBO was 5.7% gallic acid equivalent. Based on the composition of its volatile compounds, high free radical scavenging potential and antioxidant properties, SBO could be used as a source of antioxidant compounds, flavoring agents and nutraceuticals in the food, pharmaceutical, and cosmetic industries.

  1. Hydrothermal liquefaction of microalgae's for bio oil production

    DEFF Research Database (Denmark)

    Toor, Saqib; Reddy, Harvind; Deng, Shuguang

    Hydrothermal liquefaction experiments on Nannochloropsis salina and Spirulina platensis at subcritical and supercritical water conditions were carried out to explore the feasibility of extracting lipids from wet algae, preserving nutrients in lipid-extracted algae solid residue, and recycling...... and 107 bar. For Spirulina platensis algae sample, the highest bio-oil yield is 38% at 350 °C and 195 bar. Preliminary data also indicate that a lipid-extracted algae solid residue sample obtained in the hydrothermal liquefaction process contains a high level of proteins...

  2. Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products

    NARCIS (Netherlands)

    Zhou, Shuai; Pecha, Brennan; Kuppevelt, van Michiel; McDonald, Armando G.; Garcia-Perez, Manuel

    2014-01-01

    The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir (Ps

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

    Science.gov (United States)

    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...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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.

  7. Influence of fast pyrolysis conditions on yield and structural transformation of biomass chars

    DEFF Research Database (Denmark)

    Trubetskaya, Anna; Jensen, Peter Arendt; Jensen, Anker Degn

    2015-01-01

    Fast pyrolysis of biomass (wood, straw, rice husk) and its major components (cellulose, hemicellulose, lignin) was conducted in a wire mesh reactor. The aim of this study was to understand the influence of temperature (350-1400 ° C), heating rate (10-3000 ° C/s), particle size (0.05-2 mm...... that the heat treatment temperature had a larger influence on the char yield than the heating rate. Scanning electron microscopy indicated different types of biomass char plasticization influenced by the applied temperatures, heating rates, particle sizes and holding times, except for the rice husk char...... that formed chars with a structure similar to the parental fuel at all conditions. The less severe morphological changes of rice husk char were attributed to a high silica content....

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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...

  10. Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method

    Energy Technology Data Exchange (ETDEWEB)

    Black, Stuart; Ferrell, Jack R.

    2017-01-01

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. 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. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. 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, 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. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 degrees C.

  11. Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method.

    Science.gov (United States)

    Black, Stuart; Ferrell, Jack R

    2017-02-07

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. 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. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. 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, 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. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 °C.

  12. Conversion of pine sawdust bio-oil (raw and thermally processed) over equilibrium FCC catalysts.

    Science.gov (United States)

    Bertero, Melisa; Sedran, Ulises

    2013-05-01

    A raw bio-oil from pine sawdust, the liquid product from its thermal conditioning and a synthetic bio-oil composed by eight model compounds representing the main chemical groups in bio-oils, were converted thermally and over a commercial equilibrium FCC catalyst. The experiments were performed in a fixed bed reactor at 500 °C. The highest hydrocarbon yield (53.5 wt.%) was obtained with the conditioned liquid. The coke yields were significant in all the cases, from 9 to 14 wt.%. The synthetic bio-oil produced lesser hydrocarbons and more oxygenated compounds and coke than the authentic feedstocks from biomass. The previous thermal treatment of the raw bio-oil had the positive effects of increasing 25% the yield of hydrocarbons, decreasing 55% the yield of oxygenated compounds and decreasing 20% the yield of coke, particularly the more condensed coke.

  13. Study of the potential valorisation of heavy metal contaminated biomass via phytoremediation by fast pyrolysis: Part I. Influence of temperature, biomass species and solid heat carrier on the behaviour of heavy metals

    Energy Technology Data Exchange (ETDEWEB)

    C. Lievens; J. Yperman; J. Vangronsveld; R. Carleer [Hasselt University, Diepenbeek (Belgium). Laboratory of Applied Chemistry

    2008-08-15

    Presently, little or no information of implementing fast pyrolysis for looking into the potential valorisation of heavy metal contaminated biomass is available. Fast pyrolysis of heavy metal contaminated biomass (birch and sunflower), containing high amounts of Cd, Cu, Pb and Zn, resulting from phytoremediation, is investigated. The effect of the pyrolysis temperature (623, 673, 773 and 873 K) and the type of solid heat carrier (sand and fumed silica) on the distribution of the heavy metals in birch and sunflower pyrolysis fractions are studied. The goal of the set-up is 'concentrating' heavy metals in the ash/char fraction after thermal treatment, preventing them to be released in the condensable and/or volatile fractions. The knowledge of the behaviour of heavy metals affects directly future applications and valorisation of the pyrolysis products and thus contaminated biomass. They are indispensable for making and selecting the proper thermal conditions for their maximum recovery. In view of the future valorisation of these biomasses, the amounts of the pyrolysis fractions and the calorific values of the obtained liquid pyrolysis products, as a function of the pyrolysis temperature, are determined. 46 refs., 8 figs., 4 tabs.

  14. Bio-oil upgrading strategies to improve PHA production from selected aerobic mixed cultures.

    Science.gov (United States)

    Moita Fidalgo, Rita; Ortigueira, Joana; Freches, André; Pelica, João; Gonçalves, Magarida; Mendes, Benilde; Lemos, Paulo C

    2014-06-25

    Recent research on polyhydroxyalkanoates (PHAs) has focused on developing cost-effective production processes using low-value or industrial waste/surplus as substrate. One of such substrates is the liquid fraction resulting from pyrolysis processes, bio-oil. In this study, valorisation of bio-oil through PHA production was investigated. The impact of the complex bio-oil matrix on PHA production by an enriched mixed culture was examined. The performance of the direct utilization of pure bio-oil was compared with the utilization of three defined substrates contained in this bio-oil: acetate, glucose and xylose. When compared with acetate, bio-oil revealed lower capacity for polymer production as a result of a lower polymer yield on substrate and a lower PHA cell content. Two strategies for bio-oil upgrade were performed, anaerobic fermentation and vacuum distillation, and the resulting liquid streams were tested for polymer production. The first one was enriched in volatile fatty acids and the second one mainly on phenolic and long-chain fatty acids. PHA accumulation assays using the upgraded bio-oils attained polymer yields on substrate similar or higher than the one achieved with acetate, although with a lower PHA content. The capacity to use the enriched fractions for polymer production has yet to be optimized. The anaerobic digestion of bio-oil could also open-up the possibility to use the fermented bio-oil directly in the enrichment process of the mixed culture. This would increase the selective pressure toward an optimized PHA accumulating culture selection.

  15. Experimental Researches on Milled Wood Lignin Pyrolysis Based on Analysis of Bio-oil

    Institute of Scientific and Technical Information of China (English)

    GUO Xiu-juan; WANG Shu-rong; WANG Kai-ge; LUO Zhong-yang

    2011-01-01

    The structure of milled wood lignin(MWL), isolated via the Bj(6)rkman procedure, was studied by means of 1H NMR spectroscopy and Fourier transform infrared spectroscopy, and then its pyrolytic product distribution was investigated on a pyrolysis device. MWL obtained from Manchurian Ash(MA) contained more methoxyl and free phenolic hydroxyl groups per C9 unit than MWL from Mongolian Pine(MP) due to the existence of both guaiacyl and syringyl units, which have a major influence on the pyrolysis behavior of lignin. The results of pyrolysis show that MWL from MA generated a higher yield of bio-oil, mainly composed of phenols, guaiacols, syringols and catechols,and a less yield of char, in addition to the gaseous products CO, CO2, methane and methanol, compared with MWL from MP. Guaiacol and syringol were the typical products from G-lignin and S-lignin, probably attributed to the easier cleavage of the aryl-alkyl linkage in the side chain compared with the C-OCH3 bond in the benzene ring. The degradation of MWL from MP was dominated by the demethylation reaction and the cleavage of aliphatic -CH2OH at the γ-position, followed by the cracking of the Cα-Cβ and C4-Cα bonds.

  16. Standardization of chemical analytical techniques for pyrolysis bio-oil: history, challenges, and current status of methods: Bio-oil Analytical Standardization

    Energy Technology Data Exchange (ETDEWEB)

    Ferrell, Jack R. [National Renewable Energy Laboratory (NREL), Golden CO USA; Olarte, Mariefel V. [Pacific Northwest National Laboratory (PNNL), Richland WA USA; Christensen, Earl D. [National Renewable Energy Laboratory (NREL), Golden CO USA; Padmaperuma, Asanga B. [Pacific Northwest National Laboratory (PNNL), Richland WA USA; Connatser, Raynella M. [Oak Ridge National Laboratory (ORNL), Oak Ridge TN USA; Stankovikj, Filip [Washington State University (WSU), Pullman WA USA; Meier, Dietrich [Thünen Institute of Wood Research (TI), Hamburg Germany; Paasikallio, Ville [VTT Technical Research Centre of Finland Ltd (VTT), Espoo Finland

    2016-07-05

    In this perspective, we discuss the standardization of analytical techniques for pyrolysis bio-oils, including the current status of methods, and our opinions on future directions. First, the history of past standardization efforts is summarized, and both successful and unsuccessful validation of analytical techniques highlighted. The majority of analytical standardization studies to-date has tested only physical characterization techniques. Here, we present results from an international round robin on the validation of chemical characterization techniques for bio-oils. Techniques tested included acid number, carbonyl titrations using two different methods (one at room temperature and one at 80 degrees C), 31P NMR for determination of hydroxyl groups, and a quantitative gas chromatography-mass spectrometry (GC-MS) method. Both carbonyl titration and acid number methods have yielded acceptable inter-laboratory variabilities. 31P NMR produced acceptable results for aliphatic and phenolic hydroxyl groups, but not for carboxylic hydroxyl groups. As shown in previous round robins, GC-MS results were more variable. Reliable chemical characterization of bio-oils will enable upgrading research and allow for detailed comparisons of bio-oils produced at different facilities. Reliable analytics are also needed to enable an emerging bioenergy industry, as processing facilities often have different analytical needs and capabilities than research facilities. We feel that correlations in reliable characterizations of bio-oils will help strike a balance between research and industry, and will ultimately help to determine metrics for bio-oil quality. Finally, the standardization of additional analytical methods is needed, particularly for upgraded bio-oils.

  17. Bio-oil production via subcritical hydrothermal liquefaction of biomass

    Science.gov (United States)

    Durak, Halil

    2017-04-01

    Biomass based raw materials can be converted into the more valued energy forms using biochemical methods such as ethanol fermentation, methane fermentation and the thermochemical methods such as direct combustion, pyrolysis, gasification, liquefaction. The bio-oil obtained from the biomass has many advantages than traditional use. Firstly, it has features such as high energy density, easy storage and easy transportation. Bio-oil can be used as a fuel in engines, turbines and burning units directly. Besides, it can be converted into products in higher quality and volume via catalytic cracking, hydrodexygenation, emulsification, and steam reforming [1,2]. Many organic solvents such as acetone, ethanol, methanol, isopropanol are used in the supercritical liquefaction processes. When we think about the cost and effects of the organic solvent on nature, it will be understood better that it is necessary to find solvent that are more sensitive against nature. Here, water must have an important place because of its features. Most important solvent of the world water is named as "universal solvent" because none of the liquids can dissolve the materials as much as done by water. Water is found much at the nature and cost of it is very few when compared with the other solvent. Hydrothermal liquefaction, a thermochemical conversion process is an effective method used for converting biomass into the liquid products. General reaction conditions for hydrothermal liquefaction process are the 250-374 °C temperature range and 4 - 22 Mpa pressure values range, besides, the temperature values can be higher according to the product that is expected to be obtained [3,4]. In this study, xanthium strumarium plant stems have been used as biomass source. The experiments have been carried out using a cylindrical reactor (75 mL) at the temperatures of 300 °C. The produced liquids at characterized by elemental analysis, GC-MS and FT-IR. According to the analysis, different types of compounds

  18. UPGRADING OF BIO-OIL MOLECULAR DISTILLATION FRACTION WITH SOLID ACID CATALYST

    Directory of Open Access Journals (Sweden)

    Zuogang Guo

    2011-05-01

    Full Text Available Molecular distillation technology has been adopted to obtain a bio-oil fraction rich in carboxylic acids and ketones. This unique bio-oil fraction was then upgraded with a La-promoted solid acid catalyst. Three washing pretreatments were used to prepare catalysts A, B, and C, with the intention of reducing the amounts of residual sulfuric acid. Model reactions were used to estimate their catalytic activities and the residual amounts of sulfuric acid. Catalyst B, with washing after calcination, displayed higher catalytic activity (80.83% and lower residual amount of sulfuric acid (50 μmol/g. The catalysts were characterized by techniques such as BET, XRD, and SEM to explain the differences in their catalytic activities. The optimum catalyst B was used in the upgrading of the bio-oil molecular distillation fraction. After upgrading, the corrosivity of the bio-oil fraction declined and its storage stability was improved. The carboxylic acid content in the upgraded bio-oil fraction decreased from 18.39% to 2.70%, while the ester content increased from 0.72% to 31.17%. The conversion of corrosive carboxylic acids to neutral esters reduced the corrosivity of the bio-oil fraction. Moreover, the ketones with unsaturated carbon-carbon double bonds (such as 2-cyclopenten-1-one, 3-methyl-2-cyclopenten-1-one, etc. were converted into saturated compounds, which improved the stability of the bio-oil fraction.

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

    Science.gov (United States)

    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. Fast pyrolysis of sunflower-pressed bagasse: effects of sweeping gas flow rate

    Energy Technology Data Exchange (ETDEWEB)

    Gercel, H.F.; Putun, E.

    2002-05-01

    Sunflower (Helianthus annus L.)-pressed bagasse pyrolysis experiments were performed in a fixed-bed tubular reactor. The effects of nitrogen flow rate and final pyrolysis temperature on the pyrolysis product yields and chemical compositions have been investigated. The maximum bio-oil yield of 52.85 wt% was obtained in a nitrogen atmosphere and a nitrogen flow rate of 50 cm{sup 3} min{sup -1} and at a pyrolysis temperature of 550{sup o}C and heating rate of 5{sup o}C s{sup -1}. The chemical characterization has shown that the oil obtained from sunflower-pressed bagasse may be potentially valuable as fuel and chemical feedstocks. (author)

  1. The effect of a sweeping gas flow rate on the fast pyrolysis of biomass

    Energy Technology Data Exchange (ETDEWEB)

    Gercel, H.F.

    2002-07-01

    Sunflower (Helianthus annus L.)-pressed bagasse pyrolysis experiments were performed in a fixed-bed tubular reactor. The effects of nitrogen flow rate and final pyrolysis temperature on the pyrolysis product yields and chemical compositions have been investigated. The maximum bio-oil yield of 46.62 wt% was obtained in a nitrogen atmosphere with a nitrogen flow rate of 25 cm{sup 3}min{sup -1} and at a pyrolysis temperature of 550{sup o}C with a heating rate of 300{sup o}C min{sup -1}. The chemical characterization showed that the oil obtained from sunflower-pressed bagasse may be potentially valuable as fuel and chemical feedstocks. (author)

  2. Production of bio-oil with flash pyrolysis; Biooeljyn tuotanto flash-pyrolyysillae ja sen poltto

    Energy Technology Data Exchange (ETDEWEB)

    Nyroenen, T. [Vapo Oy, Jyvaeskylae (Finland)

    1997-12-01

    The target of the R and D work is to study the production of bio-oils using Flash-pyrolysis technology and utilisation of the bio-oil in oil-fuelled boilers. The PDU-unit was installed at VTT Energy in Otaniemi in April 1996. The first test were carried out in June. In the whole project Vapo Oy is responsible for: acquiring the 20 kg/h PDU-device for development; follow up of the engine tests; the investment of 5 MW demonstration plant; to carry on the boiler and engine tests with Finnish bio-oils. (orig.)

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

    Energy Technology Data Exchange (ETDEWEB)

    Jasperson, Louis V.; McDougal, Rubin J.; Diky, Vladimir; Paulechka, Eugene; Chirico, Robert D.; Kroenlein, Kenneth; Iisa, Kristiina; Dutta, Abhijit

    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 system (water + toluene + phenol) has been studied previously with inconsistent results reported in the literature, and one report is shown to be anomalous. All systems are modeled with the predictive methods NIST-Modified-UNIFAC and NIST-COSMO-SAC, with generally good success in the temperature range of interest (300 < T/K < 360). This work is part of a larger project on the testing and development of predictive phase equilibrium models for compound types occurring in catalytic fast pyrolysis of biomass, and background information for the larger project is provided.

  4. Energy potential from rice husk through direct combustion and fast pyrolysis: A review.

    Science.gov (United States)

    Quispe, Isabel; Navia, Rodrigo; Kahhat, Ramzy

    2017-01-01

    Rapid population growth and consumption of goods and services imply that demand for energy and resources increases continuously. Energy consumption linked to non-renewable resources contributes to greenhouse gas emissions and enhances resource depletion. In this context, the use of agricultural solid residues such as rice husk, coffee husk, wheat straw, sugar cane bagasse, among others, has been widely studied as an alternative energy source in order to decrease the use of fossil fuels. However, rice husk is among those agricultural residues that are least used to obtain energy in developing countries. Approximately 134 million tonnes of rice husk are produced annually in the world, of which over 90% are burned in open air or discharged into rivers and oceans in order to dispose of them. This review examines the energetic potential of agricultural residues, focused on rice husk. The review describes direct combustion and fast pyrolysis technologies to transform rice husk into energy considering its physical and chemical properties. In addition, a review of existing studies analyzing these technologies from an environmental life cycle thinking perspective, contributing to their sustainable use, is performed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. FAST PYROLYSIS PROCESS OF ORANGE SOLID WASTE. FACTORS INFLUENCE IN THE PROCESS

    Directory of Open Access Journals (Sweden)

    Leonardo Aguiar Trujillo

    2015-04-01

    Full Text Available The orange processing industry generates high volumes of solid residue. This residue has been used in animal feeding and biochemical processes. A possible energy use of the waste can be thermochemical fast pyrolysis process. The objective was to determine the influence of the heating rate and temperature in the process of rapid pyrolysis of orange solid residue. In the process a design, 2k full factorial experiment was used, evaluating the influence of the independent variables and its interactions on the answers, using a 95 % significance level. We found that temperature is the most significant influence on the responses parameter having significant influence on the yields to: gas, coal, tar and the calorific value of the gas and the heating rate does not influence the answers. Finally, the interaction affects the gas yield. The results obtained in this study are: Rgas (19 – 38 %, Rchar (25 – 42 %, Ralq (6 – 12 %, PCIgas entre (140 – 1050 kJ/m3N.

  6. Comparison of non-catalytic and catalytic fast pyrolysis of corncob in a fluidized bed reactor.

    Science.gov (United States)

    Zhang, Huiyan; Xiao, Rui; Huang, He; Xiao, Gang

    2009-02-01

    Fast pyrolysis of corncob with and without catalyst was investigated in a fluidized bed to determine the effects of pyrolysis parameters (temperature, gas flow rate, static bed height and particle size) and a HZSM-5 zeolite catalyst on the product yields and the qualities of the liquid products. The result showed that the optimal conditions for liquid yield (56.8%) were a pyrolysis temperature of 550 degrees C, gas flow rate of 3.4 L/min, static bed height of 10 cm and particle size of 1.0-2.0mm. The presence of the catalyst increased the yields of non-condensable gas, water and coke, while decreased the liquid and char yields. The elemental analysis showed that more than 25% decrease in oxygen content of the collected liquid in the second condenser with HZSM-5 was observed compared with that without catalyst. The H/C, O/C molar ratios and the higher heating value of the oil fraction in the collected liquid with the catalyst were 1.511, 0.149 and 34.6 MJ/kg, respectively. It was indicated that the collected liquid in the second condenser had high qualities and might be used as transport oil.

  7. Pengaruh Jenis Bahan pada Proses Pirolisis Sampah Organik menjadi Bio-Oil sebagai Sumber Energi Terbarukan

    Directory of Open Access Journals (Sweden)

    M. Sigit Cahyono

    2013-06-01

    Full Text Available Sampah organik merupakan potensi sumber energi yang melimpah di Indonesia. Sampah organik berupa daun dan ranting kering bisa dikonversi menjadi bahan bakar berupa bio-oil melalui proses fast pirolisis. Tujuan dari penelitian ini adalah untuk mengetahui pengaruh jenis bahan terhadap rendemen dan nilai kalor bio-oil yang dihasilkan dari proses pirolisis sampah organik. Bahan baku berupa daun dan ranting kering campuran tanaman angsana, mahoni dan mangga dengan komposisi daun bervariasi 0%, 50%, dan 100%, dipotong-potong dengan ukuran maksimal 10 cm. Kemudian bahan baku tersebut dipanaskan di dalam reaktor pirolisis pada suhu 500 C selama 1 jam. Hasil penelitian menunjukkan bahwa nilai kalor tertinggi (5175,35 J/g dan rendemen tertinggi (24,5% didapatkan pada bio-oil yang dihasilkan dari pirolisis ranting 100%. Kata kunci: Sampah Organik, Bio-oil, Pirolisis, Rendemen, Nilai Kalor

  8. Electron microscopy study of the deactivation of nickel based catalysts for bio oil hydrodeoxygenation

    DEFF Research Database (Denmark)

    Gardini, Diego; Mortensen, Peter Mølgaard; Carvalho, Hudson W. P.

    2014-01-01

    Hydrodeoxygenation (HDO) is proposed as an efficient way to remove oxygen in bio-oil, improving its quality as a more sustainable alternative to conventional fuels in terms of CO2 neutrality and relative short production cycle [1]. Ni and Ni-MoS2 nanoparticles supported on ZrO2 show potential...... as high-pressure (100 bar) catalysts for purification of bio-oil by HDO. However, the catalysts deactivate in presence of sulfur, chlorine and potassium species, which are all naturally occurring in real bio-oil. The deactivation mechanisms of the Ni/ZrO2 have been investigated through scanning...... transmission electron microscopy (STEM), energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Catalytic testing has been performed using guaiacol in 1-octanol acting as a model compound for bio-oil. Addition of sulphur (0.3 vol% octanethiol) in the feed...

  9. Catalytic Transformation of Bio-oil to Olefins with Molecular Sieve Catalysts

    Science.gov (United States)

    Huang, Wei-wei; Gong, Fei-yan; Zhai, Qi; Li, Quan-xin

    2012-08-01

    Catalytic conversion of bio-oil into light olefins was performed by a series of molecular sieve catalysts, including HZSM-5, MCM-41, SAPO-34 and Y-zeolite. Based on the light olefins yield and its carbon selectivity, the production of light olefins decreased in the following order: HZSM-5>SAPO-34>MCM-41> Y-zeolite. The highest olefins yield from bio-oil using HZSM-5 catalyst reached 0.22 kg/kgbio-oil with carbon selectivity of 50.7% and a nearly complete bio-oil conversion. The reaction conditions and catalyst characterization were investigated in detail to reveal the relationship between the catalyst structure and the production of olefins. The comparison between the pyrolysis and catalytic pyrolysis of bio-oil was also performed.

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

    Science.gov (United States)

    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.

  11. Acetic acid recovery from fast pyrolysis oil. An exploratory study on liquid-liquid reactive extraction using aliphatic tertiary amines

    NARCIS (Netherlands)

    Mahfud, F. H.; van Geel, F. P.; Venderbosch, R. H.; Heeres, H. J.

    2008-01-01

    Flash pyrolysis oil or Bio-oil (BO), obtained by flash pyrolysis of lignocellulosic biomass, is very acidic in nature. The major component responsible for this acidity is acetic acid, present in levels up to 2-10 wt%. Here, we report an exploratory study on BO upgrading by reactive extraction of ace

  12. Acetic acid recovery from fast pyrolysis oil. An exploratory study on liquid-liquid reactive extraction using aliphatic tertiary amines

    NARCIS (Netherlands)

    Mahfud, F. H.; van Geel, F. P.; Venderbosch, R. H.; Heeres, H. J.

    2008-01-01

    Flash pyrolysis oil or Bio-oil (BO), obtained by flash pyrolysis of lignocellulosic biomass, is very acidic in nature. The major component responsible for this acidity is acetic acid, present in levels up to 2-10 wt%. Here, we report an exploratory study on BO upgrading by reactive extraction of

  13. Acetic acid recovery from fast pyrolysis oil. An exploratory study on liquid-liquid reactive extraction using aliphatic tertiary amines

    NARCIS (Netherlands)

    Mahfud, F. H.; van Geel, F. P.; Venderbosch, R. H.; Heeres, H. J.

    2008-01-01

    Flash pyrolysis oil or Bio-oil (BO), obtained by flash pyrolysis of lignocellulosic biomass, is very acidic in nature. The major component responsible for this acidity is acetic acid, present in levels up to 2-10 wt%. Here, we report an exploratory study on BO upgrading by reactive extraction of ace

  14. Autothermal reforming of palm empty fruit bunch bio-oil: thermodynamic modelling

    Directory of Open Access Journals (Sweden)

    Lifita N. Tande

    2016-01-01

    Full Text Available This work focuses on thermodynamic analysis of the autothermal reforming of palm empty fruit bunch (PEFB bio-oil for the production of hydrogen and syngas. PEFB bio-oil composition was simulated using bio-oil surrogates generated from a mixture of acetic acid, phenol, levoglucosan, palmitic acid and furfural. A sensitivity analysis revealed that the hydrogen and syngas yields were not sensitive to actual bio-oil composition, but were determined by a good match of molar elemental composition between real bio-oil and surrogate mixture. The maximum hydrogen yield obtained under constant reaction enthalpy and pressure was about 12 wt% at S/C = 1 and increased to about 18 wt% at S/C = 4; both yields occurring at equivalence ratio Φ of 0.31. The possibility of generating syngas with varying H2 and CO content using autothermal reforming was analysed and application of this process to fuel cells and Fischer-Tropsch synthesis is discussed. Using a novel simple modelling methodology, reaction mechanisms were proposed which were able to account for equilibrium product distribution. It was evident that different combinations of reactions could be used to obtain the same equilibrium product concentrations. One proposed reaction mechanism, referred to as the ‘partial oxidation based mechanism’ involved the partial oxidation reaction of the bio-oil to produce hydrogen, with the extent of steam reforming and water gas shift reactions varying depending on the amount of oxygen used. Another proposed mechanism, referred to as the ‘complete oxidation based mechanism’ was represented by thermal decomposition of about 30% of bio-oil and hydrogen production obtained by decomposition, steam reforming, water gas shift and carbon gasification reactions. The importance of these mechanisms in assisting in the eventual choice of catalyst to be used in a real ATR of PEFB bio-oil process was discussed.

  15. Preparation and Characterization of Bio-Oil Modified Urea-Formaldehyde Wood Adhesives

    OpenAIRE

    Ben Li; Ji-Zong Zhang; Xue-Yong Ren; Jian-min Chang; Jin-sheng Gou

    2014-01-01

    Wood-derived bio-oil was used to decrease formaldehyde emissions from urea-formaldehyde (UF) resin during the process of making three-layered plywood. The obtained bio-oil urea formaldehyde (BUF) resins were characterized by their physical, chemical, and mechanical properties (e.g., viscosity, solid content, pH value, shelf life, formaldehyde emissions, and bonding strength), analyzed for their specifications, and characterized with Fourier transform infrared spectroscopy and thermogravimetri...

  16. Characterization of Japanese cedar bio-oil produced using a bench-scale auger pyrolyzer.

    Science.gov (United States)

    Kato, Yoshiaki; Enomoto, Ryohei; Akazawa, Minami; Kojima, Yasuo

    2016-01-01

    A bench-scale auger reactor was designed for use as a laboratory-scale fast pyrolyzer for producing bio-oil from Japanese cedar. An analytical pyrolysis method was performed simultaneously to determine the distribution of pyrolysis products. The pyrolysis temperature was found to have the greatest influence on the bio-oil characteristics; bio-oil yields increased as the pyrolysis temperature increased from 450 to 550 °C. The concentration of levoglucosan in the bio-oil, however, decreased significantly with increasing pyrolysis temperature, while it increased following analytical pyrolysis. The same results were obtained for 4-vinylguaiacol and E-isoeugenol, which were the major secondary products produced in the present study. Compared to the yields of these major products obtained via analytical pyrolysis, the yields from the auger reactor were very low, indicating that the auger reactor process had a longer vapor residence time than the analytical pyrolysis process, resulting in the acceleration of secondary reactions of the pyrolysates. The pH values and densities of the bio-oils produced in the auger reactor were similar to those reported by researchers using woody biomass, despite their lower viscosities. From these results, it was concluded that the pyrolysis temperature and residence time of the pyrolysates played a significant role in determining the characteristics of the cedar bio-oil.

  17. Interfacial Properties of Loblolly Pine Bonded with Epoxy/Wood Pyrolysis Bio-oil Blended System

    Directory of Open Access Journals (Sweden)

    Yi Liu

    2014-12-01

    Full Text Available The bonding interface of loblolly pine veneers cured with epoxy/wood pyrolysis bio-oil resins was studied. The shear strength of the adhered strands was calculated to examine the effect of bio-oil addition on epoxy resin performance. The chemical structure, curing behavior, and microstructure were investigated to analyze the interaction between wood substrate and resins. Results showed that the strength of pine wood-resin joints gradually decreased as more bio-oil was added. However, this effect was not apparent when the substitution rate was lower than 30%. ATR-FTIR analysis confirmed that complex chemical reactions take place between wood constituents and epoxy/bio-oil resins involved in the cross-linking at the interface. The reaction degree of -OH and C-O-C functional groups plays a key role in regulating the bonding stress of the wood bond line. The addition of bio-oil accelerated the polycondensation cross-linking process, resulting in a decreased cure temperature. SEM and optical microscopy showed that the epoxy/bio-oil resin formed gel nails in the pit and tracheid gaps, leading to the closing of the capillaries of the wood’s cell walls and the colloidal interface extending into the timber micro-capillary system.

