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. Copyright © 2016. Published by Elsevier B.V.

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

Science.gov (United States)

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

2012-03-01

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

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.

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. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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

2017-10-01

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

The potential of activated carbon derived from bio-char waste of bio-oil pyrolysis as adsorbent

Directory of Open Access Journals (Sweden)

Zulkania Ariany

2018-01-01

Full Text Available Activated carbon from bio-char waste of bio oil pyrolysis of mixed sugarcane bagasse and Rambutan twigs was investigated. Bio-char as by-product of bio-oil pyrolysis has potential to be good adsorbed by activating process. Bio-chars waste was activated in fixed bed reactor inside furnace without presenting oxygen. Gas N2 and CO2 were employed to drive out oxygen from the reactor and as activator, respectively. One of the best activation treatments is achieved by performing activation in different temperature and time to produce standard activated carbon. The experiment was performed at different temperatures and activation time, i.e. 800, 850, and 900° C and 80 and 120 minutes, respectively, to determine the optimal operating condition. Activated carbon was characterized by analysis of moisture content, ash content pH, and methylene blue test. The results showed that optimum activation was at 850°C and 80 minute, where activated carbon produced indicated the best adsorption capacity. The ash content and pH had significant role in resulting good activated carbon.

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.

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.

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

International Nuclear Information System (INIS)

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

2014-01-01

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

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

Science.gov (United States)

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

2012-07-17

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

Effect of fast pyrolysis bio-oil from palm oil empty fruit bunch on bitumen properties

Science.gov (United States)

Poh, Chia Chin; Hassan, Norhidayah Abdul; Raman, Noor Azah Abdul; Shukry, Nurul Athma Mohd; Warid, Muhammad Naqiuddin Mohd; Satar, Mohd Khairul Idham Mohd; Ros Ismail, Che; Asmah Hassan, Sitti; Mashros, Nordiana

2018-04-01

Bitumen shortage has triggered the exploration of another alternative waste material that can be blended with conventional bitumen. This study presents the performance of pyrolysis bio-oil from palm oil empty fruit bunch (EFB) as an alternative binder in modified bitumen mixtures. The palm oil EFB was first pyrolyzed using auger pyrolyzer to extract the bio-oil. Conventional bitumen 80/100 penetration grade was used as a control sample and compared with samples that were modified with different percentages, i.e., 5% and 10%, of pyrolysis EFB bio-oil. The physical and rheological properties of the control and modified bitumen samples were investigated using penetration, softening point, viscosity and dynamic shear rheometer (DSR) tests. Results showed that the addition of EFB bio-oil softened the bitumen with high penetration and a reduction in softening point, penetration index, and viscosity. However, the DSR results showed a comparable rutting resistance between the bitumen samples containing EFB bio-oil and virgin bitumen with a failure temperature achieved greater than 64°C.

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.

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

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. Copyright © 2016 Elsevier Inc. All rights reserved.

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

Science.gov (United States)

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

2012-10-01

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

Production of bio-oil with low contents of copper and chlorine by fast pyrolysis of alkaline copper quaternary-treated wood in a fluidized bed reactor

International Nuclear Information System (INIS)

Koo, Won-Mo; Jung, Su-Hwa; Kim, Joo-Sik

2014-01-01

Fast pyrolysis of ACQ (alkaline copper quaternary)-treated wood was carried out in a bench-scale pyrolysis plant equipped with a fluidized bed reactor and char separation system. This study focused on the production of a bio-oil with low copper and chlorine contents, especially by adopting the fractional condensation of bio-oil using water condensers, an impact separator and an electrostatic precipitator. In addition, various analytical tools were applied to investigate the physicochemical properties of the pyrolysis products and the behavior of the preservative during pyrolysis. The bio-oil yield was maximized at 63.7 wt% at a pyrolysis temperature of 411 °C. Highly water-soluble holocellulose-derived components such as acetic acid and hydroxyacetone were mainly collected by the condensers, while lignin-derived components and levoglucosan were mainly observed in the oils collected by the impact separator and electrostatic precipitator. All the bio-oils produced in the experiments were almost free of copper and chlorine. Most copper in ACQ was transferred into the char. - Highlights: • ACQ(alkaline copper quaternary)-treated wood was successfully pyrolyzed in a bench-scale fluidized bed. • Bio-oils separately collected were different in their characteristics. • Bio-oils were free of didecyldimethylammonium chloride. • Bio oils were almost free of copper and chlorine. • The concentration of levoglucosan in a bio-oil was 24–31 wt%