  18. Modeling the Kinetics of Deactivation of Catalysts during the Upgrading of Bio-Oil

    Energy Technology Data Exchange (ETDEWEB)

    Weber, Robert S.; Olarte, Mariefel V.; Wang, Huamin

    2015-01-25

    The fouling of catalysts for the upgrading of bio-oils appears to be very different from the fouling of catalysts for the hydroprocessing of petroleum-derived streams. There are two reasons for the differences: a) bio-oil contains polarizable components and phases that can stabilize reaction intermediates exhibiting charge separation and b) bio-oil components contain functional groups that contain O, notably carbonyls (>C=O). Aldol condensation of carbonyls affords very different pathways for the production of oligomeric, refractory deposits than does dehydrogenation/polymerization of petroleum-derived hydrocarbons. Colloquially, we refer to the bio-oil derived deposits as “gunk” to discriminate them from coke, the carbonaceous deposits encountered in petroleum refining. Classical gelation, appears to be a suitable model for the “gunking” reaction. Our work has helped explain the temperature range at which bio-oil should be pre-processed (“stabilized”) to confer longer lifetimes on the catalysts used for more severe processing. Stochastic modeling (kinetic Monte Carlo simulations) appears suitable to capture the rates of oligomerization of bio-oil. This work was supported by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  19. Production of Low-carbon Light Olefins from Catalytic Cracking of Crude Bio-oil

    Institute of Scientific and Technical Information of China (English)

    Yan-ni Yuan; Tie-jun Wang; Quan-xin Li

    2013-01-01

    Low-carbon light olefins are the basic feedstocks for the petrochemical industry.Catalytic cracking of crude bio-oil and its model compounds (including methanol,ethanol,acetic acid,acetone,and phenol) to light olefins were performed by using the La/HZSM-5 catalyst.The highest olefins yield from crude bio-oil reached 0.19 kg/(kg crude bio-oil).The reaction conditions including temperature,weight hourly space velocity,and addition of La into the HZSM-5 zeolite can be used to control both olefins yield and selectivity.Moderate adjusting the acidity with a suitable ratio between the strong acid and weak acid sites through adding La to the zeolite effectively enhanced the olefins selectivity and improved the catalyst stability.The production of light olefins from crude bio-oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock.The comparison between the catalytic cracking and pyrolysis of bio-oil was studied.The mechanism of the bio-oil conversion to light olefins was also discussed.

  20. Catalytic Steam Reforming of Bio-Oil to Hydrogen Rich Gas

    DEFF Research Database (Denmark)

    Trane-Restrup, Rasmus

    Bio-oil is a liquid produced by pyrolysis of biomass and its main advantage compared with biomass is an up to ten times higher energy density. This entails lower transportation costs associated with the utilization of biomass for production of energy and fuels. Nevertheless, the bio-oil has a low...... heating value and high content of oxygen, which makes it unsuited for direct utilization in engines. One prospective technology for upgrading of bio-oil is steam reforming (SR), which can be used to produce H2 for upgrading of bio-oil through hydrodeoxygenation or synthesis gas for processes like...... the Fischer-Tropsch synthesis. In the SR of bio-oil or biooil model compounds high degrees of conversion and high yields of H2 can be achieved, but stability with time-on-stream is rarely achieved. The deactivation is mainly due to carbon deposition and is one of the major hurdles in the SR of bio-oil...

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. Investigation on Electrostatical Breakup of Bio-Oil Droplets

    Directory of Open Access Journals (Sweden)

    John Z. Wen

    2012-10-01

    Full Text Available In electrostatic atomization, the input electrical energy causes breaking up of the droplet surface by utilizing a mutual repulsion of net charges accumulating on that surface. In this work a number of key parameters controlling the bio-oil droplet breakup process are identified and these correlations among the droplet size distribution, specific charges of droplets and externally applied electrical voltages are quantified. Theoretical considerations of the bag or strip breakup mechanism of biodiesel droplets experiencing electrostatic potential are compared to experimental outcomes. The theoretical analysis suggests the droplet breakup process is governed by the Rayleigh instability condition, which reveals the effects of droplets size, specific charge, surface tension force, and droplet velocities. Experiments confirm that the average droplet diameters decrease with increasing specific charges and this decreasing tendency is non-monotonic due to the motion of satellite drops in the non-uniform electrical field. The measured specific charges are found to be smaller than the theoretical values. And the energy transformation from the electrical energy to surface energy, in addition to the energy loss, Taylor instability breakup, non-excess polarization and some system errors, accounts for this discrepancy. The electrostatic force is the dominant factor controlling the mechanism of biodiesel breakup in electrostatic atomization.

  3. 生物质快速热解制车用燃料过程的能值分析%Emergy analysis of biomass fast pyrolysis for production of vehicle fuel

    Institute of Scientific and Technical Information of China (English)

    刘长奇; 黄亚继; 刘培刚; 王昕晔; 邵志伟

    2014-01-01

    基于能值分析理论和考虑环境投入,从可持续发展的角度对玉米秸秆热解加氢制精制油过程的2个方案进行综合评价,获得生产效率、环境影响、可持续性方面的能值指标.方案1中的氢气来自初级生物油水相重整,方案2中氢气来自外部市场购买.结果表明:2个方案能值转换率分别为5.00×105 sej/J和1.37×105 sej/J,从能值转换率的角度分析,与方案1、玉米燃料乙醇及生物柴油相比,方案2生产等量燃料消耗的太阳能最少,更有优势;2个方案的能值产出率均为1.07,生产效率较低;环境负载率分别是1.02和1.05,对环境影响较小;可持续发展系数分别是1.05和1.02,可持续性属于中等水平.%Considering the environmental inputs,two schemes of corn stover fast pyrolysis and hy-drogenation are evaluated by means of emergy accounting methodology from the viewpoint of sus-tainable development.The first scenario employs bio-oil reforming to generate requisite hydrogen for bio-oil upgrading,and the second scenario uses merchant hydrogen for bio-oil upgrading.The emer-gy indices of two schemes are respectively as follows:the transformities of the first scenario and the second scenario are 5.00 ×105 and 1.37 ×105 sej/J,respectively;the environment load ratio are 1 .02 and 1 .05;the emergy sustainable indices are 1 .05 and 1 .02;the emergy yield ratios are 1 .07 and 1 .07 .The second scheme has more advantages than the first scheme,corn-based fuel ethanol and biodiesel from the emergy analysis for its lower solar energy to produce the equal amount of fu-el.Both scenarios have little impact on the environment,their production efficiency are low and the sustainability of the production process belongs to the medium level.

  4. OBTENCIÓN DE BIOCOMBUSTIBLES PRODUCTO DE LA PIROLISIS RÁPIDA DE RESIDUOS DE PALMA AFRICANA (Elaeis guineensis Jacq. OBTENÇÃO DE BICOMBUSTÍVEIS POR PIRÓLISE RÁPIDA DE RESÍDUOS DE PALMA DE DENDÊ (Elaeisg uineensis Jacq. BIOFUELS PRODUCTION BY FAST PYROLYSIS OF PALM OIL WASTES (Elaeis guineensis Jacq.

    Directory of Open Access Journals (Sweden)

    JUAN C. ARTEAGA V.

    2012-12-01

    de 2.72 % vol. para o CO2, 0.706 % vol. para o H2, 1.289 % vol. para o CH4. A composição restante foi de N2. A maior quantidade de gases foi obtida quando o processofoifeito a 700 ºCembora o rendimento do bio-oilfoi de 14.9 % em peso. Os resultados mostraram que a temperatura no reator é um parâmetro importante na composição dos gases e no rendimento do bio-oil. Uma fase posterior consistiria na avaliação dos custos e os benefícios para re-configurar o reator a fim de otimizar o rendimentonaprodção do bio-oil, assim como de avaliar a possibilidade de usar a fração gasosa como fonte energética para levar a cabo o processo de pirólise.Biofuels were obtained by fast pyrolysis of palm oilwastes (Elaeis guineensis Jacq. in a free fall reactor. Previously, palm oil wastes were dried and sieved and then were fed to the reactor. As pyrolysis products, char, non-condensable gas and bio-oil, a condensed liquid composed by alcohols, carboxylic acids, alkanes and aromatics, were obtained. The experiments were carried out at temperature range 500-700°C. The highest bio-oil yield, 23.3%, was obtained at 600°C. The gas compositional analysis showed CO2,720%, H0,703 % , CH1,289%, CO 22 4 2,472 % and N2 for the non-condensable gas produced at 600°C. The highest gas yield was obtained at 700°C but bio-oil yield was 14.9%. Results indicate that temperature has an important effect on the product yields and composition. A future step will be an economical analysis in order to evaluate the possibility of using non-condensable gas as energy source for pyrolysis reactor.

  5. Characterization of asphalt materials containing bio oil from michigan wood

    Science.gov (United States)

    Mills-Beale, Julian

    The objective of this research is to develop sustainable wood-blend bioasphalt and characterize the atomic, molecular and bulk-scale behavior necessary to produce advanced asphalt paving mixtures. Bioasphalt was manufactured from Aspen, Basswood, Red Maple, Balsam, Maple, Pine, Beech and Magnolia wood via a 25 KWt fast-pyrolysis plant at 500 °C and refined into two distinct end forms - non-treated (5.54% moisture) and treated bioasphalt (1% moisture). Michigan petroleum-based asphalt, Performance Grade (PG) 58-28 was modified with 2, 5 and 10% of the bioasphalt by weight of base asphalt and characterized with the gas chromatography-mass spectroscopy (GC-MS), Fourier Transform Infra-red (FTIR) spectroscopy and the automated flocculation titrimetry techniques. The GC-MS method was used to characterize the Carbon-Hydrogen-Nitrogen (CHN) elemental ratio whiles the FTIR and the AFT were used to characterize the oxidative aging performance and the solubility parameters, respectively. For rheological characterization, the rotational viscosity, dynamic shear modulus and flexural bending methods are used in evaluating the low, intermediate and high temperature performance of the bio-modified asphalt materials. 54 5E3 (maximum of 3 million expected equivalent standard axle traffic loads) asphalt paving mixes were then prepared and characterized to investigate their laboratory permanent deformation, dynamic mix stiffness, moisture susceptibility, workability and constructability performance. From the research investigations, it was concluded that: 1) levo, 2, 6 dimethoxyphenol, 2 methoxy 4 vinylphenol, 2 methyl 1-2 cyclopentandione and 4-allyl-2, 6 dimetoxyphenol are the dominant chemical functional groups; 2) bioasphalt increases the viscosity and dynamic shear modulus of traditional asphalt binders; 3) Bio-modified petroleum asphalt can provide low-temperature cracking resistance benefits at -18 °C but is susceptible to cracking at -24 °C; 3) Carbonyl and sulphoxide

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

    Energy Technology Data Exchange (ETDEWEB)

    Dutta, Abhijit [National Renewable Energy Lab. (NREL), Golden, CO (United States); Sahir, A. H. [National Renewable Energy Lab. (NREL), Golden, CO (United States); Tan, Eric [National Renewable Energy Lab. (NREL), Golden, CO (United States); Humbird, David [DWH Process Consulting, Denver, CO (United States); Snowden-Swan, Lesley J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Meyer, Pimphan A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Ross, Jeff [Harris Group, Inc., Seattle, WA (United States); Sexton, Danielle [Harris Group, Inc., Seattle, WA (United States); Yap, Raymond [Harris Group, Inc., Seattle, WA (United States); Lukas, John [Harris Group, Inc., Seattle, WA (United States)

    2015-03-01

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

  7. 生物质快速热解油水相溶液超声乳化特性%Ultrasonic emulsification characteristics of aqueous solution of bio-oil from fast pyrolysis of biomass and diesel

    Institute of Scientific and Technical Information of China (English)

    梁伟; 王铁军; 张琦; 汪璐; 徐莹; 吴创之

    2009-01-01

    使用生物油水相溶液与0# 柴油乳化,筛选了四种常用乳化剂和一种助乳化剂进行复配乳化实验,考察了复配乳化剂型号、乳化剂用量、超声作用时间对乳化效果的影响.结果表明,六种乳化液超过30d不破乳,与0# 柴油相比,密度和热值相差不大,含水量3%以下,黏度增大约40%,pH值降低一半.因素分析法表明,水相溶液与柴油质量比和不同的水相溶液对乳化效果影响较大.探讨了乳化机理,认为生物油水相溶液中水、醛、酸、酮等极性组分化合物稳定地被乳化剂包裹在W/O型乳化液液滴中,生物油水相溶液中少量的乙酸乙酯、芳香类化合物等则增溶于非离子乳化剂胶束中.热力学分析表明,超声乳化作用比静置作用具有更大的熵增,乳化液更趋于稳定平衡状态.

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

    Science.gov (United States)

    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.

  9. Fast pyrolysis of palm kernel cake in a closed-tubular reactor: product compositions and kinetic model.

    Science.gov (United States)

    Ngo, Thanh-An; Kim, Jinsoo; Kim, Seung-Soo

    2011-03-01

    In this study, fast pyrolysis of palm kernel cake (PKC) was carried out in a closed-tubular reactor over a temperature range of 550 to 750°C with various retention times. The pyrolyzing gas products mainly included CO, CO(2), and light hydrocarbons; it is noted that no hydrogen was detected in the product. In order to investigate the reaction pathway, the kinetic lump model of Liden was applied to verify and calculate all rate constants. The results obtained at different temperatures indicated that the rate constant increased with pyrolysis temperature. Furthermore, the experimental results were in good agreement with the proposed mechanism.

  10. Emergy analysis on upgraded process systems of bio-oil frompinus sylvestris pyrolysis%樟子松热解生物油提质工艺系统能值分析

    Institute of Scientific and Technical Information of China (English)

    邰扬; 黄亚继; 刘长奇; 刘凌沁; 卢志海

    2016-01-01

    生物质热解提质制高品位生物油技术是当前研究热点,该文基于能值投入产出结构和能值指标,考虑环境因素,运用能值分析方法对樟子松快速热解催化加氢提质(方案1)和超临界乙醇提质(方案2)制高品位生物油系统进行综合评价,并分别从生产效率、自然环境支持力以及可持续性3个角度进行对比。结果表明,在生产等量燃料情况下,方案2消耗的太阳能更少,效率更高,但在人类社会投入及总投入方面方案1少于方案2,方案1系统的可再生率更高,对环境的压力更小,可持续性更好,工艺更受环境支持。该文为提高生物质热解提质制生物油系统的综合性能提供理论依据。%Fast pyrolysis of biomass and upgrading techniques for the high chemical value bio-oil production have been investigated widely in recent decades. A variety of upgrading techniques are applied in industrial manufacture process, while the production efficiency and sustainability of those techniques have their own merits and demerits, which emphasizes the importance of the evaluation systems for those techniques. Several evaluation methods, such as energy analysis, exergy analysis, and emergy analysis, have been developed to evaluate the fast pyrolysis of biomass and upgrading techniques. Based on different emergy flows, the methods chosen for the thermodynamic analysis lead to various outcomes. All the input and output energies in an industrial production system are considered in energy analysis, while exergy analysis takes the additional available energy into account. In emergy analysis, all kinds of emergy flows are taken into consideration, including monetary flow, information flow and energy flow. Emergy analysis is derived from the viewpoint that the sun provides the energy for everything on the earth so it is reasonable to convert all kinds of energy to the solar energy. It is so efficient and comprehensive

  11. Application of Fast Pyrolysis Biochar to a Loamy soil - Effects on carbon and nitrogen dynamics and potential for carbon sequestration

    DEFF Research Database (Denmark)

    Bruun, Esben

    Thermal decomposition of biomass in an oxygen-free environment (pyrolysis) produces bio-oil, syngas, and char. All three products can be used to generate energy, but an emerging new use of the recalcitrant carbon-rich char (biochar) is to apply it to the soil in order to enhance soil fertility...... for agricultural soil, e.g. it improves soil WHC, adds minerals, enhances microbial activity/biomass, and increases the N and C turnover dynamics....

  12. Catalytic cracking of the top phase fraction of bio-oil into upgraded liquid oil

    Energy Technology Data Exchange (ETDEWEB)

    Sunarno [Chemical Engineering Department, Riau University, Kampus Binawidya KM 12,5 Pekanbaru 28293 (Indonesia); Chemical Engineering Department, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur,Yogyakarta 55281 (Indonesia); Rochmadi,; Mulyono, Panut [Chemical Engineering Department, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur,Yogyakarta 55281 (Indonesia); Budiman, Arief, E-mail: abudiman@ugm.ac.id [Chemical Engineering Department, Gadjah Mada University, Jalan Grafika No. 2 Bulaksumur,Yogyakarta 55281(Indonesia); Center for Energy Studies, Gadjah Mada University, Sekip K1A, Yogyakarta 55281 (Indonesia)

    2016-06-03

    The energy consumption is increasing, while oil reserves as a primary energy resource are decreasing, so that is the reason seeking alternative energy source is inevitable. Biomass especially oil palm empty fruit bunches (EFB) which is abundant in Indonesia can be processed into bio-oil by pyrolysis process. The potential for direct substitution of bio-oil for petroleum may be limited due to the high viscosity, high oxygen content, low heating value, and corrosiveness. Consequently, upgrading of the bio-oil before use is inevitable to give a wider variety of applications of its liquid product. Furthermore, upgrading process to improve the quality of bio-oil by reduction of oxygenates involves process such as catalytic cracking. The objective of this research is to study the effect of operation temperature on yield and composition of upgraded liquid oil and to determine physical properties. Bio-oil derived from EFB was upgraded through catalytic cracking using series tubular reactor under atmospheric pressure on a silica-alumina catalyst. Results show that increasing temperature from 450 to 600 °C, resulting in decreasing of upgraded liquid oil (ULO) yield, decreasing viscosity and density of ULO, but increasing in calorimetric value of ULO. The increasing temperature of cracking also will increase the concentration of gasoline and kerosene in ULO.

  13. Hydrothermal liquefaction of Litsea cubeba seed to produce bio-oils.

    Science.gov (United States)

    Wang, Feng; Chang, Zhoufan; Duan, Peigao; Yan, Weihong; Xu, Yuping; Zhang, Lei; Miao, Juan; Fan, Yunchang

    2013-12-01

    Hydrothermal liquefaction (HTL) of Litsea cubeba seed was conducted over different temperature (250-350°C), time (30-120 min), reactor loading (0.5-4.5 g) and Na2CO3 loading (0-10 wt.%). Temperature was the most influential factor affecting the yields of product fractions. The highest bio-oil yield of 56.9 wt.% was achieved at 290°C, 60 min, and reactor loading of 2.5 g. The presence of Na2CO3 favored the conversion of the feedstock but suppressed the production of bio-oil. The higher heating values of the bio-oil were estimated at around 40.8 MJ/kg. The bio-oil, which mainly consisted of toluene, 1-methyl-2-(1-methylethyl)-benzene, fatty acids, fatty acid amides, and fatty acid esters, had a smaller total acid number than that of the oil obtained from the direct extraction of the starting material. It also contained nitrogen that was far below the bio-oil produced from the HTL of microalgae, making it more suitable for the subsequent refining. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Stabilization of Empty Fruit Bunch derived Bio-oil using Solvents

    Directory of Open Access Journals (Sweden)

    Chung Loong Yiin

    2016-03-01

    Full Text Available The intention of this research was to select the ideal condition for accelerated aging of bio-oil and the consequences of additive in stabilizing the bio-oil. The bio-oil was produced from the catalytic pyrolysis of empty fruit bunch. The optimum reaction conditions applied to obtain the utmost bio-oil yield were 5 wt% of H-Y catalyst at reaction temperature of 500 °C and nitrogen flow rate of 100 ml/min. A 10 wt% of solvents including acetone, ethanol, and ethyl acetate were used to study the bio-oil’s stability. All the test samples were subjected to accelerated aging at temperature of 80 oC for 7 days. The properties of samples used as the indicator of aging were viscosity and water content. The effectiveness of solvents increased in the following order: acetone, ethyl acetate, and 95 vol% ethanol. Based on the result of Gas chromatography-mass spectrometry (GC-MS, it could impede the chain of polymerization by converting the active units in the oligomer chain to inactive units. The solvent reacted to form low molecular weight products which resulted in lower viscosity and lessen the water content in bio-oil. Addition of 95 vol% ethanol also inhibited phase separation.

  15. Catalytic cracking of the top phase fraction of bio-oil into upgraded liquid oil

    Science.gov (United States)

    Sunarno, Rochmadi, Mulyono, Panut; Budiman, Arief

    2016-06-01

    The energy consumption is increasing, while oil reserves as a primary energy resource are decreasing, so that is the reason seeking alternative energy source is inevitable. Biomass especially oil palm empty fruit bunches (EFB) which is abundant in Indonesia can be processed into bio-oil by pyrolysis process. The potential for direct substitution of bio-oil for petroleum may be limited due to the high viscosity, high oxygen content, low heating value, and corrosiveness. Consequently, upgrading of the bio-oil before use is inevitable to give a wider variety of applications of its liquid product. Furthermore, upgrading process to improve the quality of bio-oil by reduction of oxygenates involves process such as catalytic cracking. The objective of this research is to study the effect of operation temperature on yield and composition of upgraded liquid oil and to determine physical properties. Bio-oil derived from EFB was upgraded through catalytic cracking using series tubular reactor under atmospheric pressure on a silica-alumina catalyst. Results show that increasing temperature from 450 to 600 °C, resulting in decreasing of upgraded liquid oil (ULO) yield, decreasing viscosity and density of ULO, but increasing in calorimetric value of ULO. The increasing temperature of cracking also will increase the concentration of gasoline and kerosene in ULO.

  16. Alkaline direct transesterification of different species of Stichococcus for bio-oil production.

    Science.gov (United States)

    Gargano, Immacolata; Marotta, Raffaele; Andreozzi, Roberto; Olivieri, Giuseppe; Marzocchella, Antonio; Spasiano, Danilo; Pinto, Gabriele; Pollio, Antonino

    2016-12-25

    The cost of bio-oil refining from microalgal biomass can be significantly reduced by combining extraction and transesterification. The characterisation and optimisation of the combined steps have been carried out on strains of Stichococcus bacillaris, focusing on catalyst type and concentration, reaction time and temperature, methanol/biomass ratio, pre-mixing time and water content in the biomass. The bio-oil yield has been referenced as production of fatty acid methyl esters (FAMEs). The maximum yield (∼17%) was achieved using dried biomass with alkaline catalyst at 60°C and methanol/biomass weight ratio of 79:1. Alkaline catalyst conditions gave faster reaction rates and higher bio-oil yields than acid catalyst. Yield was also strongly affected by water content in the biomass. A mechanistic interpretation has been proposed to elucidate the effect of the different operating conditions. However, the structural characteristics of the Chlorophyta cell wall can be very different, leading to different bio-oil yields when the same protocol is applied. Therefore, the optimised protocol of direct transesterification for Stichococcus bacillaris strains was tested on other Stichococcus strains and several other Chlorophyta species characterised by a different cell wall structure. It was clearly demonstrated that different results for bio-oil yield were obtained within the same microalgal species and much more within different microalgal genera.

  17. Preparation and Characterization of Epoxy Resin Cross-Linked with High Wood Pyrolysis Bio-Oil Substitution by Acetone Pretreatment

    Directory of Open Access Journals (Sweden)

    Yi Liu

    2017-03-01

    Full Text Available The use of cost effective solvents may be necessary to store wood pyrolysis bio-oil in order to stabilize and control its viscosity, but this part of the production system has not been explored. Conversely, any rise in viscosity during storage, that would occur without a solvent, will add variance to the production system and render it cost ineffective. The purpose of this study was to modify bio-oil with a common solvent and then react the bio-oil with an epoxy for bonding of wood without any loss in properties. The acetone pretreatment of the bio-oil/epoxy mixture was found to improve the cross-linking potential and substitution rate based on its mechanical, chemical, and thermal properties. Specifically, the bio-oil was blended with epoxy resin at weight ratios ranging from 2:1 to 1:5 and were then cured. A higher bio-oil substitution rate was found to lower the shear bond strength of the bio-oil/epoxy resins. However, when an acetone pretreatment was used, it was possible to replace the bio-oil by as much as 50% while satisfying usage requirements. Extraction of the bio-oil/epoxy mixture with four different solvents demonstrated an improvement in cross-linking after acetone pretreatment. ATR-FTIR analysis confirmed that the polymer achieved a higher cross-linked structure. DSC and TGA curves showed improved thermal stability with the addition of the acetone pretreatment. UV-Vis characterization showed that some functional groups of the bio-oil to epoxy system were unreacted. Finally, when the resin mixture was utilized to bond wood, the acetone pretreatment coupled with precise tuning of the bio-oil:epoxy ratio was an effective method to control cross-linking while ensuring acceptable bond strength.

  18. ECOLOGICAL AND ECONOMIC EFFICIENCY OF PEAT FAST PYROLYSIS PROJECTS AS AN ALTERNATIVE SOURCE OF RAW ENERGY RESOURCES

    Directory of Open Access Journals (Sweden)

    Pavel Tcvetkov

    2016-01-01

    Full Text Available The objective of this review is to find ecologically and economically reasonable method of biomass processing to produce electricity and thermal energy. The major causes of the annual increase in the volume of consumed electricity and thermal energy are the current pace of scientific and technological progress, the overcrowding of cities and industrial agglomeration. Traditional energy sources (coal, oil, gas have a significant negative impact on the environment, which leads to the deterioration of sanitary-hygienic indicators of the human environment. Besides, prices for traditional energy resources are increasing due to the decline of easy produced stocks. The goal of this article is the investigation and evaluation of environmental and economic efficiency of biomass fast pyrolysis methods for as modern energy resources. The result of the review is the choice of biomass fast pyrolysis as the most environmentally reasonable and economically viable local method of producing electricity and thermal energy in Russia. This method is more eco-friendly, compared to other alternative energy sources, for example using peat as solid fuel.

  19. Stability of emulsion from bio-oil and diesel oil and combustion experimental study of emulsion

    Energy Technology Data Exchange (ETDEWEB)

    Yaji, Huang; Zhaoping, Zhong; Baosheng, Jin; Bin, Li; Yu, Sun [Thermal Engineering Research Institute, Southeast University (China)

    2010-07-01

    This paper presents a study of the stability of an emulsion from bio-oil and diesel oil through an experimental combustion study. The emulsion was prepared using emulsifiers Span-80 and Tween-80 and bio-oil and diesel oil. This paper studies and analyses combustion, gaseous pollutants characteristics, and the effect of the HLB value and volume fraction of bio-oil on the stability of the emulsion. One of the major study conclusions was that the combustion temperature and the concentration of SO2, NOX and CO of emulsion are lower than those of diesel oil if equal flue gas oxygen is presumed. To conclude, emulsion could be used as an alternative oil fuel, however some questions such as: higher viscosity, higher exhaust heat loss, and very low acidity need more attention and more study in future research.

  20. FLASH PYROLYSIS OF BIOMASS PARTICLES IN FLUIDIZED BED FOR BIO-OIL PRODUCTION

    Institute of Scientific and Technical Information of China (English)

    Shurong Wang; Mengxiang Fang; Chunjiang Yu; Zhongyang Luo; Kefa Cen

    2005-01-01

    Biomass utilization could relieve the pressure caused by conventional energy shortage and environmental pollution. Advantage should be taken of the abundant biomass in China as clean energy source to substitute for traditional fossil fuels. At present, flash pyrolysis appears to be an efficient method to produce high yields of liquids that could either be directly used as fuel or converted to other valuable chemicals. Experiments were carried out of pyrolyzing biomass particles in a hot dense fluidized bed of sand to obtain high-quality bio-oil. Among four kinds of biomass species adopted in our experiment, Padauk Wood had the best characteristics in producing bio-oil. GC-MS analysis showed bio-oil to be a complex mixture consisting of many compounds. Furthermore, an integrated model was proposed to reveal how temperature influences biomass pyrolysis. Computation indicated that biomass particles underwent rapid heating before pyrolysis.

  1. Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

    Directory of Open Access Journals (Sweden)

    Shouyun Cheng

    2016-12-01

    Full Text Available The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction, and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.

  2. Method to upgrade bio-oils to fuel and bio-crude

    Science.gov (United States)

    Steele, Philip H; Pittman, Jr., Charles U; Ingram, Jr., Leonard L; Gajjela, Sanjeev; Zhang, Zhijun; Bhattacharya, Priyanka

    2013-12-10

    This invention relates to a method and device to produce esterified, olefinated/esterified, or thermochemolytic reacted bio-oils as fuels. The olefinated/esterified product may be utilized as a biocrude for input to a refinery, either alone or in combination with petroleum crude oils. The bio-oil esterification reaction is catalyzed by addition of alcohol and acid catalyst. The olefination/esterification reaction is catalyzed by addition of resin acid or other heterogeneous catalyst to catalyze olefins added to previously etherified bio-oil; the olefins and alcohol may also be simultaneously combined and catalyzed by addition of resin acid or other heterogeneous catalyst to produce the olefinated/esterified product.

  3. Corrosion properties of bio-oil and its emulsions with diesel

    Institute of Scientific and Technical Information of China (English)

    LU Qiang; ZHANG Jian; ZHU XiFeng

    2008-01-01

    Bio-oil is a new liquid fuel but very acidic. In this study, bio-oil pyrolyzed from rice husk and two bio-oil/diesel emulsions with bio-oil concentrations of 10 wt% and 30 wt% were prepared. Tests were carried out to determine their corrosion properties to four metals of aluminum, brass, mild steel and stainless steel at different temperatures. Weight loss of the metals immersed in the oil samples was recorded. The chemical states of the elements on metal surface were analyzed by X-ray photoelectron spectroscopy (XPS). The results indicated that mild steel was the least resistant to corrosion, followed by aluminum, while brass exhibited slight weight loss. The weight loss rates would be greatly enhanced at elevated temperatures. Stainless steel was not affected under any conditions. After corrosion, increased organic deposits were formed on aluminum and brass, but not on stainless steel. Mild steel was covered with many loosely attached corrosion materials which were easy to be removed by washing and wiping. Significant metal loss was detected on surface of aluminum and mild steel. Zinc was etched away from brass surface, while metallic copper was oxidized to Cu2O. Increased Cr2O3 and NiO were presented on surface of stainless steel to form a compact passive protection film. The two emulsions were less corrosive than the bio-oil. This was due to the protection effect of diesel. Diesel was the continuous phase in the emulsions and thus could limit the contact area between bio-oil and metals.

  4. Characterization of biochar and bio-oil samples obtained from carbonization of various biomass materials

    Energy Technology Data Exchange (ETDEWEB)

    Oezcimen, Didem; Ersoy-Mericboyu, Ayseguel [Istanbul Technical University, Chemical-Metallurgical Engineering Faculty, Department of Chemical Engineering, Maslak 34469, Istanbul (Turkey)

    2010-06-15

    Apricot stone, hazelnut shell, grapeseed and chestnut shell are important biomass residues obtained from the food processing industry in Turkey and they have a great importance as being a source of energy. In this study, the characteristics of bio-oil and biochar samples obtained from the carbonization of apricot stone, hazelnut shell, grapeseed and chestnut shell were investigated. It was found that the biochar products can be characterized as carbon rich, high heating value and relatively pollution-free potential solid biofuels. The bio-oil products were also presented as environmentally friendly green biofuel candidates. (author)

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

  8. Fast Pyrolysis of Biomass in a Fluidized Bed Reactor: In Situ Filtering of the Vapors

    NARCIS (Netherlands)

    Hoekstra, Elly; Hogendoorn, Kees J.A.; Wang, Xiaoquan; Westerhof, Roel J.M.; Kersten, Sascha R.A.; Swaaij, van Wim P.M.; Groeneveld, Michiel J.

    2009-01-01

    A system to remove in situ char/ash from hot pyrolysis vapors has been developed and tested at the University of Twente. The system consists of a continuous fluidized bed reactor (0.7 kg/h) with immersed filters (wire mesh, pore size 5 μm) for extracting pyrolysis vapors. Integration of the filter s

  9. Bio-Oil Separation and Stabilization by Supercritical Fluid Fractionation. 2014 Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Agblevor, Foster [Utah State Univ., Logan, UT (United States); Petkovic, Lucia [Idaho National Lab. (INL), Idaho Falls, ID (United States); Bennion, Edward [Utah State Univ., Logan, UT (United States); Quinn, Jason [Utah State Univ., Logan, UT (United States); Moses, John [CF Technologies, Hyde Park, MA (United States); Newby, Deborah [Idaho National Lab. (INL), Idaho Falls, ID (United States); Ginosar, Daniel [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2014-03-01

    The objective of this project is to use supercritical fluids to separate and fractionate algal-based bio-oils into stable products that can be subsequently upgraded to produce drop-in renewable fuels. To accomplish this objective, algae was grown and thermochemically converted to bio-oils using hydrothermal liquefaction (HTL), pyrolysis, and catalytic pyrolysis. The bio-oils were separated into an extract and a raffinate using near-critical propane or carbon dioxide. The fractions were then subjected to thermal aging studies to determine if the extraction process had stabilized the products. It was found that the propane extract fraction was twice as stable as the parent catalytic pyrolysis bio-oils as measured by the change in viscosity after two weeks of accelerated aging at 80°C. Further, in-situ NMR aging studies found that the propane extract was chemically more stable than the parent bio-oil. Thus the milestone of stabilizing the product was met. A preliminary design of the extraction plant was prepared. The design was based on a depot scale plant processing 20,000,000 gallons per year of bio-oil. It was estimated that the capital costs for such a plant would be $8,700,000 with an operating cost of $3,500,000 per year. On a per gallon of product cost and a 10% annual rate of return, capital costs would represent $0.06 per gallon and operating costs would amount to $0.20 per gallon. Further, it was found that the energy required to run the process represented 6.2% of the energy available in the bio-oil, meeting the milestone of less than 20%. Life cycle analysis and greenhouse gas (GHG) emission analysis found that the energy for running the critical fluid separation process and the GHG emissions were minor compared to all the inputs to the overall well to pump system. For the well to pump system boundary, energetics in biofuel conversion are typically dominated by energy demands in the growth, dewater, and thermochemical process. Bio-oil stabilization by

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. Catalyst screening for the hydrothermal gasification of aqueous phase of bio-oil

    NARCIS (Netherlands)

    Chakinala, A.G.; Chinthaginjala, J.K.; Seshan, K.; Swaaij, van W.P.M.; Kersten, S.R.A.; Brilman, D.W.F.

    2012-01-01

    The catalytic gasification in supercritical water of the water soluble fraction of bio-oil, either obtained directly by phase-separated pyrolysis-oil from ligno-cellulosic biomass or by hydrotreatment of that oil, is reported in this study. Several heterogeneous metal catalysts Pt, Pd, Ru, Rh, and N

  12. Co-cracking of real MSW into bio-oil over natural kaolin

    Science.gov (United States)

    Gandidi, I. M.; Susila, M. D.; Pambudi, N. A.

    2017-03-01

    Municipal solid waste (MSW) is a potential material that can be converted into bio-oil through thermal degradation process or pyrolysis. The efficiency and productivity of pyrolysis can be increased with the use of natural catalyst like kaolin. The addition of catalyst also reduces the overall cost of conversion process. In this study conversion of MSW into Bio Fuel using Pyrolysis in the presence of of natural kaolin as catalyst has been investigated for 60 min at 400°C temperature. During the process 0.5 w/w catalyst to MSW ratio was maintained. Gas chromatography-mass spectrometry (GC-MS) was used to analyse the chemical composition of bio fuel. It is found that bio-oil production increases substantially with the use of catalyst. It is observed that the production of bio-oil is 23.6 % with the use of catalyst in process, which was only 15.2 % without the use of catalyst. The hydrocarbon range distribution of oil produced through pyrolysis reveals that gasoline and diesel fuel (C5-C20) are its main constituents. The functional group detected in bio-oil by GC-MS analysis is similar to that of diesel-48 in which paraffin and olefin are major mass species.

  13. Technical bio-oils. Fundamentals - products - framework conditions; Technische Biooele. Grundlagen - Produkte - Rahmenbedingungen

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2012-03-27

    The Fachagentur Nachwachsende Rohstoffe e.V. (Guelzow-Pruezen, Federal Republic of Germany) and the Federal Ministry of Food, Agriculture and Consumer Protection (Bonn, Federal Republic of Germany) report on technical bio-oils. The contribution under consideration consists of the following chapters: Fundamentals, technical properties, applications, environmental aspects, legal framework conditions, funding measures; market of biological lubricants, economic operation with biological lubricants.

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

    Science.gov (United States)

    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...

  15. Microwave-assisted liquefaction of rape straw for the production of bio-oils

    Science.gov (United States)

    Xing-Yan Huang; Feng Li; Jiu-Long Xie; Cornelis F. De Hoop; Chung-Yun Hse; Jin-Qiu Qi; Hui. Xiao

    2017-01-01

    The acid-catalyzed liquefaction of rape straw in methanol using microwave energy was examined. Conversion yield and energy consumption were evaluated to profile the microwave-assisted liquefaction process. Chemical components of the bio-oils from various liquefaction conditions were identified. A higher reaction temperature was found to be beneficial to obtain higher...

  16. Selective catalytic conversion of bio-oil over high-silica zeolites.

    Science.gov (United States)

    Widayatno, Wahyu Bambang; Guan, Guoqing; Rizkiana, Jenny; Du, Xiao; Hao, Xiaogang; Zhang, Zhonglin; Abudula, Abuliti

    2015-03-01

    Four high silica zeolites, i.e., HSZ-385, 890, 960, and 990 were utilized for the selective catalytic conversion of bio-oil from Fallopia japonica to certain chemicals in a fixed-bed reactor. The Beta-type HSZ-960 zeolite showed the highest selectivity to hydrocarbons, especially to aromatics as well as PAH compounds with the lowest unwanted chemicals while HSZ-890 showed high selectivity to aromatics. NH3-Temperature Programmed Desorption (TPD) analysis indicated that different amounts of acid sites in different zeolites determined the catalytic activity for the oxygen removal from bio-oil, in which the acid sites at low temperature (LT) region gave more contribution within the utilized temperature region. The reusability test of HSZ-960 showed the stability of hydrocarbons yield at higher temperature due to the significant contribution of coke gasification which assisted further deoxygenation of bio-oil. These results provide a guidance to select suitable zeolite catalysts for the upgrading of bio-oil in a practical process.

  17. Alkaline direct transesterification of different species of Stichococcus for bio-oil production

    NARCIS (Netherlands)

    Gargano, Immacolata; Marotta, Raffaele; Andreozzi, Roberto; Olivieri, Giuseppe; Marzocchella, Antonio; Spasiano, Danilo; Pinto, Gabriele; Pollio, Antonino

    2016-01-01

    The cost of bio-oil refining from microalgal biomass can be significantly reduced by combining extraction and transesterification. The characterisation and optimisation of the combined steps have been carried out on strains of Stichococcus bacillaris, focusing on catalyst type and concentration,

  18. Experimental study of the bio-oil production from sewage sludge by supercritical conversion process.

    Science.gov (United States)

    Wang, Yan; Chen, Guanyi; Li, Yanbin; Yan, Beibei; Pan, Donghui

    2013-11-01

    Environment-friendly treatment of sewage sludge has become tremendously important. Conversion of sewage sludge into energy products by environment-friendly conversion process, with its energy recovery and environmental benefits, is being paid significant attention. Direct liquefaction of sewage sludge into bio-oils with supercritical water (SCW) was therefore put forward in this study, as de-water usually requiring intensive energy input is not necessary in this direct liquefaction. Supercritical water may act as a strong solvent and also a reactant, as well as catalyst promoting reaction process. Experiments were carried out in a self designed high-pressure reaction system with varying operating conditions. Through orthogonal experiments, it was found that temperature and residence time dominated on bio-oil yield compared with other operating parameters. Temperature from 350 to 500°C and reaction residence time of 0, 30, 60min were accordingly investigated in details, respectively. Under supercritical conversion, the maximum bio-oil yield could achieve 39.73%, which was performed at 375°C and 0min reaction residence time. Meanwhile, function of supercritical water was concluded. Fuel property analysis showed the potential of bio-oil application as crude fuel.

  19. Direct liquefaction of Dunaliella tertiolecta for bio-oil in sub/supercritical ethanol-water.

    Science.gov (United States)

    Chen, Yu; Wu, Yulong; Zhang, Peiling; Hua, Derun; Yang, Mingde; Li, Chun; Chen, Zhen; Liu, Ji

    2012-11-01

    This paper presents bio-oil preparation by direct liquefaction of Dunaliella tertiolecta (D. tertiolecta) with sub/supercritical ethanol-water as the medium in a batch autoclave with high temperature and high pressure. The results indicated that ethanol and water showed synergistic effects on direct liquefaction of D. tertiolecta. The maximum bio-oil yield was 64.68%, with an optimal D. tertiolecta conversion of 98.24% in sub/supercritical ethanol-water. The detailed chemical compositional analysis of the bio-oil was performed using an EA, FT-IR, and GC-MS. The empirical formulas of the bio-oil obtained using the ethanol-water co-solvent (40%, v/v) and sole water as the reaction medium were CH(1.52)O(0.14)N(0.06) and CH(1.43)O(0.23)N(0.09), with calorific values of 34.96 and 29.80 MJ kg(-1), respectively. XPS and SEM results showed that ethanol-water is a very effective reaction medium in the liquefaction. A plausible reaction mechanism of the main chemical component in D. tertiolecta is proposed based on our results and the literatures.

  20. Electron microscopy study of the deactivation of nickel based catalysts for bio oil hydrodeoxygenation

    DEFF Research Database (Denmark)

    Gardini, Diego; Mortensen, Peter Mølgaard; Carvalho, Hudson W. P.

    2014-01-01

    Hydrodeoxygenation (HDO) is proposed as an efficient way to remove oxygen in bio-oil, improving its quality as a more sustainable alternative to conventional fuels in terms of CO2 neutrality and relative short production cycle [1]. Ni and Ni-MoS2 nanoparticles supported on ZrO2 show potential...

  1. Hydrothermal liquefaction of oil mill wastewater for bio-oil production in subcritical conditions.

    Science.gov (United States)

    Hadhoum, Loubna; Balistrou, Mourad; Burnens, Gaëtan; Loubar, Khaled; Tazerout, Mohand

    2016-10-01

    The main purpose of this study is to investigate the direct hydrothermal liquefaction of oil mill wastewater (OMWW). Experiments were carried out at different temperatures (240-300°C), water contents (58-88wt.%) and reaction times (15-45min). Results show that the highest bio-oil yield was about 58wt.%, resulting in a higher heating value of 38MJ/kg. This was conducted at the following optimal conditions: water content 88wt.%, a temperature of 280°C, and 30min as reaction time. To put bio-oil into wide application, the various physical and chemical characteristics were determined. A detailed chemical composition analysis of bio-oil was performed by gas chromatography-mass spectrometry (GC-MS) coupled with a flame ionization detector (FID). The dominant compounds were identified by using NIST library. Analyses show that the bio-oil contains mainly oleic acid, hexadecanoic acid, fatty acid methyl ester, fatty acid ethyl ester, amino acid derived compounds and phenolic compounds.

  2. Bio-oil from cassava peel: a potential renewable energy source.

    Science.gov (United States)

    Ki, Ong Lu; Kurniawan, Alfin; Lin, Chun Xiang; Ju, Yi-Hsu; Ismadji, Suryadi

    2013-10-01

    In this work, liquid biofuel (bio-oil) was produced by pyrolizing cassava peel. The experiments were conducted isothermally in a fixed-bed tubular reactor at temperatures ranging from 400 to 600°C with a heating rate of 20°C/min. The chemical compositions of bio-oil were analyzed by a gas chromatography mass spectrometry (GC-MS) technique. For the optimization of liquid product, temperature was plotted to be the most decisive factor. The maximum yield of bio-oil ca. 51.2% was obtained at 525°C and the biofuel has a gross calorific value of 27.43 MJ/kg. The kinetic-based mechanistic model fitted well with experimental yield of pyrolysis products with the mean squared error (MSE) of 13.37 (R(2)=0.96) for solid (char), 16.24 (R(2)=0.95) for liquid (bio-oil), and 0.49 (R(2)=0.99) for gas.

  3. Effects of Current on Microcosmic Properties of Catalyst and Reforming of Bio-oil

    Institute of Scientific and Technical Information of China (English)

    Li-xia Yuan; Tong-qi Ye; Fei-yan Gong; Quan-xin Li

    2009-01-01

    Highly effective production of hydrogen from bio-oil was achieved by using a low-temperature electrochemical catalytic reforming approach over the conventional Ni-based reforming cat-alyst (NiO-Al2O3), where an AC electronic current passed through the catalyst bed. The promoting effects of current on the bio-oil reforming were studied. It was found that the performance of the bio-oil reforming was remarkably enhanced by the current which passed through the catalyst. The effects of currents on the microcosmic properties of the catalyst, including the Brunauer-Emmett-Teller (BET) surface area, pore diameter, pore volume, the size of the crystallites and the reduction level of NiO into Ni, were carefully characterized by BET, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscope. The desorption of the thermal electrons from the electrified catalyst was directly observed by the TOF (time of flight) measurements. The mechanism of the electrochemical catalytic reforming of bio-oil is discussed based on the above investigation.

  4. Complete utilization of spent coffee grounds to produce biodiesel, bio-oil and biochar

    Science.gov (United States)

    This study presents the complete utilization of spent coffee grounds to produce biodiesel, bio-oil and biochar. Lipids extracted from spent grounds were converted to biodiesel to evaluate neat and blended (B5 and B20) fuel properties against ASTM and EN standards. Although neat biodiesel displayed h...

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

    Science.gov (United States)

    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.

  6. Structural analysis of Catliq® bio-oil produced by catalytic liquid conversion of biomass

    DEFF Research Database (Denmark)

    Toor, Saqib Sohail; Rosendahl, Lasse; Nielsen, Mads Pagh;

    Liq® process compared with combustion is that also wet material can be processed. In the process, the waste is transformed to bio-oil, combustible gases and water-soluble organic compounds. The raw material used in this study was DDGS (Dried Distilled Grain with Solubles), a residual product in 1st generation......) process is a second generation process for the production of bio-oil from different biomass-based waste materials. The process is carried out at subcritical conditions (280-350 °C and 180-250 bar) and in the presence of homogeneous (KOH) and heterogeneous (ZrO2) catalysts. The great advantage with the Cat...... ethanol production, available in huge quantities. DDGS is today used as animal feed but in a future with increasing production of DDGS, converting it into bio-oil may be an attractive alternative. The bio-oil can be used for green electricity production or it can be upgraded to bio-diesel. In the current...

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  10. Corn stalks char from fast pyrolysis as precursor material for preparation of activated carbon in fluidized bed reactor.

    Science.gov (United States)

    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.

  11. Characterization of preservative and pesticide as potential of bio oil compound from pyrolisis of cocoa shell using gas chromatography

    Science.gov (United States)

    Mashuni, Jahiding, M.; Kurniasih, I.; Zulkaidah

    2017-03-01

    Cocoa shell is one of the plant waste that has not been widely used. Cocoa shell is potential as a producer of bio oil because it contains lignocellulose. The bio oil of Liquid volatile matter (LVM) is the products of smoke condensation from the pyrolysis reactor. The bio oil of cocoa shell from pyrolysis process can be made as raw materials for the application of pesticide and preservative. The aims of this research were to produce bio oil from cocoa shell by pyrolysis and analyzing the content using Gas Chromatography (GC). Bio oil production was done by pyrolysis with variations of temperature, i.e. 400, 500, 600 and 700 °C. Pyrolysis reaction generates three products: gas, liquid and solid. The yield of bio oil with variations of pyrolisis temperature, i.e. 400, 500, 600 and 700 °C were obtained i.e. 46, 45, 44 and 40% (v/w), respectively. The chromatogram results showed the chemical components of bio oil from the cocoa shell were ammonia, hexane, alcohol, ketone, acid and phenolic compounds which can be used as material of preservative and pesticide.

  12. Hydrodeoxygenation of prairie cordgrass bio-oil over Ni based activated carbon synergistic catalysts combined with different metals.

    Science.gov (United States)

    Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; Kadis, Ethan; Cao, Yuhe; Julson, James; Gu, Zhengrong

    2016-06-25

    Bio-oil can be upgraded through hydrodeoxygenation (HDO). Low-cost and effective catalysts are crucial for the HDO process. In this study, four inexpensive combinations of Ni based activated carbon synergistic catalysts including Ni/AC, Ni-Fe/AC, Ni-Mo/AC and Ni-Cu/AC were evaluated for HDO of prairie cordgrass (PCG) bio-oil. The tests were carried out in the autoclave under mild operating conditions with 500psig of H2 pressure and 350°C temperature. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM). The results show that all synergistic catalysts had significant improvements on the physicochemical properties (water content, pH, oxygen content, higher heating value and chemical compositions) of the upgraded PCG bio-oil. The higher heating value of the upgraded bio-oil (ranging from 29.65MJ/kg to 31.61MJ/kg) improved significantly in comparison with the raw bio-oil (11.33MJ/kg), while the oxygen content reduced to only 21.70-25.88% from 68.81% of the raw bio-oil. Compared to raw bio-oil (8.78% hydrocarbons and no alkyl-phenols), the Ni/AC catalysts produced the highest content of gasoline range hydrocarbons (C6-C12) at 32.63% in the upgraded bio-oil, while Ni-Mo/AC generated the upgraded bio-oil with the highest content of gasoline blending alkyl-phenols at 38.41%.

  13. Polymerization and cracking during the hydrotreatment of bio-oil and heavy fractions obtained by fractional condensation using Ru/C and NiMo/Al2O3 catalyst

    NARCIS (Netherlands)

    Kadarwati, S.; Oudenhoven, S.R.G; Schagen, M.; Hu, X.; Garcia-Perez, M.; Kersten, S.R.A.; Li, C.Z.; Westerhof, R.J.M.

    2016-01-01

    Two-step hydrotreatment experiments were performed using three completely different bio-oil fractions namely: whole bio-oil, heavy bio-oil obtained after fractional condensation of pyrolysis vapours and pyrolytic lignin obtained by cold water precipitation of the bio-oil. The aim is to study the de-

  14. 玉米秸秆生物油-柴油乳化油的燃烧特性%Combustion Characteristics of a Direct Injection Diesel Engine Operating on Emulsions from Corn Stalk Bio-Oil and Diesel Fuel

    Institute of Scientific and Technical Information of China (English)

    黄勇成; 韩旭东; 尚上; 王丽

    2011-01-01

    The experimental bio-oil produced from corn stalk through fast pyrolysis process is mainly composed of oxygenated organic and water, thereby restricting its direct use as fuel. However, the use of bio-oil in diesel engines can be realized by developing emulsions from bio-oil and diesel fuel. In this paper, two emulsions with 10% and 20% by mass fraction of bio-oil in diesel fuel, represented by B10 and B20 respectively, were prepared by using ultrasonic emulsification method. Then, the combustion characteristics of an unmodified direct injection diesel engine operating on the two emulsions were studied. The results show that the engine operating on the two emulsions displays a longer ignition delay, exhibits a higher peak value of premixed burning rate and pressure rise rate and a slightly lower peak value of diffusion burning rate, displays a lower peak combustion pressure and average combustion temperature, and has a shorter combustion duration when compared with No.0 diesel. In comparison with B10, B20 has a longer ignition delay, while exhibits a lower peak value of premixed burning rate, pressure rise rate, in-cylinder pressure and combustion temperature. In addition, the fuel economy for B10 operation is comparable to that for No.0 diesel operation, while the fuel economy of B20 is poorer than that of No.0 diesel.%试验用生物油是玉米秸秆快速热解液化的产物,主要成分为含氧有机混合物和水,不宜直接作为燃料使用,但与柴油乳化后可实现其在发动机中应用.在一台未作改动的直喷式柴油机上研究了玉米秸秆生物油质量分数分别为10%(B10)和20%(B20)的生物油-柴油乳化油的燃烧特性.结果表明:与0号柴油相比,乳化油的滞燃期延长,预混燃烧放热峰值和最大压力升高率升高,扩散燃烧放热峰值略低,最高燃烧压力和缸内气体平均温度降低,燃烧持续期缩短.与B10相比,B20的滞燃期延长,而预混燃烧放热峰值、最大压力升

  15. Upgrading of Bio-Oil into High-Value Hydrocarbons via Hydrodeoxygenation

    Directory of Open Access Journals (Sweden)

    Murni M. Ahmad

    2010-01-01

    Full Text Available Problem statement: World energy consumption is forecasted to grow significantly for the foreseeable future with fossil fuel remains the governing energy source. The demand in the need to explore alternative fuel source was further triggered by the overwhelmingly inconsistent cost of gasoline. Bio-oil is an alternative energy source produced from pyrolysis of biomass. However it is undesirable as a ready alternative transportation fuel due to its unfavorable nature i.e., highly oxygenated and low octane number. To overcome these physicochemical issues, hydrodeoxygenation reaction is a possible upgrading method i.e., by partial or total elimination of oxygen and hydrogenation of chemical structures. Hence, this study aimed to investigate feasible routes and to develop the process route to upgrade the pyrolytic bio-oil from biomass into value-added chemicals for the production of transportation fuel, i.e., benzene and cyclohexane, via hydrodeoxygenation process via simulation in PETRONAS iCON software. Approach: In this study, hydrodeoxygenation of phenols and substituted phenols was used to represent the hydrodeoxygenation of the major oxygen compound in bio-oil due to their low reactivity in HDO. Results: By assuming the feedstock used was 1% of the total palm shell available in Malaysia, i.e., 2,587 kg h-1 bio-oil, the simulation predicted the production of 226 kg h-1 benzene, 236 kg h-1 cyclohexane and 7 kg h-1 cyclohexene, with the yield of 34, 81 and 3% respectively. The preliminary economic potential was calculated to be positive. It was also observed that hydrogen was the limiting reactant in the hydrogenation reaction. Conclusion/Recommendations: The simulation study indicated positive technical and economic feasibility of hydrodeoxygenation of pyrolytic bio-oil from biomass into benzene and cyclohexane for the transportation fuel industry. This potential can be explored in more details and further findings can promote the prospect of co

  16. Swine manure/crude glycerol co-liquefaction: physical properties and chemical analysis of bio-oil product.

    Science.gov (United States)

    Xiu, Shuangning; Shahbazi, Abolghasem; Shirley, Vestel B; Wang, Lijun

    2011-01-01

    The aim of this work was to investigate the principal structural and physico-chemical changes of bio-oils associated with liquefaction of swine manure with crude glycerol and its key fraction, free fatty acids. Bio-oils have been obtained from liquefaction processes at 340 °C. They were subjected to various physico-chemical characterization methods. FTIR data indicated a reduction in aliphatic structures and an increase in more oxidized and, probably, more polycondensed aromatic components resulting from the addition of crude glycerol to swine manure. GC-MS data indicated that the addition of crude glycerol facilitated the esterification reaction in sub-critical water to convert organic acids contained in bio-oil into various kinds of esters. The dynamic viscosity of bio-oil decreased dramatically by adding crude glycerol into the swine manure.

  17. Chemical characterization of bio-oils using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

    Science.gov (United States)

    Tessarolo, Nathalia S; dos Santos, Luciana R M; Silva, Raphael S F; Azevedo, Débora A

    2013-03-01

    The liquid product obtained via the biomass flash pyrolysis is commonly called bio-oil or pyrolysis oil. Bio-oils can be used as sources for chemicals or as fuels, primarily in mixtures or emulsions with fossil fuels. A detailed chemical characterization of bio-oil is necessary to determine its potential uses. Such characterization demands a powerful analytical technique such as comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-TOFMS). Limited chemical information can be obtained from conventional gas chromatography coupled mass spectrometry (GC-MS) because of the large number of compounds and coelutions. Thus, GC×GC-TOFMS was used for the individual identification of bio-oil components from two samples prepared via the flash pyrolysis of empty palm fruit bunch and pine wood chips. To the best of our knowledge, few papers have reported comprehensive two-dimensional gas chromatography (GC×GC) for bio-oil analysis. Many classes of compounds such as phenols, benzenediols, cyclopentenones, furanones, indanones and alkylpyridines were identified. Several coelutions present in the GC-MS were resolved using GC×GC-TOFMS. Many peaks were detected for the samples by GC-MS (~166 and 129), but 631 and 857 were detected by GC×GC-TOFMS, respectively. The GC×GC-TOFMS analyses indicated that the major classes of components (analytes>0.5% relative area) in the two bio-oil samples are ketones, cyclopentenones, furanones, furans, phenols, benzenediols, methoxy- and dimethoxy-phenols and sugars. In addition, esters, aldehydes and pyridines were found for sample obtained from empty palm fruit bunch, while alcohols and cyclopentanediones were found in sample prepared from pine wood chips indicating different composition profiles due to the biomass sources. The elucidation of the composition of empty fruit bunch and pine wood chips bio-oils indicates that these oils are suitable for the production of value-added chemicals. The

  18. Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

    Institute of Scientific and Technical Information of China (English)

    Xing-long Li; Shen Ning; Li-xia Yuan; Quan-xin Li

    2011-01-01

    We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method.The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass.The product gas was a mixed gas containing 72%H2,26%CO2,1.9%CO,and a trace amount of CH4.It was observed that adding biomass char (a by-product of pyrolysis of biomass) could remarkably increase the absolute H2 yield (about 20%-50%).The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H2O.In addition,the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.

  19. Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

    Science.gov (United States)

    Li, Xing-long; Ning, Shen; Yuan, Li-xia; Li, Quan-xin

    2011-08-01

    We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass. The product gas was a mixed gas containing 72%H2, 26%CO2, 1.9%CO, and a trace amount of CH4. It was observed that adding biomass char (a by-product of pyrolysis of biomass) could remarkably increase the absolute H2 yield (about 20%-50%). The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H2O. In addition, the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.

  20. Catalytic Steam Reforming of Bio-Oil to Hydrogen Rich Gas

    DEFF Research Database (Denmark)

    Trane-Restrup, Rasmus

    in reforming. Therefore SR of ethanol, acetic acid, acetone, acetol, 1-propanol, and propanal was investigated over Ni/MgAl2O4 at temperatures between 400 and 700 ‰ and at S/C=6. The yield of H2 and conversion increased with increasing temperature while the yield of by-products decreased with temperature......Bio-oil is a liquid produced by pyrolysis of biomass and its main advantage compared with biomass is an up to ten times higher energy density. This entails lower transportation costs associated with the utilization of biomass for production of energy and fuels. Nevertheless, the bio-oil has a low....... The support material aected the conversion and carbon deposition while the product distributions as function of temperature were similar. The yield of CO and H2 increased with increasing temperature while the yield of CO2, methane, and ethene decreased with temperature. The most abundant by-products were...

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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).

  4. Properties of bio-oil generated by a pyrolysis of forest cedar residuals with the movable Auger-type reactor

    Energy Technology Data Exchange (ETDEWEB)

    Nishimura, Shun; Ebitani, Kohki, E-mail: ebitani@jaist.ac.jp [School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan); Miyazato, Akio [Nanotechnology Center, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa 923-1292 (Japan)

    2016-02-01

    Our research project has developed the new movable reactor for bio-oil production in 2013 on the basis of Auger-type system. This package would be a great impact due to the concept of local production for local consumption in the hilly and mountainous area in not only Japan but also in the world. Herein, we would like to report the properties of the bio-oil generated by the developing Auger-type movable reactor. The synthesized bio-oil possessed C: 46.2 wt%, H: 6.5 wt%, N: wt%, S: <0.1 wt%, O: 46.8 wt% and H{sub 2}O: 18.4 wt%, and served a good calorific value of 18.1 MJ/kg. The spectroscopic and mass analyses such as FT-IR, GC-MS, {sup 13}C-NMR and FT-ICR MS supported that the bio-oil was composed by the fine mixtures of methoxy phenols and variety of alcohol or carboxylic acid functional groups. Thus, it is suggested that the bio-oil generated by the new movable Auger-type reactor has a significant potential as well as the existing bio-oil reported previously.

  5. High quality bio-oil from catalytic flash pyrolysis of lignocellulosic biomass over alumina-supported sodium carbonate

    KAUST Repository

    Imran, Ali

    2014-11-01

    Performance of a novel alumina-supported sodium carbonate catalyst was studied to produce a valuable bio-oil from catalytic flash pyrolysis of lignocellulosic biomass. Post treatment of biomass pyrolysis vapor was investigated in a catalyst fixed bed reactor at the downstream of the pyrolysis reactor. In-situ catalytic upgrading of biomass pyrolysis vapor was conducted in an entrained flow pyrolysis reactor by feeding a premixed feedstock of the catalyst and biomass. Na2CO3/gamma-Al2O3 was very effective for de-oxygenation of the pyrolysis liquid and oxygen content of the bio-oil was decreased from 47.5 wt.% to 16.4 wt.%. An organic rich bio-oil was obtained with 5.8 wt.% water content and a higher heating value of 36.1 MJ/kg. Carboxylic acids were completely removed and the bio-oil had almost a neutral pH. This bio-oil of high calorific low, low water and oxygen content may be an attractive fuel precursor. In-situ catalytic upgrading of biomass pyrolysis vapor produced a very similar quality bio-oil compared to post treatment of pyrolysis vapors, and shows the possible application of Na2CO3/gamma-Al2O3 in a commercial type reactor system such as a fluidized bed reactor. (C) 2014 Elsevier B.V. All rights reserved.

  6. Quantitative investigation of free radicals in bio-oil and their potential role in condensed-phase polymerization.

    Science.gov (United States)

    Kim, Kwang Ho; Bai, Xianglan; Cady, Sarah; Gable, Preston; Brown, Robert C

    2015-03-01

    We report on the quantitative analysis of free radicals in bio-oils produced from pyrolysis of cellulose, organosolv lignin, and corn stover by EPR spectroscopy. Also, we investigated their potential role in condensed-phase polymerization. Bio-oils produced from lignin and cellulose show clear evidence of homolytic cleavage reactions during pyrolysis that produce free radicals. The concentration of free radicals in lignin bio-oil was 7.5×10(20)  spin g(-1), which was 375 and 138 times higher than free-radical concentrations in bio-oil from cellulose and corn stover. Pyrolytic lignin had the highest concentration in free radicals, which could be a combination of carbon-centered (benzyl radicals) and oxygen-centered (phenoxy radicals) organic species because they are delocalized in a π system. Free-radical concentrations did not change during accelerated aging tests despite increases in molecular weight of bio-oils, suggesting that free radicals in condensed bio-oils are stable.

  7. Quantification of real thermal, catalytic, and hydrodeoxygenated bio-oils via comprehensive two-dimensional gas chromatography with mass spectrometry.

    Science.gov (United States)

    Silva, Raquel V S; Tessarolo, Nathalia S; Pereira, Vinícius B; Ximenes, Vitor L; Mendes, Fábio L; de Almeida, Marlon B B; Azevedo, Débora A

    2017-03-01

    The elucidation of bio-oil composition is important to evaluate the processes of biomass conversion and its upgrading, and to suggest the proper use for each sample. Comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) is a widely applied analytical approach for bio-oil investigation due to the higher separation and resolution capacity from this technique. This work addresses the issue of analytical performance to assess the comprehensive characterization of real bio-oil samples via GC×GC-TOFMS. The approach was applied to the individual quantification of compounds of real thermal (PWT), catalytic process (CPO), and hydrodeoxygenation process (HDO) bio-oils. Quantification was performed with reliability using the analytical curves of oxygenated and hydrocarbon standards as well as the deuterated internal standards. The limit of quantification was set at 1ngµL(-1) for major standards, except for hexanoic acid, which was set at 5ngµL(-1). The GC×GC-TOFMS method provided good precision (bio-oil samples. Sugars, furans, and alcohols appear as the major constituents of the PWT, CPO, and HDO samples, respectively. In order to obtain bio-oils with better quality, the catalytic pyrolysis process may be a better option than hydrogenation due to the effective reduction of oxygenated compound concentrations and the lower cost of the process, when hydrogen is not required to promote deoxygenation in the catalytic pyrolysis process.

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

    Science.gov (United States)

    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.

  9. Aspen Plus® and economic modeling of equine waste utilization for localized hot water heating via fast pyrolysis.

    Science.gov (United States)

    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.

  10. Production of aromatics through current-enhanced catalytic conversion of bio-oil tar.

    Science.gov (United States)

    Bi, Peiyan; Yuan, Yanni; Fan, Minghui; Jiang, Peiwen; Zhai, Qi; Li, Quanxin

    2013-05-01

    Biomass conversion into benzene, toluene and xylenes (BTX) can provide basic feedstocks for the petrochemical industry, which also serve as the most important aromatic platform molecules for development of high-end chemicals. Present work explored a new route for transformation of bio-oil tar into BTX through current-enhanced catalytic conversion (CECC), involving the synergistic effect between the zeolite catalyst and current to promote the deoxygenation and cracking reactions. The proposed transformation shows an excellent BTX aromatics selectivity of 92.9 C-mol% with 25.1 wt.% yield at 400 °C over usual HZSM-5 catalyst. The study of the model compounds revealed that the groups such as methoxy, hydroxyl and methyl in aromatics can be effectively removed in the CECC process. Present transformation potentially provides an important approach for production of the key petrochemicals of BTX and the overall use of bio-oil tar derived from bio-oil or biomass. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

    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.

  12. Synthesis of advanced materials for bio-oil production from rice straw by pyrolysis

    Science.gov (United States)

    Phuong Dang, Tuyet; Le, Gia Hy; Thu Giang Pham, Thi; Kien Nguyen, Trung; Canh Dao, Duc; Vu, Thi Minh Hong; Thu Thuy Hoang, Thi; Hoa Tran, Thi Kim; Vu, Anh Tuan

    2011-12-01

    Bio-oil from rice straw is produced by pyrolysis with and without solid acid catalysts. Solid acid catalysts used in rice straw pyrolysis synthesis were the diatomite acidified by an 'atomic implantation method' and nano-sized porous Al-SBA1SBA: Santa Barbara Amorphous type mesoporous silica.-15. Catalysts were characterized by a field emission-scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), x-ray diffraction (XRD), infrared spectroscopy (IR), N2 adsorption/desorption, differential thermal analysis/thermogravimetric analysis (DTA/TGA) and NH3 temperature programmed desorption (NH3-TPD). The obtained results revealed that a similar bio-oil yield (liquid product) of 44-48% can be reached by pyrolysis in the presence of solid acid catalysts at 450 °C compared to that of pyrolysis without catalyst at 550 °C. Moreover, a low yield of gas product was observed. These results show significant potential applications of solid acid catalysts for the improvement of bio-oil yield in the pyrolysis of rice straw.

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

    Science.gov (United States)

    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.

  14. Catalytic Upgrading of Biomass Fast Pyrolysis Vapors with Nano Metal Oxides: An Analytical Py-GC/MS Study

    Directory of Open Access Journals (Sweden)

    Qiang Lu

    2010-11-01

    Full Text Available Fast pyrolysis of poplar wood followed with catalytic cracking of the pyrolysis vapors was performed using analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS. The catalysts applied in this study were nano MgO, CaO, TiO2, Fe2O3, NiO and ZnO. These catalysts displayed different catalytic capabilities towards the pyrolytic products. The catalysis by CaO significantly reduced the levels of phenols and anhydrosugars, and eliminated the acids, while it increased the formation of cyclopentanones, hydrocarbons and several light compounds. ZnO was a mild catalyst, as it only slightly altered the pyrolytic products. The other four catalysts all decreased the linear aldehydes dramatically, while the increased the ketones and cyclopentanones. They also reduced the anhydrosugars, except for NiO. Moreover, the catalysis by Fe2O3 resulted in the formation of various hydrocarbons. However, none of these catalysts except CaO were able to greatly reduce the acids.

  15. Selective Extraction of Bio-oil from Hydrothermal Liquefaction of Salix psammophila by Organic Solvents with Different Polarities through Multistep Extraction Separation

    OpenAIRE

    Xiao Yang; Hang Lyu; Kaifei Chen; Xiangdong Zhu; Shicheng Zhang; Jianmin Chen

    2014-01-01

    Bio-oil obtained from hydrothermal liquefaction of Salix psammophila is a very complicated mixture with some highly valued chemicals. In order to separate the chemicals from bio-oil, solvent extraction using nine solvents with different polarities were investigated in detail. The bio-oil extraction yield of the nine solvents were from high to low: tetrahydrofuran > toluene > ethyl acetate > acetone > ether > methylene chloride > methanol > petroleum ether > n-hexane. Based on their extraction...

  16. Design of Multiple Metal Doped Ni Based Catalyst for Hydrogen Generation from Bio-oil Reforming at Mild-temperature

    Institute of Scientific and Technical Information of China (English)

    Li-xia Yuan; Fang Ding; Jian-ming Yao; Xiang-song Chen; Wei-wei Liu; Jin-yong Wu; Fei-yan Gong

    2013-01-01

    A new kind of multiple metal (Cu,Mg,Ce) doped Ni based mixed oxide catalyst,synthesized by the co-precipitation method,was used for efficient production of hydrogen from bio-oil reforming at 250-500 ℃.Two reforming processes,the conventional steam reforming (CSR) and the electrochemical catalytic reforming (ECR),were performed for the bio-oil reforming.The catalyst with an atomic mol ratio of Ni∶Cu∶Mg∶Ce∶Al=5.6∶1.1∶1.9∶1.0∶9.9 exhibited very high reforming activity both in CSR and ECR processes,reaching 82.8% hydrogen yield at 500 ℃ in the CSR,yield of 91.1% at 400 ℃ and 3.1 A in the ECR,respectively.The influences of reforming temperature and the current through the catalyst in the ECR were investigated.It was observed that the reforming and decomposition of the bio-oil were significantly enhanced by the current.The promoting effects of current on the decomposition and reforming processes of bio-oil were further studied by using the model compounds of biooil (acetic acid and ethanol) under 101 kPa or low pressure (0.1 Pa) through the time of flight analysis.The catalyst also shows high water gas shift activity in the range of 300-600 ℃.The catalyst features and alterations in the bio-oil reforming were characterized by the ICP,XRD,XPS and BET measurements.The mechanism of bio-oil reforming was discussed based on the study of the elemental reactions and catalyst characterizations.The research catalyst,potentially,may be a practical catalyst for high efficient production of hydrogen from reforning of bio-oil at mild-temperature.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  18. Membrane Fractionation of Biomass Fast Pyrolysis Oil and Impact of its Presence on a Petroleum Gas Oil Hydrotreatment Fractionnement membranaire d’une huile de pyrolyse flash et impact de sa présence sur l’hydrotraitement d’un gazole atmosphérique

    Directory of Open Access Journals (Sweden)

    Pinheiro A.

    2013-09-01

    Full Text Available In order to limit the greenhouse effect causing climate change and reduce the needs of the transport sector for petroleum oils, transformation of lignocellulosic biomass is a promising alternative route to produce automotive fuels, chemical intermediates and energy. Gasification and liquefaction of biomass resources are the two main routes that are under investigation to convert biomass into biofuels. In the case of the liquefaction, due to the unstability of the liquefied products, one solution can be to perform a specific hydrotreatment of fast pyrolysis bio-oils with petroleum cuts in existing petroleum refinery system. With this objective, previous studies [Pinheiro et al. (2009 Energy Fuels 23, 1007-1014; Pinheiro et al. (2011 Energy Fuels 25, 804-812] have been carried out to investigate the impact of oxygenated model compounds on a Straight Run Gas Oil (SRGO hydrotreatment using a CoMo catalyst. The authors have demonstrated that the main inhibiting effects are induced from CO and CO2 produced during hydrodeoxygenation of esters and carboxylic acids. To go further, cotreatment of a fast pyrolysis oil with the same SRGO as used in the previous. studies was investigated in this present work. Firstly the bio-oil was separated into four fractions by membrane fractionation using 400 and 220 Da molecular weight cut-off membranes. The bio-oil and its fractions were analyzed by spectroscopic and chromatographic techniques. Then, one fraction (i.e. fraction enriched in compounds with molecular weight from 220 to 400 Da was mixed with the SRGO and co-treated. Despite some experimental difficulties mainly due to the emulsion instability, the hydrotreatment was successful. An inhibition has been observed on the hydro treating reactions of the SRGO in presence of the bio-oil fraction. The measurement of the CO/CO2/CH4 molar flowrate at the reactor outlet showed that the inhibition was due to the presence of CO and CO2 coming from HDO rather than to

  19. Sub-supercritical liquefaction of rice stalk for the production of bio-oil: Effect of solvents.

    Science.gov (United States)

    Li, Rundong; Li, Bingshuo; Yang, Tianhua; Kai, Xingping; Wang, Weidan; Jie, Yefei; Zhang, Yang; Chen, Guanyi

    2015-12-01

    The effect of solvents (water and ethanol) on liquefaction characteristics of rice stalk (RS) was investigated in an autoclave. The highest conversion and liquid yield in water and ethanol were 84.95 wt%, 72.62 wt% and 78.93wt%, 63.84 wt%, respectively. FTIR and GC-MS of the bio-oils obtained from subcritical water (SubH2O, 300°C) and supercritical ethanol (scEtOH, 300°C) indicated that the behavior of RS liquefaction depended on solvents used. The major components of bio-oil produced in SubH2O were ketones and phenols, while esters and phenols dominated in scEtOH. ICP-OES analysis showed that the concentrations of potassium (K) and sodium (Na) in the bio-oil obtained from scEtOH were 14-15 times higher than that obtained from SubH2O. Ethanol gave rise to an improvement in the bio-oil properties including water content, density, acidity and HHV. It was concluded that the bio-oil from RS can be effectively upgraded in scEtOH.

  20. Pyrolysis of hazelnut shells in a fixed-bed tubular reactor. Yields and structural analysis of bio-oil

    Energy Technology Data Exchange (ETDEWEB)

    Puetuen, A.E.; Oezcan, A.; Puetuen, E. [Department of Chemical Engineering, Faculty of Engineering and Architecture, Yunusemre Campus, Anadolu University, 26470 Eskisehir (Turkey)

    1999-09-01

    Fixed-bed pyrolysis experiments have been conducted on a sample of hazelnut shells to determine the possibility of being a potential source of renewable fuels and chemical feedstocks. The effects of pyrolysis temperature and well-sweep gas atmosphere (N{sub 2}) on the pyrolysis yields and chemical compositions have been investigated. The maximum bio-oil yield of 23.1 wt.% was obtained in N{sub 2} atmosphere at a pyrolysis temperature of 500C and heating rate of 7 K min{sup -1}. The pyrolysis products were characterised by elemental analysis and various chromatographic and spectroscopic techniques and also compared with currently utilised transport fuels by simulated distillation. Bio-oil was then fractionated into pentane soluble and insoluble compounds (asphaltenes). Pentane soluble was then solvent fractionated into pentane, toluene, ether and methanol subfractions by fractionated column chromatography. The aliphatic and low-molecular-weight aromatic subfractions of the bio-oil were then analyzed by capillary column gas-liquid chromatography and GC/MS. Further structural analysis of bio-oil and aromatic and polar subfractions FTIR and {sup 1}H-NMR spectra were obtained. The chemical characterization has shown that the bio-oil obtained from hazelnut shells was quite similar to the crude oil and shale oil

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

    Science.gov (United States)

    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.

  2. Flash co-pyrolysis of biomass with polylactic acid. Part 1: Influence on bio-oil yield and heating value

    Energy Technology Data Exchange (ETDEWEB)

    T. Cornelissen; J. Yperman; G. Reggers; S. Schreurs; R. Carleer [Hasselt University, Diepenbeek (Belgium). Laboratory of Applied Chemistry

    2008-06-15

    High amounts of water present in bio-oil are one of the major drawbacks for its utilisation as a fuel. One technology that shows the potential to satisfy the demand for bio-oil with a reduced water content is the flash co-pyrolysis of biomass with polylactic acid, PLA. The influence of PLA on the pyrolysis of willow is investigated with a semi-continuous home-built pyrolysis reactor. Flash co-pyrolysis of willow/PLA blends (10:1, 3:1, 1:1 and 1:2) show synergetic interaction. A higher bio-oil yield and a lower water content as a function of the willow/PLA ratios are obtained. Among the tested blends, the 1:2 willow/PLA blend shows the most pronounced synergy: a reduction in the production of pyrolytic water of almost 28%, accompanied by an increase of more than 37% in the production of water-free bio-oil. Additionally, PLA shows to have a positive influence on the energetic value of the bio-oil produced and on the resulting energy recuperation. 23 refs., 7 figs., 4 tabs.

  3. Fractional pyrolysis of Cyanobacteria from water blooms over HZSM-5 for high quality bio-oil production

    Institute of Scientific and Technical Information of China (English)

    Huijuan Li; Linling Li; Rui Zhang; Dongmei Tong∗; Changwei Hu∗

    2014-01-01

    Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500◦C. One-step pyrolysis produced bio-oil with complex composition and low high heating value (HHV630.9 MJ/kg). Fractional pyrolysis separated the degradation of different components in Cyanobacteria and improved the selectivity to products in bio-oil. That is, acids at 200◦C, amides and acids at 300◦C, phenols and nitriles at 400◦C, and phenols at 500◦C, were got as main products, respectively. HZSM-5 could promote the dehydration, cracking and aromatization of pyrolytic intermediates in fractional pyrolysis. At optimal HZSM-5 catalyst dosage of 1.0 g, the selectivity to products and the quality of bio-oil were improved obviously. The main products in bio-oil changed to nitriles (47.2%) at 300◦C, indoles (51.3%) and phenols (36.3%) at 400◦C. The oxygen content was reduced to 7.2 wt%and 9.4 wt%, and the HHV was raised to 38.1 and 37.3 MJ/kg at 300 and 400◦C, respectively. Fractional catalytic pyrolysis was proposed to be an efficient method not only to provide a potential solution for alleviating environmental pressure from water blooms, but also to improve the selectivity to products and obtain high quality bio-oil.

  4. Bio-oils cause problems to machine entrepreneurs; Biooeljyistae ongelmia koneyrittaejille

    Energy Technology Data Exchange (ETDEWEB)

    Jauhiainen, H.

    2000-07-01

    Biodegradable hydraulic oils, used in hydraulic systems of forest machines, have appeared to be problematic both for machines and operators. The biodegradable oils have caused more hose and gasket failures than traditional mineral oils. In addition to this the washing of the machines is laborious. The use of biodegradable oils in machines requires the use of strong washing agents in washing the machines. These agents are often hazardous for the nature. The biodegradable hydraulic oils cause more health hazards for the operators than the mineral oils. They irritate eyes and they cause skin symptoms. Similar results have also been obtained in Sweden. Stora Enso and the National Board of Forestry have required the use of biodegradable hydraulic oils to be used in forest machines. These requirements have now been postponed. However, bio- oils have still to be used as saw chain oils. National Board of Forestry recommends still the use of biodegradable oils as hydraulic oils, but the use of them is voluntary. The share of biodegradable oils in the markets in last summer was about 40%. Bio-oils were used either because the customer required the use of them or because they were already in the machine when the machine was bought. Thorough investigation of the health effects of biodegradable oils is going on in the Kuopio Regional Institute of Occupational Health. The opinion of the Association of Finnish Forest Machine Entrepreneurs is that the bio-oils have been taken into use on the basis of insufficient data. Attention has been paid only to biodegradability not to the effects of the oils.

  5. Effect of support on catalytic cracking of bio-oil over Ni/silica-alumina

    Science.gov (United States)

    Sunarno, Herman, Syamsu; Rochmadi, Mulyono, Panut; Budiman, Arief

    2017-03-01

    Depletion of petroleum and environmental problem have led to look for an alternative fuel sources In many ways, biomass is a potential renewable source. Among the many forms of biomass, oil palm empty fruit bunch (EFB) is a very attractive feedstock due to its abudance, low price and non-competitiveness with the food chain. EFB can be converted bio-oil by pyrolysis process. but this product can not be used directly as a transportation fuel, so it needs upgrading bio-oil through a catalytic cracking process. The catalyst plays an important role in the catalytic cracking process. The objective of this research is to study the effect of Ni concentrations (1,3,5 and 7 wt.%) on the characteristics of the catalyst Ni / Silica-Alumina and the performance test for the catalytic cracking of bio-oil. Preparation of the catalyst Ni / Silica-Alumina was done by impregnation at 80°C for 3 hours, then done to calcination and reduction at 500°C for 2 hours. The performance test was conducted on catalytic cracking temperature of 500°C. Results show that increasing concentration of Ni from 1 to 7 %, the pore diameter of the catalyst decreased from 35.71 to 32.70 A and surface area decreased from 209.78 to 188.53 m2/gram. With the increase of Ni concentration, the yield of oil reduced from 22.5 to 11.25 %, while the heating value of oil increased from 34.4 to 36.41MJ/kg.

  6. Bio-oils from Pyrolysis of Oil Palm Empty Fruit Bunches

    Directory of Open Access Journals (Sweden)

    Mohamad A. Sukiran

    2009-01-01

    Full Text Available Problem Statement: The palm oil industry generates an abundance of oil palm biomass such as the mesocarp fibre, shell, empty fruit bunch (EFB, frond, trunk and palm oil mill effluent (POME. For 80 million tonnes of fresh fruit bunch (FFB processed last year, the amount of oil palm biomass was more than 25 million tones. The objectives of this study were to: (i Determine the effect of various pyrolysis parameters on product yields and (ii Characterise liquid product obtained under different condition. Approach: In this study, pyrolysis of oil palm Empty Fruit Bunches (EFB was investigated using quartz fluidized fixed bed reactor. The effects of pyrolysis temperatures, particle sizes and heating rates on the yield of the products were investigated. The temperature of pyrolysis and heating rate were varied in the range 300-700 °C and 10-100 °C min1 respectively. The particle size was varied in the range of Results: Under the experimental conditions, the maximum bio-oil yield was 42.28% obtained at 500 ºC, with a heating rate of 100 ºC min-1 and particle size of 91-106 µm. The calorific values of bio-oil ranged from 20-21 MJ kg-1. A great range of functional groups of phenol, alcohols, ketones, aldehydes and carboxylic acids were indicated in FTIR spectrum. Conclusion: The chemical characterisation results showed that the bio-oil obtained from oil palm EFB maybe a potentially valuable source as fuel or chemical feedstocks.

  7. Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating

    Energy Technology Data Exchange (ETDEWEB)

    Olarte, Mariefel V.; Padmaperuma, Asanga B.; Ferrell, Jack R.; Christensen, Earl D.; Hallen, Richard T.; Lucke, Richard B.; Burton, Sarah D.; Lemmon, Teresa L.; Swita, Marie S.; Fioroni, Gina; Elliott, Douglas C.; Drennan, Corinne

    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. A comprehensive understanding of product oils is useful to optimize cost versus degree of deoxygenation. Additionally, a better understanding of the chemical composition of the distillate fractions can open up other uses of upgraded oils for potentially higher-value chemical streams. We present in this paper the characterization data for five well-defined distillate fractions of two hydroprocessed oils with different oxygen levels: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. Elemental analysis and 13C NMR results suggest that the distillate fractions become more aromatic/unsaturated as they become heavier. Our results also show that the use of sulfided catalysts directly affects the S content of the lightest distillate fraction. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. PIONA analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. These results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Xing, Rong [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Dagle, Vanessa Lebarbier [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Flake, Matthew [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Kovarik, Libor [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Albrecht, Karl O. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Deshmane, Chinmay [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis; Dagle, Robert A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Inst. for Integrated Catalysis

    2016-07-01

    In this study we examine feasibility for steam reforming the mixed oxygenate aqueous fraction derived from mildly hydrotreated 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 of acids, polyols, cycloalkanes, and phenolic compounds. The Rh catalyst was found to be the most active and resistant to carbon formation. The Ni and Co catalysts were found to be more active than the other noble metal catalysts investigated (Pt, Ru, and Ir). However, Ni was found to form significantly more carbon (coke) on the catalyst surface. Furthermore, Co was found to be the most selective towards H2 formation. Evaluating the effect of temperature on stability for the Rh catalyst we found that catalyst stability was best when operated at 500°C as compared to the higher temperatures investigated (700, 800°C). When operating at 700°C significantly more graphitic formation was observed on the spent catalyst surface. Operating at 800°C resulted in reactor plugging as a result of thermal decomposition of the reactants. Thus, a concept analogous to the petroleum industries’ use of a pre-reformer, operated at approximately 500°C for steam reforming of the heavier naphtha components, followed by a high temperature methane reforming operated in the 600-850°C temperature range, could be applied in the case of steam reforming biomass derived oxygenates. Moreover, stability evaluations were performed over the Rh, Ni, and Co catalysts at 500°C and 1 atm, under similar initial conversions, reveal the Co catalyst to be the most stable and selective towards H2 production. Conversion and selectivity to CH4

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

    Science.gov (United States)

    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.

  11. Recovery of Bio-Oil from Industrial Food Waste by Liquefied Dimethyl Ether for Biodiesel Production

    Directory of Open Access Journals (Sweden)

    Kiyoshi Sakuragi

    2016-02-01

    Full Text Available The development of new energy sources has become particularly important from the perspective of energy security and environmental protection. Therefore, the utilization of waste resources such as industrial food wastes (IFWs in energy production is expected. The central research institute of electric power industry (CRIEPI, Tokyo, Japan has recently developed an energy-saving oil-extraction technique involving the use of liquefied dimethyl ether (DME, which is an environmentally friendly solvent. In this study, three common IFWs (spent coffee grounds, soybean, and rapeseed cakes were evaluated with respect to oil yield for biodiesel fuel (BDF production by the DME extraction method. The coffee grounds were found to contain 16.8% bio-oil, whereas the soybean and rapeseed cakes contained only approximately 0.97% and 2.6% bio-oil, respectively. The recovered oils were qualitatively analysed by gas chromatography-mass spectrometry. The properties of fatty acid methyl esters derived from coffee oil, such as kinematic viscosity, pour point, and higher heating value (HHV, were also determined. Coffee grounds had the highest oil content and could be used as biofuel. In addition, the robust oil extraction capability of DME indicates that it may be a favourable alternative to conventional oil extraction solvents.

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

    Science.gov (United States)

    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.%).

  13. Production and characterization of bio-oil from catalytic biomass pyrolysis

    Directory of Open Access Journals (Sweden)

    Antonakou Eleni V.

    2006-01-01

    Full Text Available Biomass flash pyrolysis is a very promising thermochemical process for the production of bio-fuels and/or chemicals. However, large-scale applications are still under careful consideration, because of the high bio-liquid upgrading cost. In this paper the production of bio-liquids from biomass flash pyrolysis in a single stage catalytic process is being investigated using a novel once through fluid bed reactor. This biomass pyrolysis unit was constructed in Chemical Process Engineering Research Institute and comprises of a catalyst regenerator, a biomass-vibrating hopper, a fluidization reactor (that consists of an injector and a riser reactor, a product stripper along with a hot cyclone and a filter housing and finally a product condensation/recovery section. The unit can process up to 20 g/min. of biomass (50-800 mm and can circulate up to 300 g/min. of catalyst or inert material. The experiments performed in the pilot plant showed that the unit operates without problems and with satisfactory mass balances in a wide range of experimental conditions both in the absence and presence of catalyst. With the incorporation of an FCC catalyst in the pyrolysis, the physical properties of the bio-oil produced changed, while more stable bio-oil was produced. .

  14. Soot formation and oxidation during bio-oil gasification:experiments and modeling

    Institute of Scientific and Technical Information of China (English)

    Younes; Chhiti; Marine; Peyrot; Sylvain; Salvador

    2013-01-01

    A model is proposed to describe soot formation and oxidation during bio-oil gasification.It is based on the description of bio-oil heating,devolatilization,reforming of gases and conversion of both char and soot solids.Detailed chemistry (159 species and 773 reactions) is used in the gas phase.Soot production is described by a single reaction based on C2H2species concentration and three heterogeneous soot oxidation reactions.To support the validation of the model,three sets of experiments were carried out in a lab-scale Entrained Flow Reactor (EFR) equipped with soot quantification device.The temperature was varied from 1000 to 1400 C and three gaseous atmospheres were considered:default of steam,large excess of steam(H2O/C=8),and the presence of oxygen in the O/C range of 0.075–0.5.The model is shown to accurately describe the evolution of the concentration of the main gas species and to satisfactorily describe the soot concentration under the three atmospheres using a single set of identified kinetic parameters.Thanks to this model the contribution of different mechanisms involved in soot formation and oxidation in various situations can be assessed.

  15. Syngas production by plasma treatments of alcohols, bio-oils and wood

    Science.gov (United States)

    Arabi, K.; Aubry, O.; Khacef, A.; Cormier, J.-M.

    2012-12-01

    Exploitation of forest resources for energy production includes various methods of biomass processing. Gasification is one of the ways to recover energy from biomass. The Syngas produced from biomass can be used to power internal combustion engines, or, after purification, to supply fuel cells. The paper is summarizing results obtained through a non thermal arc plasma reactor at laboratory scale. A stationary discharge (I = 150mA) is used to perform physical diagnostics and also chemical analysis. The arc is formed between two electrodes made of graphite. We first present results on plasma-steam reforming of alcohols and bio-oils mixed in water. The outlet gas compositions are given from various alcohols and-bio-oils obtained at different experimental conditions. The second part of the paper is dedicated to a direct plasma treatment of wood (beech) at laboratory scale. One of the electrodes is surrounded by wood. The final part of the paper is a general discussion about efficiencies and comparisons of plasma treatments presented. The results obtained are discussed by considering the steam reforming reactions and the water gas shift reaction.

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

    Science.gov (United States)

    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.

  17. Compositional insights and valorization pathways for carbonaceous material deposited during bio-oil thermal treatment.

    Science.gov (United States)

    Ochoa, Aitor; Aramburu, Borja; Ibáñez, María; Valle, Beatriz; Bilbao, Javier; Gayubo, Ana G; Castaño, Pedro

    2014-09-01

    This work analyses the composition, morphology, and thermal behavior of the carbonaceous materials deposited during the thermal treatment of bio-oil (thermal pyrolytic lignin-TPL). The bio-oil was obtained by flash pyrolysis of lignocellulosic biomass (pine sawdust), and the TPLs were obtained in the 400-700 °C range. The TPLs were characterized by performing elemental analysis; (13)C NMR, Raman, FTIR, and X-ray photoelectron spectroscopy; SEM; and temperature-programmed oxidation analyzed by differential thermogravimetry and differential scanning calorimetry. The results are compared to a commercial lignin (CL). The TPLs have lower oxygen and hydrogen contents and a greater aromaticity and structural order than the CL material. Based on these features, different valorization routes are proposed: the TPL obtained at 500 °C is suitable for use as a fuel, and the TPL obtained at 700 °C has a suitable morphology and composition for use as an adsorbent or catalyst support.

  18. Catalytic pyrolysis of waste furniture sawdust for bio-oil production.

    Science.gov (United States)

    Uzun, Başak B; Kanmaz, Gülin

    2014-07-01

    In this study, the catalytic pyrolysis of waste furniture sawdust in the presence of ZSM-5, H-Y and MCM-41 (10 wt % of the biomass sample) was carried out in order to increase the quality of the liquid product at the various pyrolysis temperatures of 400, 450, 500 and 550(o)C. In the non-catalytic work, the maximum oil yield was obtained as 42% at 500(o)C in a fixed-bed reactor system. In the catalytic work, the maximum oil yield was decreased to 37.48, 30.04 and 29.23% in the presence of ZSM-5, H-Y and MCM-41, respectively. The obtained pyrolysis oils were analyzed by various spectroscopic and chromatographic techniques. It was determined that the use of a catalyst decreased acids and increased valuable organics found in the bio-oil. The removal of oxygen from bio-oil was confirmed with the results of the elemental analysis and gas chromatography-mass spectrometry.

  19. A review of catalytic upgrading of bio-oil to engine fuels

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Grunwaldt, Jan-Dierk; Jensen, Peter Arendt

    2011-01-01

    crude oil. Two general routes for bio-oil upgrading have been considered: hydrodeoxygenation (HDO) and zeolite cracking. HDO is a high pressure operation where hydrogen is used to exclude oxygen from the bio-oil, giving a high grade oil product equivalent to crude oil. Catalysts for the reaction...... are traditional hydrodesulphurization (HDS) catalysts, such as Co–MoS2/Al2O3, or metal catalysts, as for example Pd/C. However, catalyst lifetimes of much more than 200h have not been achieved with any current catalyst due to carbon deposition. Zeolite cracking is an alternative path, where zeolites, e.g. HZSM-5......-oil results in a low H/C ratio of the oil product as no additional hydrogen is supplied. Overall, oil from zeolite cracking is of a low grade, with heating values approximately 25% lower than that of crude oil. Of the two mentioned routes, HDO appears to have the best potential, as zeolite cracking cannot...

  20. Catalytic transfer hydrogenation for stabilization of bio-oil oxygenates: reduction of p-cresol and furfural over bimetallic Ni-Cu catalysts using isopropanol

    Science.gov (United States)

    Transfer hydrogenation and hydrodeoxygenation of model bio-oil compounds (p-cresol and furfural) and bio-oils derived from biomass via traditional pyrolysis and tail-gas reactive pyrolysis (TGRP) were conducted. Mild batch reaction conditions were employed, using isopropanol as a hydrogen donor over...

  1. Bio-oils and other bio fuels used in heat- and power generation; Flytande biobraenslen foer el- och vaermeproduktion

    Energy Technology Data Exchange (ETDEWEB)

    Sandgren, Annamaria; Ekdahl, Emma; Sernhed, Kerstin; Lindstroem, Erica

    2010-05-15

    The purpose of this study was to assemble and disseminate knowledge about bio-oils and other bio fuels which are used for heat- and power generation or liquid bio fuels/oils that may become interesting in the future. One aim of this study was to give an updated picture of the Swedish market for bio-oils and to provide an overview of practical experience on the usage of bio-oils in the Swedish heat and power industry. In order to show a green profile, bio-oils can be used in the heat and power generation. However, not all bio-oils can be viewed as climate friendly. Some production of bio-oils may actually - if a lifecycle perspective is considered - lead to increased emissions of greenhouse gases, and there are also ethical issues that need to be considered. The data collection was carried out in three different fields. The objective of the first part was to create an overview of the Swedish market for liquid bio fuels/oils for heat and power production. The second part of the study aimed to clarify the issues surrounding environmental and ethical issues associated with the use of different bio-oils. A selection of oil crops for a closer study was made based on production volume (soybean, palm oil and rapeseed) and expected future potential (jatropha). This part of the study was based on a literature review. In the third part of the study technical and practical experiences from using bio-oils in heat and power production were studied. The interviews made with purchasing managers in the second part gave valuable information on which utilities would be the most interesting to interview for the study of technical and practical experiences, where interviews were carried out with persons familiar with the daily operation of the plant. The use of liquid bio fuels was about 4.3 % of total fuel use in Swedish district heating production in 2007 (1.2 % pine oil and 3.0 % other bio-oil). In other words, it is mainly bio-oils that have been used and not other types of liquid

  2. Bio-oils and other bio fuels used in heat- and power generation; Flytande biobraenslen foer el- och vaermeproduktion

    Energy Technology Data Exchange (ETDEWEB)

    Sandgren, Annamaria; Ekdahl, Emma; Sernhed, Kerstin; Lindstroem, Erica

    2010-05-15

    The purpose of this study was to assemble and disseminate knowledge about bio-oils and other bio fuels which are used for heat- and power generation or liquid bio fuels/oils that may become interesting in the future. One aim of this study was to give an updated picture of the Swedish market for bio-oils and to provide an overview of practical experience on the usage of bio-oils in the Swedish heat and power industry. In order to show a green profile, bio-oils can be used in the heat and power generation. However, not all bio-oils can be viewed as climate friendly. Some production of bio-oils may actually - if a lifecycle perspective is considered - lead to increased emissions of greenhouse gases, and there are also ethical issues that need to be considered. The data collection was carried out in three different fields. The objective of the first part was to create an overview of the Swedish market for liquid bio fuels/oils for heat and power production. The second part of the study aimed to clarify the issues surrounding environmental and ethical issues associated with the use of different bio-oils. A selection of oil crops for a closer study was made based on production volume (soybean, palm oil and rapeseed) and expected future potential (jatropha). This part of the study was based on a literature review. In the third part of the study technical and practical experiences from using bio-oils in heat and power production were studied. The interviews made with purchasing managers in the second part gave valuable information on which utilities would be the most interesting to interview for the study of technical and practical experiences, where interviews were carried out with persons familiar with the daily operation of the plant. The use of liquid bio fuels was about 4.3 % of total fuel use in Swedish district heating production in 2007 (1.2 % pine oil and 3.0 % other bio-oil). In other words, it is mainly bio-oils that have been used and not other types of liquid

  3. Compositional analysis of bio-oil pyrolysed from corn stalk and emulsification of bio-oil in diesel oil%玉米秸秆粉热解生物油的分析及乳化

    Institute of Scientific and Technical Information of China (English)

    王丽红; 吴娟; 易维明; 李永军; 柏雪源

    2009-01-01

    With the aim of studying chemical compounds and application of complicated bio-oil pyrolysed from corn stalk, bio-oil was analyzed using gas chromatography/mass spectrometry (GC/MS), and the physical characteristics of emulsified fuel (EF) made by water-soluble bio-oil and diesel oil were determined. Bio-oil was comprised of two fractions: water-soluble and water-insoluble fractions. The major chemical compounds in water-soluble bio-oil occupied 80% of the total weight were water, acetic acid, 2-propanone-1-hydroxy, cyclopentenone, furfural and phenol, etc. After water-soluble bio-oil was extracted by dichloromethane (CH_2Cl_2), some compounds were detected, such as the derivatives of cyclopentenone, furfural and phenol. Water-insoluble fraction was so complicated that it was difficult to confirm compositions directly. Experiments were also conducted to study the stabilization of EF made by water-soluble bio-oil, diesel oil and emulsifier which was made by Span-80 and Tween-20 according to a certain proportion, and it was concluded that long reaction time, higher concentration of diesel oil and emulsifier or lower concentration of water-soluble bio-oil could lead to good stability. The heat value of EF was much higher than that of water-soluble bio-oil, but the pH value of EF did not change much better than that of water-soluble bio-oil. Some methods must be taken to reduce acidity of EF in order to apply in diesel engine.%为了探究玉米秸秆粉热解生物油的组成及乳化改性技术,对生物油进行了气质联用(GC/MS)分析,并研究了轻质生物油与柴油乳化后燃料的物理性质.生物油有分层现象,上层是溶于水的轻质液体,约占总质量的80%,主要成分有水、羟基丙酮、乙酸、糠醛、环戊烯酮及衍生物、苯酚等,用二氯甲烷萃取后在有机相中又检测到糠醛衍生物及苯酚衍生物等.下层是难溶于水的大分子物质,组成复杂,直接分析难以确定成分.

  4. Comparative Studies of Oleaginous Fungal Strains (Mucor circinelloides and Trichoderma reesei for Effective Wastewater Treatment and Bio-Oil Production

    Directory of Open Access Journals (Sweden)

    Anshuman Bhanja

    2014-01-01

    Full Text Available Biological wastewater treatment typically requires the use of bacteria for degradation of carbonaceous and nitrogenous compounds present in wastewater. The high lipid containing biomass can be used to extract oil and the contents can be termed as bio-oil (or biodiesel or myco-diesel after transesterification. The separate experiments were conducted on actual wastewater samples with 5% v/v inoculum of Mucor circinelloides MTCC1297 and Trichoderma reesei NCIM992 strains. The observed reductions in chemical oxygen demand (COD were 88.72% and 86.75% in 96 hrs and the observed substrate based biomass yields were 0.21 mg VSS/mg COD and 0.22 mg VSS/mg COD for M. circinelloides reactor and for T. reesei reactor, respectively. The resulted bio-oil production from wastewater treatment by M. circinelloides and T. reesei reactors was 142.2 mg/L and 74.1 mg/L, whereas biomass containing bio-oil contents (%w/w were 22.11% and 9.82%, respectively. In this experiment, the fungal wastewater treatment was also compared with conventional bacterial process with respect to specific growth rate, biomass production, and oil content. This study suggests that wastewater can be used as a potential feedstock for bio-oil production with the use of oleaginous fungal strains and which could be a possible route of waste to energy.

  5. Bubble point pressures of the selected model system for CatLiq® bio-oil process

    DEFF Research Database (Denmark)

    Toor, Saqib Sohail; Rosendahl, Lasse; Baig, Muhammad Noman;

    2010-01-01

    The CatLiq® process is a second generation catalytic liquefaction process for the production of bio-oil from WDGS (Wet Distillers Grains with Solubles) at subcritical conditions (280-350 oC and 225-250 bar) in the presence of a homogeneous alkaline and a heterogeneous Zirconia catalyst. In this w...

  6. Bubble point pressures of the selected model system for CatLiq® bio-oil process

    DEFF Research Database (Denmark)

    Toor, Saqib Sohail; Rosendahl, Lasse; Baig, Muhammad Noman

    2010-01-01

    The CatLiq® process is a second generation catalytic liquefaction process for the production of bio-oil from WDGS (Wet Distillers Grains with Solubles) at subcritical conditions (280-350 oC and 225-250 bar) in the presence of a homogeneous alkaline and a heterogeneous Zirconia catalyst. In this w...

  7. High quality bio-oil from catalytic flash pyrolysis of lignocellulosic biomass over alumina-supported sodium carbonate

    NARCIS (Netherlands)

    Ali Imran, A.; Bramer, Eduard A.; Seshan, Kulathuiyer; Brem, Gerrit

    2014-01-01

    Performance of a novel alumina-supported sodium carbonate catalyst was studied to produce a valuable bio-oil from catalytic flash pyrolysis of lignocellulosic biomass. Post treatment of biomass pyrolysis vapor was investigated in a catalyst fixed bed reactor at the downstream of the pyrolysis

  8. Degradation of palm oil empty fruit bunch (EFB) into bio-oil in sub-and supercritical solvents

    Science.gov (United States)

    Sarwono, Rakhman; Pusfitasari, Eka Dian

    2017-01-01

    Hydrothemal Liquefaction (HTL) of empty fruit bunch (EFB) of palm oil in different solvents (water, ethanol and hexane) were comparatively investigated. Experiments were carried out in an autoclave in different EFB loading of 9%, 11%, and 13%. The temperature operation was 350 oC, without any catalysts and reaction time of 5 hours. The efficiency of above solvents in terms of conversion rate, soluble liquid and carbon products were found in this experiments. The water solvent gave higher conversion rate of 35 - 36.5 %, while hexane gave conversion of 17 - 25.25 %, and ethanol gave the lower conversion rate of 12.65 - 30.3%, respectively. Increasing the EFB load decreased the conversion rate for ethanol and hexane solvents, for water there are no significant change in the conversion rate. The bio-oil as soluble liquid produced were in order of water, ethanol, and hexane solvents, respectively. The chemical properties of bio-oil products were significantly affected by the type of liquefaction solvent. The compositional of bio-oil consists of mostly of a mixture of organic acids, ketones, and esters. The hexane and ethanol solvents resulted mostly organic acids. In water solvent resulted 2-pentanone, 4-hydroxy-4-methyl and others substances. According to the bio-oil results, organic solvents resulted higher HHV compared to water solvent. The higher heating value (HHV) of the carbon products were also comparatively, ethanol solvent resulted soluble liquid with higher HHV compared to the water solvent.

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

    Science.gov (United States)

    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...

  10. Comparative Studies of Oleaginous Fungal Strains (Mucor circinelloides and Trichoderma reesei) for Effective Wastewater Treatment and Bio-Oil Production.

    Science.gov (United States)

    Bhanja, Anshuman; Minde, Gauri; Magdum, Sandip; Kalyanraman, V

    2014-01-01

    Biological wastewater treatment typically requires the use of bacteria for degradation of carbonaceous and nitrogenous compounds present in wastewater. The high lipid containing biomass can be used to extract oil and the contents can be termed as bio-oil (or biodiesel or myco-diesel after transesterification). The separate experiments were conducted on actual wastewater samples with 5% v/v inoculum of Mucor circinelloides MTCC1297 and Trichoderma reesei NCIM992 strains. The observed reductions in chemical oxygen demand (COD) were 88.72% and 86.75% in 96 hrs and the observed substrate based biomass yields were 0.21 mg VSS/mg COD and 0.22 mg VSS/mg COD for M. circinelloides reactor and for T. reesei reactor, respectively. The resulted bio-oil production from wastewater treatment by M. circinelloides and T. reesei reactors was 142.2 mg/L and 74.1 mg/L, whereas biomass containing bio-oil contents (%w/w) were 22.11% and 9.82%, respectively. In this experiment, the fungal wastewater treatment was also compared with conventional bacterial process with respect to specific growth rate, biomass production, and oil content. This study suggests that wastewater can be used as a potential feedstock for bio-oil production with the use of oleaginous fungal strains and which could be a possible route of waste to energy.

  11. Characterization and pyrolysis of Chlorella vulgaris and Arthrospira platensis: potential of bio-oil and chemical production by Py-GC/MS analysis.

    Science.gov (United States)

    Almeida, Hanna N; Calixto, Guilherme Q; Chagas, Bruna M E; Melo, Dulce M A; Resende, Fabio M; Melo, Marcus A F; Braga, Renata Martins

    2017-06-01

    Biofuels have been seen as potential sources to meet future energy demand as a renewable and sustainable energy source. Despite the fact that the production technology of first-generation biofuels is consolidated, these biofuels are produced from foods crops such as grains, sugar cane, and vegetable oils competing with food for crop use and agricultural land. In recent years, it was found that microalgae have the potential to provide a viable alternative to fossil fuels as source of biofuels without compromising food supplies or arable land. On this scenario, this paper aims to demonstrate the energetic potential to produce bio-oil and chemicals from microalgae Chlorella vulgaris and Arthrospira platensis. The potential of these biomasses was evaluated in terms of physical-chemical characterization, thermogravimetric analysis, and analytical pyrolysis interfaced with gas chromatograph (Py-GC/MS). The results show that C. vulgaris and A. platensis are biomasses with a high heating value (24.60 and 22.43 MJ/kg) and low ash content, showing a high percentage of volatile matter (72.49 and 79.42%). These characteristics confirm their energetic potential for conversion process through pyrolysis, whereby some important aromatic compounds such as toluene, styrene, and phenol were identified as pyrolysis products, which could turn these microalgae a potential for biofuels and bioproduct production through the pyrolysis.

  12. Research on combustion characteristics of bio-oil from sewage sludge

    Institute of Scientific and Technical Information of China (English)

    Rui LI; Baosheng JIN; Xiangru JIA; Zhaoping ZHONG; Gang XIAO; Xufeng FU

    2009-01-01

    Combustion characteristics of bio-oil from sewage sludge were investigated using thermograviMetry (TG) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques. The combustion process could be divided into two weight loss stages. Light compounds volatilized and were oxidized in the first stage and the heterogeneous combustion between oxygen and heavy compounds happened in the second stage, which were confirmed by FT-IR technique. Most weight loss occurred in the first stage. The effect of heating rate was also studied and higher heating rates were found to facilitate the combustion process. The kinetic parameters of the two stages were calculated and the change of activation energy indicated higher heating rates benefited combustion.

  13. Method of increasing anhydrosugars, pyroligneous fractions and esterified bio-oil

    Science.gov (United States)

    Steele, Philip H; Yu, Fei; Li, Qi; Mitchell, Brian

    2014-12-30

    The device and method are provided to increase anhydrosugars yield during pyrolysis of biomass. This increase is achieved by injection of a liquid or gas into the vapor stream of any pyrolysis reactor prior to the reactor condensers. A second feature of our technology is the utilization of sonication, microwave excitation, or shear mixing of the biomass to increase the acid catalyst rate for demineralization or removal of hemicellulose prior to pyrolysis. The increased reactivity of these treatments reduces reaction time as well as the required amount of catalyst to less than half of that otherwise required. A fractional condensation system employed by our pyrolysis reactor is another feature of our technology. This system condenses bio-oil pyrolysis vapors to various desired fractions by differential temperature manipulation of individual condensers comprising a condenser chain.

  14. Characterization of bio-oil from hydrothermal liquefaction of organic waste by NMR spectroscopy and FTICR mass spectrometry.

    Science.gov (United States)

    Leonardis, Irene; Chiaberge, Stefano; Fiorani, Tiziana; Spera, Silvia; Battistel, Ezio; Bosetti, Aldo; Cesti, Pietro; Reale, Samantha; De Angelis, Francesco

    2013-01-01

    Solid wastes of organic origins are potential feedstocks for the production of liquid biofuels, which could be suitable alternatives to fossil fuels for the transport and heating sectors, as well as for industrial use. By hydrothermal liquefaction, the wet biomass is partially transformed into a water-immiscible, oil-like organic matter called bio-oil. In this study, an integrated NMR spectroscopy/mass spectrometry approach has been developed for the characterization of the hydrothermal liquefaction of bio-oil at the molecular level. (1)H and (13)C NMR spectroscopy were used for the identification of functional groups and gauging the aromatic carbon content in the mixture. GC-MS analysis revealed that the volatile fraction was rich in fatty acids, as well as in amides and esters. High-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS) has been applied in a systematic way to fully categorize the bio-oil in terms of different classes of components, according to their molecular formulas. Most importantly, for the first time, by using this technique, and for the liquefaction bio-oil characterization in particular, FT-MS data have been used to develop a methodology for the determination of the aromatic versus aliphatic carbon and nitrogen content. It is well known that, because they resist hydrogenation and represent sources of polluting species, both aromatic molecules and nitrogen-containing species raise concerns for subsequent upgrading of bio-oil into a diesel-like fuel. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Recycling used palm oil and used engine oil to produce white bio oil, bio petroleum diesel and heavy fuel

    Science.gov (United States)

    Al-abbas, Mustafa Hamid; Ibrahim, Wan Aini Wan; Sanagi, Mohd. Marsin

    2012-09-01

    Recycling waste materials produced in our daily life is considered as an additional resource of a wide range of materials and it conserves the environment. Used engine oil and used cooking oil are two oils disposed off in large quantities as a by-product of our daily life. This study aims at providing white bio oil, bio petroleum diesel and heavy fuel from the disposed oils. Toxic organic materials suspected to be present in the used engine oil were separated using vacuum column chromatography to reduce the time needed for the separation process and to avoid solvent usage. The compounds separated were detected by gas chromatography-mass spectrometry (GC-MS) and found to contain toxic aromatic carboxylic acids. Used cooking oils (thermally cracked from usage) were collected and separated by vacuum column chromatography. White bio oil produced was examined by GC-MS. The white bio oil consists of non-toxic hydrocarbons and is found to be a good alternative to white mineral oil which is significantly used in food industry, cosmetics and drugs with the risk of containing polycyclic aromatic compounds which are carcinogenic and toxic. Different portions of the used cooking oil and used engine were mixed to produce several blends for use as heavy oil fuels. White bio oil was used to produce bio petroleum diesel by blending it with petroleum diesel and kerosene. The bio petroleum diesel produced passed the PETRONAS flash point and viscosity specification test. The heat of combustion of the two blends of heavy fuel produced was measured and one of the blends was burned to demonstrate its burning ability. Higher heat of combustion was obtained from the blend containing greater proportion of used engine oil. This study has provided a successful recycled alternative for white bio oil, bio petroleum fuel and diesel which can be an energy source.

  16. The surface-active bio oil solution in sulfured copper mineral benefit

    Directory of Open Access Journals (Sweden)

    L.E. Brossard

    2005-03-01

    Full Text Available Surface-active bio-oil (SABO solutions, prepared from vacuum pyrolysis bio-oil with a phenol-to-levoglucosan mass ratio of 4.8, was compared to pine-oil (PO as foaming agent in the process of flotation of sulfured copper minerals. With the aid of 2³ factorial designs, regression models were obtained for % Cu in flotation concentrate (L Cu and % Cu recovery (R, as functions of foaming agent-to-Cu mineral, collector-to-Cu mineral mass ratio and liquid-to-solid ratio (v/w. Experimental designs composed of a saturated design in its first half and a fold over design in its second half allowed to study the influence of flotation conditions on L Cu and R when SABO was the foaming agent. The factors selected were: particle size; pulp pH; flotation time; initial Cu content in the mineral (mineral type; liquid-to-solid ratio and finally SABO-to-mineral and collector-to-mineral mass ratio. Within the chosen experimental region only pulp pH affected significantly both responses. It is shown that high pulp pH, in the presence of minerals rich in Cu content leads to a significant increase in L Cu and R. Although SABO to mineral mass ratio is high compared to PO, it is considered that an optimization study on pulp pH should reduce this difference making SABO an attractive alternative to PO and a way to widen the field of applications of pyrolysis products.

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

    Science.gov (United States)

    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.

  18. 生物质快速热解气相成分析出规律%STUDY ON RELEASE BEHAVIOR OF GAS COMPONENTS OF BIOMASS IN FAST PYROLYSIS

    Institute of Scientific and Technical Information of China (English)

    吴少华; 栾积毅; 孙锐; 姚娜

    2009-01-01

    利用恒温沉降炉对秸秆、稻壳、木屑及一种烟煤煤粉在900、1000、1100℃ 3个温度进行了快速热解试验,对4种燃料在快速热解过程中气相成分析出的规律进行了研究.生物质成分中高的挥发分、氧、H/C决定了其快速热解会取得比煤粉高的气相产率,木屑的气相产物产量最多,秸秆次之,稻壳最低.4种燃料热解气相产物中的主要成分是CO、H_2、CO_2、CH_4,少量的G_2H_4、C_2H_6、NO、HCN、COS,生物质和煤粉在快速热解及短的停留时间内,其析出的氮前驱物为HCN.快速热解析出的气相成分产量及组分分布与燃料种类、热解温度、热解停留时间相关.几种物料共同的规律是随停留时间的延长,气相产物的量不断地增加,当气相产物的产量趋于平稳时,相应的气相产物的各组分趋于恒定,这一停留时间标志着热解过程的结束,相同温度条件下煤粉的热解速率要慢于3种生物质.%The release behavior of gas components of straw、rice husk、sawdust and bituminous coal was investigated in a drop tube deposition furnace at fast pyrolysis temperature of 900、1000、1100℃ . The volatile, oxygen and H/C of biomass components was higher than that of bituminous coal, which determins a higher gas yield in the fast pyrolysis. The gas yield of sawdust is the greatest, that of straw is the second and that of rice husk is minimum. The main components of pyrolysis gas is CO, H_2, CO_2 and CH_4, while other components, such as C_2H_4、NO、HCN、COS are relatively less. HCN is the nitrogen precursors in short residence time for fast pyrolysis. The gas yield and compsition in the fast pyrolysis are related to the fuel types, pyrolysis temperature and residence time. The common law for several fuel are as follows: when the residence time increased and the gas yield stabilized, the corresponding components of gas product tend to be constant. This time can be considered as the end of

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

    Energy Technology Data Exchange (ETDEWEB)

    Dutta, A.; Sahir, A.; Tan, E.; Humbird, D.; Snowden-Swan, L. J.; Meyer, P.; Ross, J.; Sexton, D.; Yap, R.; Lukas, J.

    2015-03-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Foust, Thomas D.; Ziegler, Jack L.; Pannala, Sreekanth; Ciesielski, Peter; Nimlos, Mark R.; Robichaud, David J.

    2017-02-21

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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. 生物质快速热解液化技术研究进展%Progresses in Fast Pyrolysis of Biomass to Liquid Fuel

    Institute of Scientific and Technical Information of China (English)

    朱锡锋; 李明

    2013-01-01

    总结了生物质热解液化技术在原料预处理、热解工艺和生物油精制3个方面的最新研究成果.在原料预处理方面,介绍了干燥、烘焙、压缩成型和酸洗4种方法;在热解工艺方面,列举了国内外具有代表性的热解反应器类型,重点介绍了催化热解和混合热解两种新工艺;在生物油精制方面,介绍了包括催化加氢、催化裂解、催化酯化和乳化等几种常用的生物油精制方法,并分析了各精制技术发展的关键问题.%The recent progresses in raw materials pretreatment,pyrolytic process and biooil upgrading for the fast pyrolysis of biomass to liquid fuel were reviewed.In the raw materials pretreatment,drying,torrefaction,compression moulding and acid-washing were introduced.In the pyrolytic process,typical fast pyrolysis reactors are enumerated and two novel pyrolytic processes,namely fast catalytic pyrolysis and co-liquefaction of both biomass and coal,were discussed.Finally,some upgrading methods were discussed,which included catalytic hydroprocessing,catalytic cracking,catalytic esterification,and emulsification with diesel.The key problems involved in these upgrading methods were also analyzed.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  5. Treatment of aqueous phase of bio-oil by granular activated carbon and evaluation of biogas production.

    Science.gov (United States)

    Shanmugam, Saravanan R; Adhikari, Sushil; Wang, Zhouhang; Shakya, Rajdeep

    2017-01-01

    Hydrothermal liquefaction of wet biomass such as algae is a promising thermochemical process for the production of bio-oil. Bio-oil aqueous phase generated during liquefaction process is rich in complex organics and can be utilized for biogas production following its pre-treatment with granular activated carbon. In our study, use of 30% activated carbon resulted in higher chemical oxygen demand (COD) reduction (53±0.3%) from aqueous phase. Higher CH4 production (84±12mL/gCOD) was also observed in 30% carbon-treated aqueous phase fed cultures, whereas only 32±6mLCH4/gCOD was observed in control (non-carbon treated) cultures. The results from this study indicate that almost 67±0.3% initial COD of aqueous phase can be reduced using a combination of both carbon treatment and biogas production. This study shows that aqueous phase can be utilized for CH4 production.

  6. Hydrothermal liquefaction of palm oil empty fruit bunch (EFB) into bio-oil in different organic solvents

    Science.gov (United States)

    Sarwono, Rakhman; Pusfitasari, Eka Dian; Ghozali, Muhammad

    2016-06-01

    Thermochemical Liquefaction of empty fruit bunch (EFB) of palm oil in different organic solvents (water, methanol, ethanol, acetone, toluene and hexane) were comparatively investigated. Experiments were carried out in an autoclave at different temperatures of 300, 350 and 400 °C with a fixed solid/liquid rasio of 3 gram in 50 ml solvent, without catalysts and reaction time of 5 hours. The efficiency of above solvents in terms of conversion rate, soluble liquid and carbon products were investigated in the experiments. Increasing the reaction temperature increased the conversion rate in all organic solvents and water, but gaseous products also increased using a reaction temperature of 400 oC. The water solvent gave higher conversion rate of 49.14%, while toluene, acetone, methanol, hexane and ethanol gave conversion of 35.76%, 26.5%, 25.98%, 24.26 %, and 22.24%, respectively. The bio-oil produced in order of the largest amount were using methanol, water, ethanol, toluene, acetone, and hexane solvents. The chemical properties of bio-oil products were significantly affected by the type of liquefaction solvent. The composition of bio-oil consisted of mostly of a mixture of organic acids, ketones, and esters. The methanol and ethanol solvents resulted in mostly esters, while toluene and hexane resulted in mostly organic acids. Acetone solvent resulted in the same amount of organic acid and esters. In water as a solvent resulted in 2-pentanone, 4-hydroxy-4-methyl. The bio-oil consisted of a range of carbon C6 - C20 fragments.

  7. Study on demetalization of sewage sludge by sequential extraction before liquefaction for the production of cleaner bio-oil and bio-char.

    Science.gov (United States)

    Leng, Lijian; Yuan, Xingzhong; Shao, Jianguang; Huang, Huajun; Wang, Hou; Li, Hui; Chen, Xiaohong; Zeng, Guangming

    2016-01-01

    Demetalization of sewage sludge (SS) by sequential extraction before liquefaction was implemented to produce cleaner bio-char and bio-oil. Demetalization steps 1 and 2 did not cause much organic matter loss on SS, and thus the bio-oil and bio-char yields and the compositions of bio-oils were also not affected significantly. However, the demetalization procedures resulted in the production of cleaner bio-chars and bio-oils. The total concentrations and the acid soluble/exchangeable fraction (F1 fraction, the most toxic heavy metal fraction) of heavy metals (Cu, Cr, Pb, Zn, and Cd) in these products were significantly reduced and the environmental risks of these products were also relived considerably compared with those produced from raw SS, respectively. Additionally, these bio-oils had less heavy fractions. Demetalization processes with removal of F1 and F2 fractions of heavy metals would benefit the production of cleaner bio-char and bio-oil by liquefaction of heavy metal abundant biomass like SS.

  8. Pressurized pyrolysis of rice husk in an inert gas sweeping fixed-bed reactor with a focus on bio-oil deoxygenation.

    Science.gov (United States)

    Qian, Yangyang; Zhang, Jie; Wang, Jie

    2014-12-01

    The pyrolysis of rice husk was conducted in a fixed-bed reactor with a sweeping nitrogen gas to investigate the effects of pressure on the pyrolytic behaviors. The release rates of main gases during the pyrolysis, the distributions of four products (char, bio-oil, water and gas), the elemental compositions of char, bio-oil and gas, and the typical compounds in bio-oil were determined. It was found that the elevation of pressure from 0.1MPa to 5.0MPa facilitated the dehydration and decarboxylation of bio-oil, and the bio-oils obtained under the elevated pressures had significantly less oxygen and higher calorific value than those obtained under atmospheric pressure. The former bio-oils embraced more acetic acid, phenols and guaiacols. The elevation of pressure increased the formation of CH4 partially via the gas-phase reactions. An attempt is made in this study to clarify "the pure pressure effect" and "the combined effect with residence time".

  9. Quantitative and qualitative analysis of hemicellulose, cellulose and lignin bio-oils by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

    Science.gov (United States)

    Michailof, Chrysoula; Sfetsas, Themistoklis; Stefanidis, Stylianos; Kalogiannis, Konstantinos; Theodoridis, Georgios; Lappas, Angelos

    2014-11-21

    Thermal and catalytic pyrolysis are efficient processes for the transformation of biomass to bio-oil, a liquid energy carrier and a general source of chemicals. The elucidation of the bio-oil's composition is essential for a rational design of both its production and utilization process. However, the complex composition of bio-oils hinders their complete qualitative and quantitative analysis, and conventional chromatographic techniques lack the necessary separation power. Two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-ToFMS) is considered a suitable technique for bio-oil analysis due to its increased separation and resolution capacity. This work presents the tentative qualitative and quantitative analysis of bio-oils resulting from the thermal and catalytic pyrolysis of standard xylan, cellulose, lignin and their mixture by GC×GC-ToFMS. Emphasis is placed on the development of the quantitative method using phenol-d6 as internal standard. During the method development, a standard solution of 39 compounds was used for the determination of the respective Relative Response Factors (RRF) employing statistical methods, ANOVA and WLSLR, for verification of the data. The developed method was applied to the above mentioned bio-oils and their detailed analysis is presented. The different compounds produced and their diverse concentration allows for an elucidation of the pyrolysis mechanism and highlight the effect of the catalyst.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  13. Effect of Potassium Addition on Coprecipitated Iron Catalysts for Fischer-Tropsch Synthesis Using Bio-oil-syngas

    Institute of Scientific and Technical Information of China (English)

    Zhao-xiang Wang; Ting Dong; Tao Kan; Quan-xin Li

    2008-01-01

    The effects of potassium addition and the potassium content on the activity and selectivity of coprecipitated iron catalyst for Fischer-Tropsch synthesis (FTS) were studied in a fixed bed reactor at 1.5 MPa,300℃, and contact time (W/F) of 12.5 gcath/mol using the model bio-oil-syngas of H2/CO/CO2/N2 (62/8/25/5, vol%).It was found that potassium addition increases the catalyst activity for FTS and the reverse water gas shift reaction.Moreover,potassium increases the average molecular weight (chain length) of the hydrocarbon products.With the increase of potassium content,it was found that CH4 selectivity decreases and the selectivity of liquid phase products (C5+) increases.The characteristics of FTS catalysts with different potassium content were also investigated by various characterization measurements including X-ray diffraction,X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller surface area.Based on experimental results,100Fe/6Cu/16Al/6K (weight ratio) was selected as the optimal catalyst for FTS from bio-oil-syngas. The results indicate that the 100Fe/6Cu/16Al/6K catalyst is one of the most promising candidates to directly synthesize liquid bio-fuel using bio-oil-syngas.

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

    Science.gov (United States)

    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.

  15. Bio oil from pyrolysis of cashew nut shell-characterisation and related properties

    Energy Technology Data Exchange (ETDEWEB)

    Das, Piyali; Sreelatha, T.; Ganesh, Anuradda

    2004-09-01

    Biomass in the form of cashew nut shell represents a renewable and abundant source of energy in India. Cashew nut shell (CNS) was pyrolysed in a fixed bed pyrolysis reactor under vacuum. The CNS on heating upto 175 deg. C produced dark brown oil (oil CO1), which was extracted, and the CNS, after the removal of oil CO1, was pyrolysed under vacuum. The pyrolysis vapours were condensed to get a combustible oil fraction (oil CO2) as well as a noncombustible aqueous fraction. The detailed chemical compositional analysis of both the oils as well as aqueous fractions were carried out by various techniques like liquid column chromatography {sup 1}HNMR, {sup 13}CNMR, FTIR, GC-MS. The CNS oils (CO1 and CO2) were found to be a renewable natural resource of unsaturated phenols with long linear chains and marked absence of anacardic acid. Unlike other bio oils, the CNS oils have been found to be fairly stable. The oils were completely miscible in diesel and were found to have low corrosivity towards Copper and Stainless steel, and thus promise to be a potential fuel.

  16. Bio oil from pyrolysis of cashew nut shell-characterisation and related properties

    Energy Technology Data Exchange (ETDEWEB)

    Piyali Das; Anuradda Ganesh [Indian Institute of Technology, Mumbai (India). Energy Systems Engineering; Sreelatha, T. [Indian Institute of Chemical Technology, Hyderabad (India). Dept. of Chemistry

    2004-09-01

    Biomass in the form of cashew nut shell represents a renewable and abundant source of energy in India. Cashew nut shell (CNS) was pyrolysed in a fixed bed pyrolysis reactor under vacuum. The CNS on heating up to 175{sup o}C produced dark brown oil (oil CO1), which was extracted, and the CNS, after the removal of oil CO I, was pyrolysed under vacuum. The pyrolysis vapours were condensed to get a combustible oil fraction (oil CO2) as well as a non-combustible aqueous fraction. The detailed chemical compositional analysis of both the oils as well as aqueous fractions were carried out by various techniques like liquid column chromatography {sup 1}HNMR, {sup 13}CNMR, FTIR, GC-MS. The CNS oils (CO1 and CO2) were found to be a renewable natural resource of unsaturated phenols with long linear chains and marked absence of anacardic acid. Unlike other bio oils, the CNS oils have been found to be fairly stable. The oils were completely miscible in diesel and were found to have low corrosivity towards Copper and Stainless steel, and thus promise to be a potential fuel. (author)

  17. Selective Production of Aromatic Aldehydes from Heavy Fraction of Bio-oil via Catalytic Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan; Chang, Jie; Ouyang, Yong; Zheng, Xianwei [South China Univ. of Technology, Guangzhou (China)

    2014-06-15

    High value-added aromatic aldehydes (e. g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide (H{sub 2}O{sub 2}) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin (Co(TPPS{sub 4})) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without Co(TPPS{sub 4}). Moreover, a possible mechanism of HFBO oxidation using Co(TPPS{sub 4})/H{sub 2}O{sub 2} was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under Co(TPPS{sub 4})/H{sub 2}O{sub 2} system.

  18. Bio-methanol from Bio-oil Reforming Syngas Using Dual-reactor

    Institute of Scientific and Technical Information of China (English)

    Tong-qi Ye; Shi-zhi Yan; Yong Xu; Song-bai Qiu; Yong Liu; Quan-xin Li

    2011-01-01

    A dual-reactor,assembled with the on-line syngas conditioning and methanol synthesis,was successfully applied for high efficient conversion of rich CO2 bio-oil derived syngas to bio-methanol.In the forepart catalyst bed reactor,the catalytic conversion can effectively adjust the rich-CO2 crude bio-syngas into the CO-containing bio-syngas using the CuZnAlZr catalyst.After the on-line syngas conditioning at 450 ℃,the CO2/CO ratio in the biosyngas significantly decreased from 6.3 to 1.2.In the rearward catalyst bed reactor,the conversion of the conditioned bio-syngas to bio-methanol shows the maximum yield about 1.21 kg/(kgcatal·h) MeOH with a methanol selectivity of 97.9% at 260 ℃ and 5.05 MPa using conventional CuZnAl catalyst,which is close to the level typically obtained in the conventional methanol synthesis process using natural gas.The influences of temperature,pressure and space velocity on the bio-methanol synthesis were also investigated in detail.

  19. Application of 1D and 2D MFR reactor technology for the isolation of insecticidal and anti-microbial properties from pyrolysis bio-oils.

    Science.gov (United States)

    Hossain, Mohammad M; Scott, Ian M; Berruti, Franco; Briens, Cedric

    2016-12-01

    Valuable chemicals can be separated from agricultural residues by chemical or thermochemical processes. The application of pyrolysis has already been demonstrated as an efficient means to produce a liquid with a high concentration of desired product. The objective of this study was to apply an insect and microorganism bioassay-guided approach to separate and isolate pesticidal compounds from bio-oil produced through biomass pyrolysis. Tobacco leaf (Nicotianata bacum), tomato plant (Solanum lycopersicum), and spent coffee (Coffea arabica) grounds were pyrolyzed at 10°C/min from ambient to 565°C using the mechanically fluidized reactor (MFR). With one-dimensional (1D) MFR pyrolysis, the composition of the product vapors varied as the reactor temperature was raised allowing for the selection of the temperature range that corresponds to vapors with a high concentration of pesticidal properties. Further product separation was performed in a fractional condensation train, or 2D MFR pyrolysis, thus allowing for the separation of vapor components according to their condensation temperature. The 300-400°C tobacco and tomato bio-oil cuts from the 1D MFR showed the highest insecticidal and anti-microbial activity compared to the other bio-oil cuts. The 300-350 and 350-400°C bio-oil cuts produced by 2D MFR had the highest insecticidal activity when the bio-oil was collected from the 210°C condenser. The tobacco and tomato bio-oil had similar insecticidal activity (LC50 of 2.1 and 2.2 mg/mL) when the bio-oil was collected in the 210°C condenser from the 300-350°C reactor temperature gases. The 2D MFR does concentrate the pesticidal products compared to the 1D MFR and thus can reduce the need for further separation steps such as solvent extraction.

  20. Thermodynamic analysis of steam assisted conversions of bio-oil components to synthesis gas

    Energy Technology Data Exchange (ETDEWEB)

    Aktas, Seda; Karakaya, Mustafa; Avci, Ahmet K. [Department of Chemical Engineering, Bogazici University, Bebek 34342, Istanbul (Turkey)

    2009-02-15

    The aim of this study is to investigate the thermodynamics of steam assisted, high-pressure conversions of model components of bio-oil - isopropyl alcohol, lactic acid and phenol - to synthesis gas (H{sub 2} + CO) and to understand the effects of process variables such as temperature and inlet steam-to-fuel ratio on the product distribution. For this purpose, thermodynamic analyses are performed at a pressure of 30 bar and at ranges of temperature and steam-to-fuel ratio of 600-1200 K and 4-9, respectively. The number of moles of each component in the product stream and the product composition at equilibrium are calculated via Gibbs free energy minimization technique. The resulting optimization problems are solved by using the Sequential quadratic programming method. The results showed that all of the model fuels reached near-complete conversions to H{sub 2}, CO, CO{sub 2} and CH{sub 4} within the range of operating conditions. Temperature and steam-to-fuel ratio had positive effects in increasing hydrogen content of the product mixture at different magnitudes. Production of CO increased with temperature, but decreased at high steam-to-fuel ratios. Conversion of model fuels in excess of 1000 K favored molar H{sub 2}/CO ratios around 2, the synthesis gas composition required for Fischer-Tropsch and methanol syntheses. It was also possible to adjust the H{sub 2}/CO ratios and the amounts of CH{sub 4} and CO{sub 2} in synthesis gas by steam-to-fuel ratio, the value depending on temperature and the fuel type. Product distribution trends indicated the presence of water-gas shift and methanation equilibria as major side reactions running in parallel with the steam reforming of the model hydrocarbons. (author)

  1. Procedural investigations concerning the fast pyrolysis of lignocellulose in the Lurgi-Ruhrgas double-lead screw mixing reactor; Verfahrenstechnische Untersuchungen zur Schnellpyrolyse von Lignocellulose im Lurgi-Ruhrgas-Doppelschnecken-Mischreaktor

    Energy Technology Data Exchange (ETDEWEB)

    Kornmayer, C.; Dinjus, E.; Henrich, E.; Weirich, F. [Forschungszentrum Karlsruhe (Germany); Reimert, R. [Karlsruhe Univ. (T.H.) (Germany). Engler-Bunte-Institut

    2008-07-01

    The 'Bioliq' technology (Froschungszentrum Karlsruhe) is a 2-step process to produce synthesis gas from lignocellulose. During the first decentralized step the biomass is liquefied by fast pyrolysis, the product is a coke/oil slurry or paste. Main part of the pyrolysis facility is the Lurgi-Ruhrgas mixing reactor with a circular flow of solid heat carriers. The paper describes the procedural characteristics of the reactor and the yield structure of the fast pyrolysis process for different typical biomasses. The specific heat requirement in the reactor for pyrolysis and the conversion of the product to 500 deg C is based on process data for different dry charges. The results are based on experimental data from a test facility with up to 15 kg/h biomass input.

  2. Esterification of bio-oil from mallee (Eucalyptus loxophleba ssp. gratiae) leaves with a solid acid catalyst: Conversion of the cyclic ether and terpenoids into hydrocarbons.

    Science.gov (United States)

    Hu, Xun; Gunawan, Richard; Mourant, Daniel; Wang, Yi; Lievens, Caroline; Chaiwat, Weerawut; Wu, Liping; Li, Chun-Zhu

    2012-11-01

    Bio-oil from pyrolysis of mallee (Eucalyptus loxophleba ssp. gratiae) leaves differs from that obtained with wood by its content of cyclic ethers, terpenoids and N-containing organic compounds. Upgrading of the leaf bio-oil in methanol with a solid acid catalyst was investigated and it was found that the N-containing organics in the bio-oil lead to deactivation of the catalyst in the initial stage of exposure and have to be removed via employing high catalyst loading to allow the occurrence of other acid-catalysed reactions. Eucalyptol, the main cyclic ether in the bio-oil, could be converted into the aromatic hydrocarbon, p-cymene, through a series of intermediates including α-terpineol, terpinolene, and α-terpinene. Various steps such as ring-opening, dehydration, isomerisation, and aromatization were involved in the conversion of eucalyptol. The terpenoids in bio-oil could also be converted into aromatic hydrocarbons that can serve as starting materials for the synthesis of fine chemicals, via the similar processes.

  3. Separation of high-purity syringol and acetosyringone from rice straw-derived bio-oil by combining the basification-acidification process and column chromatography.

    Science.gov (United States)

    Hao, Shilai; Chen, Kaifei; Cao, Leichang; Zhu, Xiangdong; Luo, Gang; Zhang, Shicheng; Chen, Jianmin

    2016-10-01

    Numerous technologies have been used to reclaim valuable chemicals from bio-oil. In this study, a combination of the basification-acidification process and column chromatography was employed for the separation of high-purity syringol and acetosyringone from rice straw-derived bio-oil. The optimal conditions for the basification-acidification process and the possible precipitation mechanism of the basification were explored. The results showed the following as the optimal conditions for the basification process: mass ratio of calcium hydroxide (Ca(OH)2 ) to bio-oil, 2.0; reaction temperature, 70°C; and reaction time, 30 min. The results also showed that 1.6 mol of hydrochloric acid (HCl) per gram of bio-oil was optimal for the acidification. The precipitation was found to proceed via a possible mechanism involving the reaction of the phenolic compounds in the bio-oil with Ca(OH)2 to produce a precipitate. After further separation by column chromatography, purities of 91.4 and 96.2% (from gas chromatography-mass spectrometry) were obtained for syringol and acetosyringone, respectively. Their recoveries for the whole process were 73.0 and 39.3%, respectively.

  4. Production of bio-oil with flash pyrolysis and the combustion of it; Biooeljyn tuotanto flashpyrolyysillae ja sen poltto

    Energy Technology Data Exchange (ETDEWEB)

    Nyroenen, T. [Vapo Oy, Jyvaeskylae (Finland)

    1995-12-31

    The target of the research is to study the production of bio-oils using flash-pyrolysis and utilization of the bio-oil in oil-fueled boilers. The PDU-device was ordered in December 1994. The device was tested in Canada in the beginning of March 1996. The device will be mounted in Otaniemi in the research unit of VTT Energy. The device will by equipped, if possible, with a hot-filtering device in order to improve the purity and the quality of the oil. The capacity of the PDU-device is 20 kg/h of dry biomass of about 10 wt-% DS-content, with particle size less than 6 mm. The actual tests will be made in autumn 1996. The investment costs of the PDU are about 2.5 million FIM. The Canadian funding of the project is about 50 %. It has been planned that within the research project of Vapo oy, about 50 - 100 tons of bio-oil will be acquired from Canada for the engine tests carried out by Wartsilae Diesel, and the project will be responsible for planning and operation of the PDU and the demonstration plants. About 50 tons of wood-oil was received from Canada in January 1996 for the engine tests, the results of which will be reported separately by Wartsilae Diesel. The present costs of the tasks are about 1.2 million FIM, but the main part of the costs will be formed in 1996-1997

  5. Direct determination of arsenic in soil samples by fast pyrolysis-chemical vapor generation using sodium formate as a reductant followed by nondispersive atomic fluorescence spectrometry

    Science.gov (United States)

    Duan, Xuchuan; Zhang, Jingya; Bu, Fanlong

    2015-09-01

    This new study shows for the first time that sodium formate can react with trace arsenic to form volatile species via fast pyrolysis - chemical vapor generation. We found that the presence of thiourea greatly enhanced the generation efficiency and eliminated the interference of copper. We studied the reaction temperature, the volume of sodium formate, the reaction acidity, and the carried argon rate using nondispersive atomic fluorescence spectrometry. Under optimal conditions of T = 500 °C, the volumes of 30% sodium formate and 10% thiourea were 0.2 ml and 0.05 ml, respectively. The carrier argon rate was 300 ml min- 1 and the detection limit and precision of arsenic were 0.39 ng and 3.25%, respectively. The amount of arsenic in soil can be directly determined by adding trace amount of hydrochloric acid as a decomposition reagent without any sample pretreatment. The method was successfully applied to determine trace amount of arsenic in two soil-certified reference materials (GBW07453 and GBW07450), and the results were found to be in agreement with certified reference values.

  6. Effect of Corn Stalk Bio-Oil on Combustion and Emission Characteristics of Direct Injection Diesel Engine%玉米秸秆生物油对直喷式柴油机燃烧与排放的影响

    Institute of Scientific and Technical Information of China (English)

    韩旭东; 黄勇成; 易延洪; 黄松; 闻振江

    2012-01-01

    The experimental bio-oil was produced from corn stalk through fast pyrolysis process. In this paper, four emulsions with 5%, 10%, 15% and 20% by mass fraction of corn stalk bio-oil (CSB) in diesel fuel, represented by CSB5, CSB10, CSB15 and CSB20, respectively, were prepared by the ultrasonic emulsification method. Then, the combustion and emission characteristics of an unmodified direct injection diesel engine operating on the four emulsions were studied and compared with those of No. 0 diesel operation in order to provide the basis and theoretical guidance for the application of bio-oil in diesel engines. The results showed that, with the increase of CSB mass fraction in the emulsions, the ignition delay lengthens, both the heat released during the premixed combustion phase and the premixed combustion duration increase, while the total combustion duration shortens. With the increase of CSB mass fraction in the emulsions, the peak values of both premixed burning rate and pressure rise rate increase first and then decrease, while those of in-cylinder pressure and combustion temperature decrease. In addition, the fuel economy of CSB5 and CSB 10 is comparable to that of No. 0 diesel, while the fuel economy of CSB 15 and CSB20 is slightly poorer than that of No. 0 diesel. In comparison with No. 0 diesel, NOx emissions of all the emulsions are lower, while HC and CO emissions are higher. Furthermore, these trends are more remarkable with the increase of CSB fraction in the emulsions. Smoke emissions of the emulsions decrease first and then increase with the increase of CSB fraction in the emulsions. Meanwhile, smoke emissions of CSB5 and CSB 10 are lower while those of CSB 15 and CSB20 are slightly higher than those of No. 0 diesel.%采用超声波乳化法制备了玉米秸秆热解生物油质量分数分别为5%、10%、15%和20%的生物油/柴油乳化油,分别记为CSB5、CSB10、CSB15和CSB20,然后在一台未作改动的直喷式

  7. Characterization of Bio-Oil: A By-Product from Slow Pyrolysis of Oil Palm Empty Fruit Bunches

    OpenAIRE

    Khor, K.H; Lim, K. O.; Z. A. Zainal

    2009-01-01

    Problem statement: Oil palm Empty Fruit Bunches (EFB) are abundant biomass in Malaysia. Studies about production of biofuels using slow pyrolysis of EFB are still lacking. So, this study was aimed to understand the physical and chemical properties of the bio-oil and its simple blends. Approach: EFB was slow pyrolysed with internal heating at terminal temperature of 600°C in a pilot kiln and the main product is the EFB char and the condensates from the emissions were separated into aqueous and...

  8. Hydrogen Production by Catalytic Steam Reforming of Bio-oil, Naphtha and CH4 over C12A7-Mg Catalyst

    Science.gov (United States)

    Pan, Yue; Wang, Zhao-xiang; Kan, Tao; Zhu, Xi-feng; Li, Quan-xin

    2006-06-01

    Hydrogen production by catalytic steam reforming of the bio-oil, naphtha, and CH4 was investigated over a novel metal-doped catalyst of (Ca24Al28O64)4+·4O-/Mg (C12A7-Mg). The catalytic steam reforming was investigated from 250 to 850°C in the fixed-bed continuous flow reactor. For the reforming of bio-oil, the yield of hydrogen of 80% was obtained at 750°C, and the maximum carbon conversion is nearly close to 95% under the optimum steam reforming condition. For the reforming of naphtha and CH4, the hydrogen yield and carbon conversion are lower than that of bio-oil at the same temperature. The characteristics of catalyst were also investigated by XPS. The catalyst deactivation was mainly caused by the deposition of carbon in the catalytic steam reforming process.

  9. The application of water-soluble ruthenium catalysts for the hydrogenation of the dichloromethane soluble fraction of fast pyrolysis oil and related model compounds in a two phase aqueous-organic system

    NARCIS (Netherlands)

    Mahfud, F.H.; Bussemaker, S.; Kooi, B.J.; ten Brink, Gert; Heeres, H.J.

    2007-01-01

    The hydrogenation of a dichloromethane soluble fraction of flash pyrolysis oil (bio-oil, BO), obtained by treatment of BO with a water–dichloromethane solvent mixture, was investigated using a water-soluble homogeneous ruthenium catalyst (RuCl3·3H2O/tris(m-sulfonatophenyl)phosphine, TPPTS). The

  10. Pyrolysis Oil Biorefinery.

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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. Characterization of bio-oil from induction-heating pyrolysis of food-processing sewage sludges using chromatographic analysis.

    Science.gov (United States)

    Tsai, Wen-Tien; Lee, Mei-Kuei; Chang, Jeng-Hung; Su, Ting-Yi; Chang, Yuan-Ming

    2009-05-01

    In this study, gas chromatography-mass spectrometry (GC-MS) was used to analyze the pyrolytic bio-oils and gas fractions derived from the pyrolysis of industrial sewage sludges using induction-heating technique. The liquid products were obtained from the cryogenic condensation of the devolatilization fraction in a nitrogen atmosphere using a heating rate of 300 degrees C/min ranging from 25 to 500 degrees C. The analytical results showed that the pyrolysis bio-oils were very complex mixtures of organic compounds and contained a lot of nitrogenated and/or oxygenated compounds such as aliphatic hydrocarbons, phenols, pyridines, pyrroles, amines, ketones, and so on. These organic hydrocarbons containing nitrogen and/or oxygen should originate from the protein and nucleic acid textures of the microbial organisms present in the sewage sludge. The non-condensable devolatilization fractions were also composed of nitrogenated and oxygenated compounds, but contained small fractions of phenols, 1H-indoles, and fatty carboxylic acids. On the other hand, the compositions in the non-condensable gas products were principally carbon dioxide, carbon monoxide and methane analyzed by gas chromatography-thermal conductivity detector (GC-TCD).

  13. Characterization of Bio-Oil: A By-Product from Slow Pyrolysis of Oil Palm Empty Fruit Bunches

    Directory of Open Access Journals (Sweden)

    K. H. Khor

    2009-01-01

    Full Text Available Problem statement: Oil palm Empty Fruit Bunches (EFB are abundant biomass in Malaysia. Studies about production of biofuels using slow pyrolysis of EFB are still lacking. So, this study was aimed to understand the physical and chemical properties of the bio-oil and its simple blends. Approach: EFB was slow pyrolysed with internal heating at terminal temperature of 600°C in a pilot kiln and the main product is the EFB char and the condensates from the emissions were separated into aqueous and tarry fractions. Results: 13 wt% of tarry component (referred as EFB oil was obtained as small fraction of co-product. The chemical composition of the EFB oil acquired was analyzed by GC-MS and its elemental composition, stability, miscibility, oil fuel properties and corrosion characteristics were determined. The empirical formula of the EFB oil with heating value of 31.44 MJ kg-1 was established as CH1.41N0.03O0.24. Characterizations of bio-oil, diesel and emulsifier blends were performed. Conclusion/Recommendations: The experimental results showed that the emulsions of EFB oil obtained may be directly used as a fuel oil for combustion in a boiler or a furnace without any upgrading. Alternatively, the fuel may be refined to be used by vehicles.

  14. Upgraded bio-oil production via catalytic fast co-pyrolysis of waste cooking oil and tea residual.

    Science.gov (United States)

    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.

  15. Properties of sugarcane waste-derived bio-oils obtained by fixed-bed fire-tube heating pyrolysis.

    Science.gov (United States)

    Islam, Mohammad Rofiqul; Parveen, Momtaz; Haniu, Hiroyuki

    2010-06-01

    Agricultural waste in the form of sugarcane bagasse was pyrolyzed in a fixed-bed fire-tube heating reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and feed size on the product yields. Final temperature range studied was between 375 and 575 degrees C and the highest liquid product yield was obtained at 475 degrees C. Liquid products obtained under the most suitable conditions were characterized by physical properties, elemental analysis, GCV, FT-IR, (1)H NMR analysis and distillation. The empirical formula of the bio-oil with heating value of 23.5MJ/kg was established as CH(1.68)O(0.557)N(0.012). Comparison with other approaches showed that the liquid product yield by this simpler reactor system was higher with better physico-chemical properties as fuel. These findings show that fixed-bed fire-tube heating pyrolysis is a good option for production of bio-oils from biomass solid wastes.

  16. Bio-oil extraction of Jatropha curcas with ionic liquid co-solvent: Fate of biomass protein.

    Science.gov (United States)

    Severa, Godwin; Edwards, Melisa; Cooney, Michael J

    2017-02-01

    The fate of oil-seed biomass protein has been tracked through all steps of a multi-phase extraction process using an ionic liquid based co-solvent system previously demonstrated to extract bio-oil and phorbol esters and to recover fermentable sugars from Jatropha oil seed. These analyses, however, did not address the fate of biomass protein. This work demonstrated that the majority of protein (∼86%) tracked with the biomass with the balance lost to co-solvent (∼12%) and methanol (∼2%) washes. A significant portion of the ionic liquid remained with the treated biomass and required aggressive methanol washes to recover. A system analysis showed a net-positive energy balance and thus the potential of this system to produce both bio-oil and protein-rich toxin-free biomass. While these results further support Jatropha as an oil seed crop, the additional costs of solvent recovery will need to be addressed if commercialization is to be realized.

  17. Enzyme-assisted hydrothermal treatment of food waste for co-production of hydrochar and bio-oil.

    Science.gov (United States)

    Kaushik, Rajni; Parshetti, Ganesh K; Liu, Zhengang; Balasubramanian, Rajasekhar

    2014-09-01

    Food waste was subjected to enzymatic hydrolysis prior to hydrothermal treatment to produce hydrochars and bio-oil. Pre-treatment of food waste with an enzyme ratio of 1:2:1 (carbohydrase:protease:lipase) proved to be effective in converting food waste to the two products with improved yields. The carbon contents and calorific values ranged from 43.7% to 65.4% and 17.4 to 26.9 MJ/kg for the hydrochars obtained with the enzyme-assisted pre-treatment, respectively while they varied from 38.2% to 53.5% and 15.0 to 21.7 MJ/kg, respectively for the hydrochars obtained with no pre-treatment. Moreover, the formation of carbonaceous microspheres with low concentrations of inorganic elements and diverse surface functional groups was observed in the case of enzyme-assisted food waste hydrochars. The enzymatic pre-treatment also facilitated the formation of the bio-oil with a narrow distribution of organic compounds and with the highest yield obtained at 350 °C.

  18. Product yields and characteristics of rice husk, rice straw and corncob during fast pyrolysis in a drop-tube/fixed-bed reactor

    Directory of Open Access Journals (Sweden)

    Janewit Wannapeera

    2008-05-01

    Full Text Available Fast pyrolysis of rice husk, rice straw and corncob were investigated in a newly constructed drop-tube/fixed-bedreactor, which enables pyrolysis experiments under conditions closely simulating those occurring in commercial gasifierssuch as fluidised-bed gasifiers. Biomass samples were pyrolysed with a fast heating rate (i.e. > 1,000oC s-1, up to 850oC andholding times ranging from 1 to 10,800 seconds. Within 1 second after the biomass was injected into the reactor, considerableweight loss occurred instantaneously, leaving only a small amount of char, i.e. ~10-30 %. For all three samples, theweight loss continued throughout the range of holding times used but at an extremely slow rate, i.e. 1.3 % hr-1. The weightloss rates observed for the three biomass samples were affected by the proportion of the biomass chemical componentsas well as the metal species contents. Corncob, which had the lowest lignin content but highest cellulose content, had thehighest pyrolysis weight loss rate. On the other hand, rice husk containing a relatively high lignin content, had the lowestpyrolysis rate. The metal species (Na, K, Ca and Mg were found to increase devolatilisation yield depending on theircontents in biomass. The influence of the metal species was the most pronounced for rice straw, having the highest totalmetal species content. As the pyrolysis progressed, each biomass exhibited different char characteristics. Scanning electronmicroscopy (SEM pictures clearly showed the individual changes in geometry for all biomass-derived chars as well astheir decrease in combustion reactivities. The gas formation profiles for all three biomass samples showed almost the sametrend, with CO contributed by cellulose decomposition as the major gas product.

  19. 萃取耦合化学转化法提质生物油油溶相的研究%Upgrading the oil-soluble fraction of bio-oil by solvent extraction coupling with chemical conversion

    Institute of Scientific and Technical Information of China (English)

    秦菲; 崔洪友; 王传波; 王丽红; 易维明

    2014-01-01

    Upgrading the oil-soluble fraction, which was obtained by water extraction of bio-oil from fast pyrolysis of rice husk, was investigated with simultaneous esterification and acetalation in butanol with online solvent extraction ( SEAWOSE) . The results show that almost all of the acids, aldehydes and ketones in the oil-soluble fraction can be converted to the corresponding esters, hemiacetals and acetals by SEAWOSE. In comparing with direct esterification and acetalation without extraction, the char formation is significantly suppressed. Meanwhile, the upgraded oil has very low acidity and moisture content, but high heating value andgood volatility. The effect of oxidation and reduction pretreatment of the oil-soluble fraction before SEAWOSE was also investigated. By hydrogen peroxide oxidation, the aldehydes are firstly converted into acids and subsequently esterified to esters, consequently without char formation. The upgraded oil is high quality, less than% in moisture higher than MJ/kg in heating value and less than KOH mg/g in acidity.%采用萃取耦合化学转化技术对生物油油溶相进行了提质研究。将稻壳快速裂解油加入适宜水使其自然分为水溶相和油溶相。以正丁醇为萃取剂和转化剂,通过在线萃取将油溶相中的酸、醛、酮等可萃物不断萃取出来,再经酯化、缩醛化反应,转化为相应正丁醇的酯、缩醛和半缩醛等。与生物油直接酯化提质相比,萃取耦合化学转化法可以显著抑制提质过程中的结焦问题,降低了提质油相的含水量和酸值,提高了其热值和可挥发性。此外,还考察了油溶相预氧化和预还原对萃取耦合化学转化提质的影响。结果表明,预氧化后可将油溶相中的醛类转化为酸,再经酯化转化为稳定性好的酯类,提质后的油品水含量低于4%,热值高于30 MJ/ kg,酸值低于2 KOH mg/ g,并且结焦率为零。

  20. Valorization of algal waste via pyrolysis in a fixed-bed reactor: Production and characterization of bio-oil and bio-char.

    Science.gov (United States)

    Aboulkas, A; Hammani, H; El Achaby, M; Bilal, E; Barakat, A; El Harfi, K

    2017-06-23

    The aim of the present work is to develop processes for the production of bio-oil and bio-char from algae waste using the pyrolysis at controlled conditions. The pyrolysis was carried out at different temperatures 400-600°C and different heating rates 5-50°C/min. The algal waste, bio-oil and bio-char were successfully characterized using Elemental analysis, Chemical composition, TGA, FTIR, (1)H NMR, GC-MS and SEM. At a temperature of 500°C and a heating rate of 10°C/min, the maximum yield of bio-oil and bio-char was found to be 24.10 and 44.01wt%, respectively, which was found to be strongly influenced by the temperature variation, and weakly affected by the heating rate variation. Results show that the bio-oil cannot be used as bio-fuel, but can be used as a source of value-added chemicals. On the other hand, the bio-char is a promising candidate for solid fuel applications and for the production of carbon materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Selective Extraction of Bio-oil from Hydrothermal Liquefaction of Salix psammophila by Organic Solvents with Different Polarities through Multistep Extraction Separation

    Directory of Open Access Journals (Sweden)

    Xiao Yang

    2014-07-01

    Full Text Available Bio-oil obtained from hydrothermal liquefaction of Salix psammophila is a very complicated mixture with some highly valued chemicals. In order to separate the chemicals from bio-oil, solvent extraction using nine solvents with different polarities were investigated in detail. The bio-oil extraction yield of the nine solvents were from high to low: tetrahydrofuran > toluene > ethyl acetate > acetone > ether > methylene chloride > methanol > petroleum ether > n-hexane. Based on their extraction yield, an efficient solvent combination of n-hexane, ethyl acetate, and tetrahydrofuran was used to separate the bio-oil through multistep extraction into three parts: light oil (26.13%, mid-weight oil (54.19%, and heavy oil (19.68%. These fractions were characterized by gas chromatography-mass spectrometry, Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, and thermogravimetric analysis. The results showed that most of the highly valued chemicals were contained in the light oil; the mid-weight oil consisted of aromatic oligomer derived from the decomposition of lignin, which could be a promising candidate for partial substitute for petroleum-asphalt binder; the heavy oil was rich in alkanes.

  2. Properties of chicken manure pyrolysis bio-oil blended with diesel and its combustion characteristics in RCEM, Rapid Compression and Expansion Machine

    Directory of Open Access Journals (Sweden)

    Sunbong Lee

    2014-06-01

    Full Text Available Bio-oil (bio-oil was produced from chicken manure in a pilot-scale pyrolysis facility. The raw bio-oil had a very high viscosity and sediments which made direct application to diesel engines difficult. The bio-oil was blended with diesel fuel with 25% and 75% volumetric ratio at the normal temperature, named as blend 25. A rapid compression and expansion machine was used for a combustion test under the experimental condition corresponding to the medium operation point of a light duty diesel engine using diesel fuel, and blend 25 for comparison. The injection related pressure signal and cylinder pressure signal were instantaneously picked up to analyze the combustion characteristics in addition to the measurement of NOx and smoke emissions. Blend 25 resulted in reduction of the smoke emission by 80% and improvements of the apparent combustion efficiency while the NOx emission increased by 40%. A discussion was done based on the analysis results of combustion.

  3. Analysis of impact of temperature and saltwater on Nannochloropsis salina bio-oil production by ultra high resolution APCI FT-ICR MS

    KAUST Repository

    Sanguineti, Michael Mario

    2015-05-01

    Concentrated Nannochloropsis salina paste was reconstituted in distilled water and synthetic saltwater and processed at 250°C and 300°C via hydrothermal liquefaction. The resulting bio-oils yielded a diverse distribution of product classes, as analyzed by ultra high resolution APCI FT-ICR MS. The organic fractions were analyzed and both higher temperatures and distilled water significantly increase the number of total compounds present and the number of product classes. Major bio-oil products consisted of N1O1, hydrocarbon, and O2 classes, while O1, O4, S1, N1O2, and N2O2 classes represented the more significant minor classes. Both chlorine and sulfur containing compounds were detected in both distilled and saltwater reactions, while fewer numbers of chlorine and sulfur containing products were present in the organic fraction of the saltwater reactions. Further refinement to remove the chlorine and sulfur contents appears necessary with marine microalgal bio-oils produced via hydrothermal liquefaction. The higher heating value (MJ/kg) as calculated by the Boie equation of classes of interest in the bio-oil reveals a significant potential of algal hydrothermal liquefaction products as a sustainable and renewable fuel feedstock. © 2015.

  4. Homogeneous catalytic hydrogenation of bio-oil and related model aldehydes with RuCl{sub 2}(PPh{sub 3}){sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Huang, F.; Li, W.; Lu, Q.; Zhu, X. [Anhui Province Key Laboratory of Biomass Clean Energy, University of Science and Technology of China, Hefei (China)

    2010-12-15

    A homogeneous RuCl{sub 2}(PPh{sub 3}){sub 3} catalyst was prepared for the hydrogenation of bio-oil to improve its stability and fuel quality. Experiments were first performed on three model aldehydes of acetaldehyde, furfural and vanillin selected to represent the linear aldehydes, oxygen heterocyclic aldehydes and aromatic aldehydes in bio-oil. The results demonstrated the high hydrogenation capability of this homogeneous catalyst under mild conditions (55-90 C, 1.3-3.3 MPa). The highest conversion of the three model aldehydes was over 90 %. Furfural and acetaldehyde were singly converted to furfuryl alcohol and ethanol after hydrogenation, while vanillin was mainly converted to vanillin alcohol, together with a small amount of 2-methoxy-4-methylphenol and 2-methoxyphenol. Further experiments were conducted on a bio-oil fraction extracted by ethyl acetate and on the whole bio-oil at 70 C and 3.3 MPa. Most of the aldehydes were transformed to the corresponding alcohols, and some ketones and compounds with C-C double bond were converted to more stable compounds. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Promotion of hydrogen-rich gas and phenolic-rich bio-oil production from green macroalgae Cladophora glomerata via pyrolysis over its bio-char.

    Science.gov (United States)

    Norouzi, Omid; Jafarian, Sajedeh; Safari, Farid; Tavasoli, Ahmad; Nejati, Behnam

    2016-11-01

    Conversion of Cladophora glomerata (C. glomerata) as a Caspian Sea's green macroalgae into gaseous, liquid and solid products was carried out via pyrolysis at different temperatures to determine its potential for bio-oil and hydrogen-rich gas production for further industrial utilization. Non-catalytic tests were performed to determine the optimum condition for bio-oil production. The highest portion of bio-oil was retrieved at 500°C. The catalytic test was performed using the bio-char derived at 500°C as a catalyst. Effect of the addition of the algal bio-char on the composition of the bio-oil and also gaseous products was investigated. Pyrolysis derived bio-char was characterized by BET, FESEM and ICP method to show its surface area, porosity, and presence of inorganic metals on its surface, respectively. Phenols were increased from 8.5 to 20.76area% by the addition of bio-char. Moreover, the hydrogen concentration and hydrogen selectivity were also enhanced by the factors of 1.37, 1.59 respectively.

  6. Bio-Carbon Accounting for Bio-Oil Co-Processing: 14C and 13C/12C

    Energy Technology Data Exchange (ETDEWEB)

    Mora, Claudia I. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Li, Zhenghua [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Vance, Zachary [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-06-21

    This is a powerpoint presentation on bio-carbon accounting for bio-oil co-processing. Because of the overlapping range in the stable C isotope compositions of fossil oils and biooils from C3-type feedstocks, it is widely thought that stable isotopes are not useful to track renewable carbon during co-production. In contrast, our study demonstrates the utility of stable isotopes to: • capture a record of renewable carbon allocation between FCC products of co-processing • record changes in carbon apportionments due to changes in reactor or feed temperature Stable isotope trends as a function of percent bio-oil in the feed are more pronounced when the δ13C of the bio-oil endmember differs greatly from the VGO (i.e., it has a C4 biomass source–corn stover, switch grass, Miscanthus, sugarcane– versus a C3 biomass source– pine, wheat, rice, potato), but trends on the latter case are significant for endmember differences of just a few permil. The correlation between measured 14C and δ13C may be useful as an alternative to carbon accounting, but the relationship must first be established for different bio-oil sources.

  7. Production of Bio-gasoline by Co-cracking of Acetic Acid in Bio-oil and Ethanol

    Institute of Scientific and Technical Information of China (English)

    王树荣; 王誉蓉; 蔡勤杰; 郭祚刚

    2014-01-01

    Acetic acid was selected as the model compound representing the carboxylic acids present in bio-oil. This work focuses the co-cracking of acetic acid with ethanol for bio-gasoline production. The influences of reac-tion temperature and pressure on the conversion of reactants as well as the selectivity and composition of the crude gasoline phase were investigated. It was found that increasing reaction temperature benefited the conversion of re-actants and pressurized cracking produced a higher crude gasoline yield. At 400 °C and 1 MPa, the conversion of the reactants reached over 99%and the selectivity of the gasoline phase reached 42.79%(by mass). The gasoline phase shows outstanding quality, with a hydrocarbon content of 100%.

  8. Characterisation of palm empty fruit bunch (PEFB) and pinewood bio-oils and kinetics of their thermal degradation.

    Science.gov (United States)

    Pimenidou, P; Dupont, V

    2012-04-01

    Ultimate and proximate analyses and thermal degradation of bio-oils from pinewood and palm empty fruit bunches (PEFB) were carried out to evaluate the oils' potential for production of fuels for transport, heat and power generation, and of hydrogen via the calculation of performance indicators. The pinewood and PEFB oils indicated good theoretical hydrogen yields of 13.7 and 15.9 wt.% via steam reforming, but their hydrogen to carbon effective ratios were close to zero, and their propensity for fouling and slagging heat exchanger surfaces via combustion was high. Both oils exhibited two phases during mass loss under nitrogen flow at heating rates of 3-9 Kmin(-1), but the kinetics of their thermal degradation from TGA-FTIR analysis indicated different degradation mechanisms that were well reproduced by a nth order reaction model for pinewood and Jander's 3D-diffusion model for PEFB. These findings lead to recommendations on pretreatments prior to the oils' utilisation.

  9. Analysis of coke precursor on catalyst and study on regeneration of catalyst in upgrading of bio-oil

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Xiaoya; Zheng, Yong; Zhang, Baohua; Chen, Jinyang [Department of Chemical Engineering, Shanghai University, Shanghai 201800 (China)

    2009-10-15

    Catalyst HZSM-5 was used in bio-oil catalytic cracking upgrading. The precursor of coke on the catalyst was analyzed by means of TGA, FTIR and C13 NMR. Precursors of coke deposited in the pore of the molecular sieve were mainly aromatic hydrocarbon with the boiling point range from 350 C to 650 C. Those on the outer surface of the pellet precursor were identified as saturated aliphatic hydrocarbons with the boiling point below 200 C. The activity of HZSM-5 was studied after regeneration. In terms of yield of organic distillate and formation rate of coke, results showed that catalytic activity change moderately during the first three times of regeneration. (author)

  10. Directly catalytic upgrading bio-oil vapor produced by prairie cordgrass pyrolysis over Ni/HZSM-5 using a two stage reactor

    Directory of Open Access Journals (Sweden)

    Shouyun Cheng

    2015-06-01

    Full Text Available Catalytic cracking is one of the most promising processes for thermochemical conversion of biomass to advanced biofuels in recent years. However, current effectiveness of catalysts and conversion efficiency still remain challenges. An investigation of directly catalytic upgrading bio-oil vapors produced in prairie cordgrass (PCG pyrolysis over Ni/HZSM-5 and HZSM-5 in a two stage packed-bed reactor was carried out. The Ni/HZSM-5 catalyst was synthesized using an impregnation method. Fresh and used catalysts were characterized by BET and XRD. The effects of catalysts on pyrolysis products yields and quality were examined. Both catalysts improved bio-oil product distribution compared to non-catalytic treatment. When PCG pyrolysis vapor was treated with absence of catalyst, the produced bio-oils contained higher alcohols (10.97% and furans (10.14%. In contrast, the bio-oils contained the second highest hydrocarbons (34.97%)and the highest phenols (46.97% when PCG pyrolysis vapor was treated with Ni/HZSM-5. Bio-oils containing less ketones and aldehydes were produced by both Ni/HZSM-5 and HZSM-5, but no ketones were found in Ni/HZSM-5 treatment compared to HZSM-5 (2.94%. The pyrolysis gas compositions were also affected by the presenting of HZSM-5 or Ni/HZSM-5 during the catalytic upgrading process. However, higher heating values and elemental compositions (C, H and N of bio-chars produced in all treatments had no significant difference.

  11. Reduction of the Variety of Phenolic Compounds in Bio-oil via the Catalytic Pyrolysis of Pine Sawdust

    Directory of Open Access Journals (Sweden)

    Duo Wang

    2014-05-01

    Full Text Available The objective of this study was to evaluate phenolic compounds produced from the catalytic pyrolysis of pine sawdust by commercial catalysts. Eight types of commercial catalysts consisting of SiO2, montmorillonite, α-Fe2O3, HZSM-5 (Si:Al = 25:1, ZnO, γ-Fe2O3, HZSM-5 (Si:Al = 50:1, and nano-HZSM-5 (Si:Al = 50:1 were screened in a fixed bed reactor at a reaction temperature of 500 °C and a vapor residence time of 3 s. All the tested commercial catalysts exhibited different catalytic performances for the adjustment of the composition of the bio-oil. HZSM-5 (Si:Al = 25:1 significantly increased hydrocarbon production in the bio-oil, which is helpful for improving its heating value. The different types of phenols were reduced significantly from 17 to 7 with nano-HZSM-5 (Si:Al = 50:1; however, the phenols content also decreased from 32.6% to 23.28% compared with non-catalytic pyrolysis. Meanwhile, the addition of nano-HZSM-5 (Si:Al = 50:1 to the raw material provided the highest amount of furans (up to 38.8% among the tested commercial catalysts. The inexpensive ZnO and γ-Fe2O3 also were surprisingly effective for the reduction of the variety of phenolic compounds detected by GC/MS, reducing that number from 17 to 10.

  12. Bio-oil from pyrolysis of cashew nut shell - a near fuel

    Energy Technology Data Exchange (ETDEWEB)

    Das, P.; Ganesh, A. [Indian Inst. of technology, Mumbai (India). Energy Systems Engineering

    2003-07-01

    Cashew nut shell (CNS) has been studied for the product distribution in a packed bed vacuum pyrolysis unit. The effect of pyrolysis temperatures on the product yields is also studied. The oil-to-liquid ratio in the pyrolysis products was found to remain almost constant in the range between 400{sup o}C and 550{sup o}C. The properties of CNS oil has been found to be amazingly near to that of petroleum fuels with calorific value as high as 40 MJkg{sup -1}, the oil has a low ash content (0.01%) and water content is limited to 3-3.5 wt% of oil. (Author)

  13. Refining fast pyrolysis of biomass

    NARCIS (Netherlands)

    Westerhof, Roel Johannes Maria

    2011-01-01

    Pyrolysis oil produced from biomass is a promising renewable alternative to crude oil. Such pyrolysis oil has transportation, storage, and processing benefits, none of which are offered by the bulky, inhomogeneous solid biomass from which it originates. However, pyrolysis oil has both a different

  14. Refining fast pyrolysis of biomass

    NARCIS (Netherlands)

    Westerhof, Roel Johannes Maria

    2011-01-01

    Pyrolysis oil produced from biomass is a promising renewable alternative to crude oil. Such pyrolysis oil has transportation, storage, and processing benefits, none of which are offered by the bulky, inhomogeneous solid biomass from which it originates. However, pyrolysis oil has both a different co

  15. 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

    Science.gov (United States)

    Supramono, D.; Lusiani, S.

    2016-11-01

    Over the past few decades, interest in developing biomass-derived fuel has been increasing rapidly due to the decrease in fossil fuel reserves. Bio-oil produced by biomass pyrolysis however contains high oxygen compounds resulting in low calorific-value fuel and therefore requiring upgrading. In co-pyrolysis of the feed blend of plastics of High Density Polyethylene (HDPE) and biomass of com cob particles, at some compositions free radicals from plastic decomposition containing more hydrogen radicals are able to bond oxygen radicals originating from biomass to reduce oxygenate compounds in the bio-oil thus increasing bio-oil quality. This phenomenon is usually called synergetic effect. In addition to that, the pattern of heating of the feed blend in the pyrolysis reactor is predicted to affect biooil quality and yield. In a batch reactor, co-pyrolysis of corncobs and HDPE requires low heating rate to reach a peak temperature at temperature rise period followed by heating for some time at peak temperature called holding time at constant temperature period. No research has been carried out to investigate how long holding time is set in co-pyrolysis of plastic and biomass to obtain high yield of bio-oil. Holding time may affect either crosslinking of free radicals in gas phase, which increases char product, or secondary pyrolysis in the gas phase, which increases non-condensable gas in the gas phase of pyrolysis reactor, both of which reduce bio-oil yield. Therefore, holding time of co-pyrolysis affects the mass rate of bio-oil formation as the pyrolysis proceeds and quality of the bio-oil. In the present work, effects of holding time on the yield and quality of bio-oil have been investigated using horizontal fixed bed of the feed blends at heating rate of 5°C, peak temperature of 500°C and N2 flow rate of 700 ml/minute. Holding time was varied from 0 to 70 minutes with 10 minutes interval. To investigate the effects of holding time, the composition of HDPE in the

  16. 松子壳热解重质油的催化改性%Catalytic upgrading of heavy bio-oil from pyrolysised pine-nut shell

    Institute of Scientific and Technical Information of China (English)

    蒋恩臣; 孙焱; 秦丽元; 李爽

    2014-01-01

    With the consumption of fossil fuels, it would be more and more difficult to depend on fossil fuels for energy, which together with the environment problems forces people to find a clean and renewable alternative energy. Because of the huge amount, the environmental friendly and renewable features, the biomass has aroused considerable attention. Bio-oil is one of the products from biomass pyrolysis. As a kind of promising alternative energy, bio-oil has showed some good characteristics of high energy density, convenient storage and transportation. In generally, bio-oil is brown acid liquid with smoke and irrigating smell. The major components of bio-oil are acids, phenols, and hydrocarbon and so on. Based on the different component characteristics, bio-oil could be divided into two parts:the light part which is called pyroligneous, and the heavy part. The heavy part consists of large molecules from the procedure of pyrolysis, which is difficult to use for its high viscosity and high oxygen content. Catalytic cracking is one of the useful methods for bio-oil upgrading, although the lifetime of the catalyst is influenced by the char deposit. More and more promising materials are used for catalyst cracking, however, the absence of theoretical support makes the upgrading process blind. In this paper, pine-nut shell was pyrolyzed through continuous pyrolysis device. In order to gain more liquid product, the reaction parameters of temperature (350-650℃) and time (2-8 min) were researched. The GC-MS was used to analyze the major constituent of the pine-nut shell bio-oil produced at the suitable situation, as well as its properties including viscosity, heat value, water content and pH. The heavy part of bio-oil was divided from the bio-oil for the upgrading experiment. The catalytic cracking experiment was carried out on the fixed bed reactor. In the experiment HZSM-5 and NiO/HZSM-5 zeolite were used to catalyze the heavy oil respectively. The heavy oil was compared with

  17. High resolution FT-ICR mass spectral analysis of bio-oil and residual water soluble organics produced by hydrothermal liquefaction of the marine microalga Nannochloropsis salina

    Energy Technology Data Exchange (ETDEWEB)

    Sudasinghe, Nilusha; Dungan, Barry; Lammers, Peter; Albrecht, Karl O.; Elliott, Douglas C.; Hallen, Richard T.; Schaub, Tanner

    2014-03-01

    We report a detailed compositional characterization of a bio-crude oil and aqueous by-product from hydrothermal liquefaction of Nannochloropsis salina by direct infusion Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) in both positive- and negative-ionization modes. The FT-ICR MS instrumentation approach facilitates direct assignment of elemental composition to >7000 resolved mass spectral peaks and three-dimensional mass spectral images for individual heteroatom classes highlight compositional diversity of the two samples and provide a baseline description of these materials. Aromatic nitrogen compounds and free fatty acids are predominant species observed in both the bio-oil and aqueous fraction. Residual organic compounds present in the aqueous fraction show distributions that are slightly lower in both molecular ring and/or double bond value and carbon number relative to those found in the bio-oil, albeit with a high degree of commonality between the two compositions.

  18. Altering bio-oil composition by catalytic treatment of pinewood pyrolysis vapors over zeolites using an auger - packed bed integrated reactor system

    Directory of Open Access Journals (Sweden)

    Vamshi Krishna Guda

    2016-09-01

    Full Text Available Pine wood pyrolysis vapors were catalytically treated using Zeolite catalysts. An auger fed reactor was used for the pinewood pyrolysis while a packed bed reactor mounted on the top of the auger reactor housed the catalyst for the treatment of pinewood pyrolytic vapors. The pyrolytic vapors produced at 450 oC were passed through zeolite catalysts maintained at 425 oC at a weight hourly space velocity (WHSV of 12 h-1. Five zeolites, including ZSM-5, mordenite, ferrierite, Zeolite-Y, and Zeolite-beta (all in H form, were used to study the effect of catalyst properties such as acidity, pore size, and pore structure on catalytic cracking of pinewood pyrolysis vapors. Product bio-oils were analyzed for their chemical composition using GC-MS, water content, density, viscosity, acid value, pH, and elemental compositions. Thermogravimetric analysis (TGA was performed to analyze the extent of coking on zeolite catalysts. Application of catalysis to biomass pyrolysis increased gas product yields at the expense of bio-oil yields. While all the zeolites deoxygenated the pyrolysis vapors, ZSM-5 was found to be most effective. The ZSM-5 catalyzed bio-oil, rich in phenolics and aromatic hydrocarbons, was less viscous, had relatively lower acid number and high pH, and possessed oxygen content nearly half that of un-catalyzed bio-oil. Brønsted acidity, pore size, and shape-selective catalysis of ZSM-5 catalyst proved to be the determining factors for its activity. TGA results implied that the pore size of catalysts highly influenced coking reactions. Regeneration of the used catalysts was successfully completed at 700 oC.

  19. Upgrading of bio-oil derived from tobacco using ferrierite, ZSM-5 and Co-Mo/Al2 O3 catalysts

    Directory of Open Access Journals (Sweden)

    Sawitree Mulika

    2015-03-01

    Full Text Available This research aims to investigate bio-oil yield of tobacco leave by pyrolysis at 450-550o C. The bio-oil was upgraded by ferrierite, ZSM-5, Al2 O3 , Co-Mo/Al2 O3 and Mo2 C catalysts. Pyrolysis was carried out in a semi-batch reactor with a space velocity of 1.7 h-1 under nitrogen atmosphere. The highest liquid yield of 47.1% was observed at 500o C with the high heating value of 36.3 MJ/kg oil (organic phase. Furthermore, char and gas yields were 36.7 and 16.2%, respectively. As a result, the high heating values of the bio-oils catalyzed at 500o C by ferrierite, ZSM-5, Al2 O3 , Mo2 C and Co-Mo/Al2 O3 were 22.5, 24.7, 26.1, 35.8 and 36.8 MJ/kg oil (organic phase, respectively.

  20. Flash co-pyrolysis of biomass with polyhydroxybutyrate: Part 1. Influence on bio-oil yield, water content, heating value and the production of chemicals

    Energy Technology Data Exchange (ETDEWEB)

    T. Cornelissen; M. Jans; J. Yperman; G. Reggers; S. Schreurs; R. Carleer [Hasselt University, Diepenbeek (Belgium). Laboratory of Applied Chemistry

    2008-09-15

    Bio-oil obtained via flash pyrolysis shows potential to be applied as a renewable fuel. However, bio-oil often contains high amounts of water, which is a major drawback for its application. The influence of a biopolymer - polyhydroxybutyrate (PHB) on the pyrolysis of willow is investigated using a semi-continuous home-built pyrolysis reactor. The flash co-pyrolysis of willow/PHB blends (w/w ratio 7:1, 3:1, 2:1 and 1:1) clearly shows particular merits: a synergetic increase in pyrolysis yield, a synergetic reduction of the water content in bio-oil, an increase in heating value, and a production of easily separable chemicals. The occurrence of synergetic interactions is observed based on a comparison between the actual pyrolysis results of the willow/PHB blends, the theoretical pyrolysis results calculated from the reference pyrolysis experiments (pure willow and pure PHB) and their respective w/w ratio. The co-pyrolysis of 1:1 willow/PHB shows the best overall results. 24 refs., 9 figs., 5 tabs.

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

    Science.gov (United States)

    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.

  2. Catalytic hydropyrolysis of microalgae: influence of operating variables on the formation and composition of bio-oil.

    Science.gov (United States)

    Chang, Zhoufan; Duan, Peigao; Xu, Yuping

    2015-05-01

    Catalytic hydropyrolysis of microalgae has been studied by using a batch reactor. Nine different heterogenous catalysts of Pd/C, Pt/C, Ru/C, Rh/C, CoMo/γ-Al2O3, Mo2C, MoS2, and activated carbon were screened. Mo2C was identified as the most suitable catalyst. With Mo2C catalyst, influence of reaction conditions on the yield and properties of the hydropyrolysis oil (HPO) was examined. Temperature was the most influential factor affecting the yield and quality of the HPO. Higher temperature will produce HPO with higher C and H content and lower N and O content but at the cost of lowering the yield of HPO. Mo2C promoted the in situ deoxygenation and desulfurization of the HPO which has a HHVs varying between 35.3 and 39.3 MJ/kg. The highest energy recovery of 87.5% was achieved. Thus, this work shows that the catalytic hydropyrolysis is an effective way to produce high quality bio-oil from microalgae.

  3. 响应面法优化油菜秸秆真空热解液化工艺及生物油分析1%Bio-Oil Analysis and Optimization of Bio-Oil Yield from Vacuum Pyrolysis of Rape Straw Using Response Surface Methodology

    Institute of Scientific and Technical Information of China (English)

    樊永胜; 蔡忆昔; 李小华; 张蓉仙; 尹海云; 俞宁

    2015-01-01

    Bio-oil yield from rape straw vacuum pyrolysis was optimized. Pyrolysis temperature, reactor pressure and heating rate were selected as independent variables and the response surface methodology (RSM) was employed to obtain maximum bio-oil yield. Moreover, the physical properties and composition of the bio-oil produced under optimal conditions were analyzed. The results show that pyrolysis temperature,reactor pressure and heating rate have obvious effects on bio-oil yield, and pyrolysis temperature and heating rate have a significant interaction. The optimal conditions for bio-oil yield were obtained at pyrolysis temperature of 490.0℃, system pressure of 5.0 kPa and heating rate of 20.0℃?min?1. Confirmation runs gave 41.65% of bio-oil yield compared to 42.00% of predicted value. Water content and high heat value of the bio-oil were 33.85% and 18.65 MJ?kg?1 respectively, and its dynamic viscosity at room temperature, density and pH value were 4.16 mm2?s?1, 1.14 g?cm?3 and 2.32, respectively. The bio-oil obtained from rape straw is a complex mixture. It is highly-oxygenated with a great amount of organics, which mainly include aldehydes, ketones, carboxylic acids, alcohols and aromatics. Some organic compounds could be further extracted as industrial raw materials. Further study on upgrading of bio-oil from vacuum pyrolysis of rape straw should be performed in future.%以油菜秸秆为原料,采用真空热解系统进行了制取生物油的中心组合实验研究,以热解终温、体系压力和升温速率为实验因子,生物油产率为实验指标,利用响应面法(RSM)对制备生物油的工艺参数进行了优化,并对在最优条件下制取的生物油进行了理化特性和化学组成分析.研究结果表明,热解终温、体系压力和升温速率对生物油产率有显著影响,热解终温和升温速率之间的交互作用显著;获得最佳热解液化工艺条件为:热解终温490.0℃、体系压力5.0 kPa、升温速率20.0

  4. Availability of P and K in ash from thermal gasification of animal manure

    Energy Technology Data Exchange (ETDEWEB)

    Rubaek, G.H.; Soerensen, Peter [Danish Inst. of Agricultural Sciences, Dept. of Agroecology, Tjele (Denmark); Stoholm, P. [Danish Fluid Bed Technology (Denmark)

    2006-08-15

    In areas like Denmark where the livestock density is regulated on the basis of manure N content, surplus phosphorus is becoming a key environmental problem, which has to be solved in order to avoid increasing P losses to surface waters in the future. Combustion of animal manure or its solid fraction and the subsequent export of the ash to nutrient-poor areas could be a solution. However, combustion is difficult due to fouling and corrosion problems, and the ash will only be marketable if the fertiliser value of the remaining P and K is acceptable and if the content of contaminants (heavy metals) is sufficiently low. A combined fast pyrolysis and char gasification technique for treatment of biomass has been developed where organic material such as manure is processed in a fluidised bed reactor at temperatures and around 700 deg. C. After simple separation of a fine textured ash, the cleaned gas is suitable for combustion in a separate unit for energy production. One advantage of this technique is that the temperature can be finely controlled, and temperatures exceeding the melting point of e.g. potassium chloride can be avoided. The low and well-controlled temperature probably also prevents severe reductions in the availability of nutrients in the ash. However, the availability of P and K in the ash remains to be thoroughly tested. (au)

  5. Bio-oil production and removal of organic load by microalga Scenedesmus sp. using culture medium contaminated with different sugars, cheese whey and whey permeate.

    Science.gov (United States)

    Borges, Wesley da Silva; Araújo, Breno Severiano Alves; Moura, Lucas Gomes; Coutinho Filho, Ubirajara; de Resende, Miriam Maria; Cardoso, Vicelma Luiz

    2016-05-15

    The objective of this study was to evaluate the bio-oil production and the organic load removal using the microalga Scenedesmus sp. The cultivation was carried out in reactors with a total volume of 3 L and 0.7 vvm aeration, with illumination in photoperiods of 12 h light/12 h dark for 12 days. The following sugar concentrations were tested: 2.5, 5.0 and 10 g/L of glucose, lactose, fructose and galactose with 10% inoculum volume. After experiments were performed with cheese whey in natura and cheese whey permeate with different lactose concentrations (1.5, 2.5, 3.5 and 5.0 g/L). In these experiments the inoculum concentrations were 10, 15, 20 and 30% (v/v). The results showed that this microalga was effective for the production of lipids when it was cultivated in medium with cheese whey in natura with 2.5 g/L of lactose and 20% inoculum (v/v). Using cheese whey in natura at the concentration of 3.5 g/L of lactose and 30% (v/v) of inoculum obtained 77.9% of TOC removal and 38.447 mg of TOC removed/mg oil produced. It was also observed that when there is increased production of bio-oil, there is less removal of organic matter. The addition of glucose, fructose or galactose in the medium did not enhance the production of bio-oil by Scenedesmus sp. when compared to lactose, but increased the organic matter removal.

  6. Effect of temperature and AAEM species on fast pyrolysis of biomass tar%热解温度及AAEM元素对生物质快速热解焦油的影响

    Institute of Scientific and Technical Information of China (English)

    冯冬冬; 赵义军; 唐文博; 张宇; 钱娟; 孙绍增

    2016-01-01

    生物质热解受热解温度、热解速率和碱金属及碱土金属(AAEM)元素影响显著。利用热裂解气相色谱质谱联用法(Py-GC/MS)针对热解温度及AAEM元素对生物质快速热解焦油的影响展开深入研究,通过样品热解前后的失重情况分析了热解温度及AAEM元素对生物质(稻壳和木屑、酸洗稻壳和酸洗木屑)热解特性的影响规律,利用气相色谱质谱仪(GC/MS)对热解焦油组分及含量进行了在线半定量分析,并对热解焦油组分分子量分布情况展开了讨论。结果表明生物质Py-GC/MS快速热解实验,酸洗脱除AAEM元素致使热解失重率减小。500~900℃范围内随温度的升高,大分子焦油成分逐渐减少,逐渐转化为轻质组分。AAEM 元素限制了焦油前体的聚合,进一步抑制了含氧杂环类碳环(糠醛等)的生成。稻壳的热解焦油的相对分子质量主要分布在110~129。木屑快速热解焦油产率明显高于稻壳,且热解焦油中分子量分布广泛,含有更多较大分子量(150~209)的化合物成分。%Pyrolysis temperature, heating rate, alkali metal and alkaline earth metal (AAEM) species have significant effects on biomass pyrolysis. In this paper, by using the pyrolysis gas chromatography mass spectrometry (Py-GC/MS), the effect of temperature and AAEM species on fast pyrolysis of the biomass tar was investigated. The influence of pyrolysis temperature and AAEM species on the pyrolysis characteristics of biomass (rice husk and sawdust, H-form rice husk and H-form sawdust) was analyzed by means of mass loss of samples. The online semi quantitative analysis of pyrolysis tar was carried out by gas chromatography mass spectrometry (GC/MS). The distribution of molecular weight of pyrolysis tar was discussed. The results showed that during fast pyrolysis of biomass, the removal of AAEM species reduced the mass loss rate. With increasing pyrolysis temperature in

  7. Oxygen-Containing Fuels from High Acid Water Phase Pyrolysis Bio-Oils by ZSM−5 Catalysis: Kinetic and Mechanism Studies

    Directory of Open Access Journals (Sweden)

    Yi Wei

    2015-06-01

    Full Text Available This study developed an upgrading process focusing on acid transformations of water phase pyrolysis bio-oils to esters of oxygen-containing fuels via ZSM−5 catalyst. Temperature was set as a factor with five levels ranging from 60 to 135 °C with reaction time from 1 to 8 h. The results showed that 89% of high acid conversion and over 90% of ester selectivity was obtained from the feedstock via 2 wt % ZSM−5 catalysts in a fixed feedstock to methanol ratio analyzed by HPLC and GC–MS. The upgrading process followed Langmuir–Hinshelwood and reaction constants were calculated to build a practical upgrading model for bio-oil compounds. Thermodynamics of the process showed endothermic properties during the breaking bonds’ reaction on carbonyl of acid while the reaction between the carbon in methanol and electrophile acid intermediate demonstrated exothermic performance. The optimum reaction conditions for the process was at a temperature of 100.1 °C with catalyst loading of 3.98 wt %.

  8. 不同快速裂解气氛下的烟煤表面微观特性%Investigation into microscopic characteristics of bituminous surface under different fast pyrolysis conditions

    Institute of Scientific and Technical Information of China (English)

    徐亮; 齐永锋; 张冬冬; 李正明; 马丽; 常轩; 马强

    2013-01-01

    采用实验工况与电站煤粉锅炉相近的管式炉实验装置,分别制取了N2,(ψ)(N2)=83.4%∶(ψ)(CO2)=16.6%,(ψ)(N2)=81.6%∶(ψ)(CO2)=16.6%∶(ψ)(O2)=1.8%3种气氛下神木烟煤快速裂解的煤焦.结合扫描电子显微镜和烟气分析仪检测发现,与煤粉处于堆积态的慢速热解不同,3种气氛下煤快速热解时破碎的小颗粒较多,随着停留时间的增加,煤焦表面的小孔结构逐渐增多;与N2气氛下相比,加入CO2后煤焦表面变得更致密,再加入O2后,随着停留时间的增加,煤焦表面发生微弱燃烧.%In a drop tube furnace with the combustion conditions similar to those of actual pulverized coal furnace,ShenMu bituminous coal char of fast pyrolysis conditions are prepared under different reaction atmospheres of N2,(ψ)(N2) = 83.4% ∶ (ψ)(CO2) = 16.6%,(ψ)(N2) = 81.6% ∶ (ψ)(CO2) =16.6% ∶ (ψ)(O2)= 1.8%.By means of scanning electron microscopy and flue gas analyzer,the achieved experimental results are quite different from slow pyrolysis of packing pulverized coal.Under fast pyrolysis conditions,more small particles of coal crushing are found.With increasing residence time,the small holes on the surface of char gradually increase.Compared with N2 atmosphere,the surface of the char under (ψ)(N2) = 83.4 % ∶ (ψ)(CO2) = 16.6 % atmosphere becomes more densely.Finally,with increasing residence time,under (ψ)(N2) = 81.6% ∶ (ψ)(CO2) = 16.6% ∶ (ψ)(O2) =1.8% atmosphere,some weak fire is found on the surface of the coal char.

  9. THERMOCHEMICAL CATALYTIC LIQUEFACTION OF MICROALGAE AND PROPERTIES OF BIO-OIL%微藻热化学催化液化及生物油特性研究

    Institute of Scientific and Technical Information of China (English)

    邹树平; 吴玉龙; 杨明德; 陈镇; 李春; 童军茂

    2009-01-01

    The liquefaction of Dunaliella tertiolecta was investigated in ethylene glycol acidified with H_2SO_4 as catalyst. Mathematical model for predicting the liquefaction yield was set up by central composite design and response surface anal-ysis (RSA) on the basis of one-factor tests. From a regression analysis, it appears that the individual effects, as well as the interactions between operating variables all have significant effects on the liquefaction of Dunaliella tertiolecta. Such effects can be graphically verified through response surfaces and contour line plots. The liquefaction technology was opti-mized as follows: sulfuric acid content of 2.4%, the temperature of 170℃ and the time of 33min. The liquefaction yield reached 97.05% at above-mentioned conditions. To put bio-oil from thermochemical catalytic liquefaction of microalgae into wide application, physical and chemical characteristics of bio-oil were studied in detail and the main compositions of the bio-oil were characterized by FT-IR, GC-MS, ~(13)C-NMR. The major chemical compositions detected were 30.43% benzofuranone, 23.35% fatty acid methyl ester and 27.89% fatty acid hydroxyehtyl ester with long chain from C_(14) to C_(18). Upgrading of bio-oil should be processed further to improve its quality due to its high oxygen content.%以杜氏盐藻为原料,乙二醇为液化介质、浓硫酸为催化剂进行热化学液化反应.运用中心组合设计及响应面分析(RSA),在单因素试验的基础上建立了预测杜氏盐藻液化产率的数学模型.回归分析表明,液化温度、停留时间与催化剂用量及其交互作用对液化都有显著影响.以液化产率为响应值作响应面和等高线图,揭示了各参数交互关系.通过响应面优化,求得最佳工艺条件为:催化剂用量2.4%,液化温度170℃,停留时间33min,在此条件下液化率达到97.05%.基于生物油广泛应用的目的,对产物生物油的物理化学性质

  10. HZSM-5分子筛催化热裂解油菜秸秆制取精制生物油%Catalytic pyrolysis of rape straw for upgraded bio-oil production using HZSM-5 zeolite

    Institute of Scientific and Technical Information of China (English)

    俞宁; 蔡忆昔; 李小华; 樊永胜; 尹海云; 张蓉仙

    2014-01-01

    Catalytic upgrading of the vapors from rape straw vacuum pyrolysis was conducted over HZSM-5 zeolite in a fixed bed reactor. Univariate analysis was employed in this study to investigate the effects of the operating parameters, including catalyst quality, Si/Al ratio of catalyst, and catalyzing temperature, on the product yields and the composition of upgraded bio-oil. Based on the univariate analysis, the preliminary operating parameters of catalytic reactor were optimized. The results showed that, when the catalyzing temperature was 500℃and HZSM-5 (Si/Al=50) quality was 60 g, a lower oxygen content (27.97 percent), higher heating value (30.14kJ/kg-1), and a lower hydrogen-to-carbon ratio (0.12) were obtained. Moreover, the components of the obtained bio-oil contained a small amount of high oxygen contents, such as aldehydes, acids, and ketones. Meanwhile, phenols and aromatic hydrocarbons obviously increased. Product distribution and yield between upgraded bio-oil and crude bio-oil was also compared to study the catalytic refining effects and catalytic deoxygenation performance of HZSM-5 zeolite. This capacity of HZSM-5 zeolite was the key to make up for the two shortcomings of crude bio-oil, which were corrosivity and instability. The catalyst quality had significant effects on the properties of the upgraded bio-oil. Catalytic upgrading of pyrolysis vapors was incomplete when the catalyst quality was not high enough. However, when the catalyst quality was excessive, a decreased yield of upgraded oil resulted due to excessive secondary cracking reactions. In this study, the quality ratio of the catalyst to biomass was about 0.4. Catalyzing temperature also had an important effect on the properties of upgraded oil. When the catalyzing temperature was lower, the activation energy could not meet the needs of cracking reactions, and the catalytic effect was poor. When the catalyzing temperature was higher than optimal value, deactivation of the catalyst resulted

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

    Science.gov (United States)

    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.

  12. CH4 release character from pressurized fast pyrolysis of lignite in CO atmosphere%CO气氛下褐煤加压快速热解过程中CH4的逸出规律

    Institute of Scientific and Technical Information of China (English)

    高松平; 王建飞; 赵建涛; 王志青; 房倚天; 黄戒介

    2014-01-01

    在管式反应器上进行了霍林河褐煤加压快速热解实验,研究了CO气氛下CH4逸出规律。在加压快速热解条件下,由于CO解离态吸附的O( a)吸附在煤上,提供了活性中心,电负性强的O( a)诱发其周围其他原子的电子云向O( a)偏移,减弱了原来化学键的强度,导致芳香环的开裂,侧链、醚键和脂肪链的断裂提供更多的自由基,稳定煤热解生成的碎片,促进了CH4的生成和逸出。因此,CO气氛下CH4产率较N2气氛下的高,在900℃、1.0 MPa时,50%CO气氛下的CH4产率较N2气氛下的提高了12.5%,并且CH4产率随着温度升高、压力的增大而增大。%Fast pyrolysis of Huolinhe lignite was carried out under pressure in a tubular reactor, and the CH4 evolution at CO atmosphere was examined. CO dissociation state O( a) adsorbed on coal is an active center. The stronger electronegative O could induce the electron cloud of other atoms around O ( a ) atom to offset to it, which could weaken the strength of original chemical bonds and promote their breaking. These result in the cracks of the aromatic ring, side chain, ether linkages and aliphatic chain in the char, which could produce more free radicals. The free radicals could stabilize the fragments produced in the pyrolysis, and lead to more CH4 generated and involved. Therefore, the CH4 yield is higher under CO than it in N2 . The CH4 yield increases by 12. 5% under CO compared with N2 at 900℃ and 1. 0 MPa. The CH4 yield increases with raise of temperature and pressure.

  13. Interactive association between biopolymers and biofunctions in carinata seeds as energy feedstock and their coproducts (carinata meal) from biofuel and bio-oil processing before and after biodegradation: current advanced molecular spectroscopic investigations.

    Science.gov (United States)

    Yu, Peiqiang; Xin, Hangshu; Ban, Yajing; Zhang, Xuewei

    2014-05-07

    Recent advances in biofuel and bio-oil processing technology require huge supplies of energy feedstocks for processing. Very recently, new carinata seeds have been developed as energy feedstocks for biofuel and bio-oil production. The processing results in a large amount of coproducts, which are carinata meal. To date, there is no systematic study on interactive association between biopolymers and biofunctions in carinata seed as energy feedstocks for biofuel and bioethanol processing and their processing coproducts (carinata meal). Molecular spectroscopy with synchrotron and globar sources is a rapid and noninvasive analytical technique and is able to investigate molecular structure conformation in relation to biopolymer functions and bioavailability. However, to date, these techniques are seldom used in biofuel and bioethanol processing in other research laboratories. This paper aims to provide research progress and updates with molecular spectroscopy on the energy feedstock (carinata seed) and coproducts (carinata meal) from biofuel and bioethanol processing and show how to use these molecular techniques to study the interactive association between biopolymers and biofunctions in the energy feedstocks and their coproducts (carinata meal) from biofuel and bio-oil processing before and after biodegradation.

  14. High-quality bio-oil from one-pot catalytic hydrocracking of kraft lignin over supported noble metal catalysts in isopropanol system.

    Science.gov (United States)

    Yang, Jing; Zhao, Liang; Liu, Shaotong; Wang, Yuanyuan; Dai, Liyi

    2016-07-01

    Catalytic hydrocracking of kraft lignin was carried out in isopropanol system and an orthogonal array design (OAD) was employed to optimize the experimental conditions. GC-MS/FID, elemental analysis, GPC and (1)H-(13)C HSQC NMR were carried out for entire investigation of the liquid products. The results indicated that the hydrocracking process was thermally controlled and catalysts showed significant influences on the product distributions. Comparing with Pd/C, Pt/C and Ru/C, Rh/C inhibited the self-condensation of isopropanol and reduced the formation of oxygenic-chain compounds. The excellent catalytic activity for phenols conversion was obtained over Rh/C. The routes of oxygenic-chain compounds formation and phenol conversion were proposed in detail. The least oxygenic-chain compounds formation, the highest phenols conversion (93.4%), the lowest O/C ratio (0.094) and the highest HHV (37.969MJ/kg) provided the possibility of the high quality bio-oil obtained over Rh/C in isopropanol medium.

  15. Generation of basic centers in high-silica zeolites and their application in gas-phase upgrading of bio-oil.

    Science.gov (United States)

    Keller, Tobias C; Rodrigues, Elodie G; Pérez-Ramírez, Javier

    2014-06-01

    High-silica zeolites have been reported recently as efficient catalysts for liquid- and gas-phase condensation reactions because of the presence of a complementary source of basicity compared to Al-rich basic zeolites. Herein, we describe the controlled generation of these active sites on silica-rich FAU, BEA, and MFI zeolites. Through the application of a mild base treatment in aqueous Na2CO3, alkali-metal-coordinating defects are generated within the zeolite whereas the porous properties are fully preserved. The resulting catalysts were applied in the gas-phase condensation of propanal at 673 K as a model reaction for the catalytic upgrading of pyrolysis oil, for which an up to 20-fold increased activity compared to the unmodified zeolites was attained. The moderate basicity of these new sites leads to a coke resistance superior to traditional base catalysts such as CsX and MgO, and comparable activity and excellent selectivity is achieved for the condensation pathways. Through strategic acid and base treatments and the use of magic-angle spinning NMR spectroscopy, the nature of the active sites was investigated, which supports the theory of siloxy sites as basic centers. This contribution represents a key step in the understanding and design of high-silica base catalysts for the intermediate deoxygenation of crude bio-oil prior to the hydrotreating step for the production of second-generation biofuels.

  16. Hydrogen production by steam reforming of bio-oil aqueous fraction over Ni/CeO{sub 2}-ZrO{sub 2} catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Chang-Feng; Cheng, Fei-Fei; Hu, Rong-Rong [Chinese Academy of Sciences, Guangzhou (China). Guangzhou Inst. of Energy Conversion

    2010-07-01

    Two kinds of Ni/CeO{sub 2}-ZrO{sub 2} catalysts were prepared by impregnation method or by coprecipitation method. A laboratory scale fixed-bed reactor was employed to investigate the catalyst performance in hydrogen production by steam reforming bio-oil aqueous fraction. Effects of reaction temperature, and the different preparation methods of the catalyst on the hydrogen production performance of Ni/CeO{sub 2}-ZrO{sub 2} catalysts were examined. The obtained results were compared with commercial nickel-based catalysts (Z417). Ni/CeO{sub 2}-ZrO{sub 2} catalyst by co-precipitation method showed the best catalytic performances. At W/B=4.9, T=800 C, H{sub 2} yield reaches the highest of 72.9 % and H{sub 2} content of 70.0 % were obtained., these values were higher than Ni/CeO{sub 2}-ZrO{sub 2} catalysts were prepared by impregnation method and commercial nickel-based catalysts (Z417). (orig.)

  17. Use of iron and bio-oil wastes to produce highly dispersed Fe/C composites for the photo-Fenton reaction.

    Science.gov (United States)

    de Mendonça, Fernanda Gomes; Rosmaninho, Marcelo Gonçalves; da Fonseca, Philipe Xavier; Soares, Ricardo Reis; Ardisson, José Domingos; Tristão, Juliana Cristina; Lago, Rochel Montero

    2017-03-01

    This work describes the synthesis, characterization, and application of an active heterogeneous photo-Fenton system obtained from two different wastes, i.e., laterite (an iron mining waste) and the acid aqueous fraction (AAF) from bio-oil production. AAF with high acidity (ca. 3 molH+ L(-1)) and organic concentration (25 wt.%) obtained from biomass flash pyrolysis was used for the efficient extraction of Fe(3+) from laterite waste. After extraction, the mixture Fe(3+)/AAF was dried and treated at different temperatures, i.e., 500, 650, and 800 °C, to obtain Fe/C reactive composites. Mössbauer, XRD, TG, elemental analyses, and SEM/EDS showed the presence of highly disperse Fe oxide nanoparticles at 500 and 650 °C and Fe(0) particles in the material obtained at 800 °C with carbon contents varying from 74 to 80 %. The three composites were tested as heterogeneous catalysts in the photo-Fenton reaction for the oxidation of the model dye contaminant methylene blue, showing high activities at neutral pH.

  18. Metal leaching in mine tailings: short-term impact of biochar and wood ash amendments.

    Science.gov (United States)

    Beauchemin, Suzanne; Clemente, Joyce S; MacKinnon, Ted; Tisch, Bryan; Lastra, Rolando; Smith, Derek; Kwong, John

    2015-01-01

    Biochar is perceived as a promising amendment to reclaim degraded, metal-contaminated lands. The objective of this study was to compare the potential of biochar and wood ash amendments to reduce metal(loid) leaching in mine tailings. A 2-mo leaching experiment was conducted in duplicate on acidic and alkaline tailings, each mixed with 5 wt.% of one of the following amendments: three wood-derived, fast-pyrolysis biochars (OC > 57 wt.%) and two wood ash materials (organic carbon [OC] ≤ 16 wt.%); a control test with no carbon input was also added. The columns were leached with water after 1, 2, 4, 8, 16, 32, and 64 d, and the leachates were monitored for dissolved metals, OC, and pH. For the acidic and alkaline tailings, the most significant impact on metal mobility was observed with wood ash materials due to their greater neutralization potential (>15% CaCO eq.) compared with biochar (≤3.3% CaCO eq.). An increase of 1 pH unit in the wood ash-treated alkaline tailings led to an undesirable mobilization of As and Se. The addition of biochar did not significantly reduce the leaching of the main contaminants (Cu and Ni in the acidic tailings and As in the alkaline tailings) over 2 mo. The Se attenuation noted in some biochar-treated acid tailings may be mainly due to a slight alkaline effect rather than Se removal by biochar, given the low capacity for the fresh biochars to retain Se under acidic conditions (pH 4.5). The increased loss of dissolved OC in the biochar-amended systems was of short duration and was not associated with metal(loid) mobilization. Copyright © Her Majesty the Queen in Right of Canada, as represented by the Minister of Agriculture and Agri-Food Canada.

  19. Development of an efficient catalyst for the pyrolytic conversion of biomass into transport fuel

    NARCIS (Netherlands)

    Nguyen, T.S.

    2014-01-01

    Fast pyrolysis is a promising technique to convert biomass into a liquid fuel/fuel precursor, known as bio-oil. However, compared to conventional crude oil, bio-oil has much higher oxygen content which results in various detrimental properties and limits its application. Thus the first part of this

  20. 生物油中络合萃取乙酸的研究%Extracting Acetic Acid from Bio-Oil Using TOA

    Institute of Scientific and Technical Information of China (English)

    吕东灿; 刘运权; 王夺

    2013-01-01

    Complexation extraction with trioctylamine (TOA) as solvent for the recovery of acetic acid from bio-oil was studied.The effects of TOA concentration,iso-octyl alcohol concentration,volume ratio of extractant/distillate and temperature on extraction efficiency were examined.Experimental results indicated that the extraction efficiency was the highest with 40% TOA + 40% iso-octyl alcohol + 20% kerosene and 3∶1 volume ratio of extractant/distillate at the temperature of 0 ℃.And an extraction efficiency of 74.6% for acetic acid was achieved in a single-equilibrium-stage extraction under this optimal condition.%采用三正辛胺(TOA)作为络合剂,异辛醇和煤油分别作为助溶剂和稀释剂,对生物油中的乙酸进行了络合萃取研究.考察了TOA体积分数、异辛醇浓度、萃取剂与生物油轻馏分体积比以及温度对乙酸萃取率的影响,结果表明:温度为0℃,萃取体系为40% TOA+ 40%异辛醇+20%煤油(各组分浓度均为体积分数,下同),萃取剂与生物油轻馏分体积比为3∶1时,乙酸的一次萃取率较高,可达74.6%.