Bio-oil production through pyrolysis of blue-green algae blooms (BGAB): Product distribution and bio-oil characterization

International Nuclear Information System (INIS)

Hu, Zhiquan; Zheng, Yang; Yan, Feng; Xiao, Bo; Liu, Shiming

2013-01-01

Pyrolysis experiments of blue-green algae blooms (BGAB) were carried out in a fixed-bed reactor to determine the effects of pyrolysis temperature, particle size and sweep gas flow rate on pyrolysis product yields and bio-oil properties. The pyrolysis temperature, particle size and sweep gas flow rate were varied in the ranges of 300–700 °C, below 0.25–2.5 mm and 50–400 mL min −1 , respectively. The maximum oil yield of 54.97% was obtained at a pyrolysis temperature of 500 °C, particle size below 0.25 mm and sweep gas flow rate of 100 mL min −1 . The elemental analysis and calorific value of the oil were determined, and the chemical composition of the oil was investigated using gas chromatography–mass spectroscopy (GC–MS) technique. The analysis of bio-oil composition showed that bio-oil from BGAB could be a potential source of renewable fuel with a heating value of 31.9 MJ kg −1 . - Highlights: ► Bio-oil production from pyrolysis of blue-green algae blooms in fixed bed reactor. ► Effects of pyrolysis conditions on product distribution were investigated. ► The maximum bio-oil yield reached 54.97 wt %. ► The bio-oil has high heating value and may be suitable as renewable fuel. ► Pyrolysis of algal biomass beneficial for energy recovery, eutrophication control

TECHNO-ECONOMIC ANALYSIS: PRELIMINARY ASSESSMENT OF PYROLYSIS OIL PRODUCTION COSTS AND MATERIAL ENERGY BALANCE ASSOCIATED WITH A TRANSPORTABLE FAST PYROLYSIS SYSTEM

Directory of Open Access Journals (Sweden)

Phil Badger

2011-02-01

Full Text Available A techno-economic analysis was performed for a 100 dry-ton/day (90,719 kg/day fast pyrolysis transportable plant. Renewable Oil International® LLC provided the life cycle cost of operating a 100 dry-ton/day fast pyrolysis system using southern pine wood chips as feedstock. Since data was not available from an actual large-scale plant, the study examined data obtained from an actual 15 dry-ton/day pilot plant and from several smaller plants. These data were used to obtain base figures to aid in the development of models to generate scaled-up costs for a larger 100 dry-ton/day facility. Bio-oil represented 60% of mass of product yield. The cost for the bio-oil from fast pyrolysis was valued at $0.94/gal. Energy cost bio-oil and char was valued at $6.35/MMBTU. Costs associated with purchasing feedstocks can drastically influence the final cost of the bio-oil. The assumed cost of feedstocks was $25/wet ton or $50/dry ton. This paper is part of a larger study investigating the economic and environmental impacts for producing bio-oil / biocide wood preservatives.

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.

Utilization of oil palm tree residues to produce bio-oil and bio-char via pyrolysis

International Nuclear Information System (INIS)

Abnisa, Faisal; Arami-Niya, Arash; Wan Daud, W.M.A.; Sahu, J.N.; Noor, I.M.

2013-01-01

Highlights: • About 14.72% of the total landmass in Malaysia was used for oil palm plantations. • Oil palm tree residues were pyrolyzed to produce bio-oil and bio-char. • The process was performed at a temperature of 500 °C and reaction time of 60 min. • Characterization of the products was performed. - Abstract: Oil palm tree residues are a rich biomass resource in Malaysia, and it is therefore very important that they be utilized for more beneficial purposes, particularly in the context of the development of biofuels. This paper described the possibility of utilizing oil palm tree residues as biofuels by producing bio-oil and bio-char via pyrolysis. The process was performed in a fixed-bed reactor at a temperature of 500 °C, a nitrogen flow rate of 2 L/min and a reaction time of 60 min. The physical and chemical properties of the products, which are important for biofuel testing, were then characterized. The results showed that the yields of the bio-oil and bio-char obtained from different residues varied within the ranges of 16.58–43.50 wt% and 28.63–36.75 wt%, respectively. The variations in the yields resulted from differences in the relative amounts of cellulose, hemicellulose, lignin, volatiles, fixed carbon, and ash in the samples. The energy density of the bio-char was found to be higher than that of the bio-oil. The highest energy density of the bio-char was obtained from a palm leaf sample (23.32 MJ/kg), while that of the bio-oil was obtained from a frond sample (15.41 MJ/kg)

Bio-methane via fast pyrolysis of biomass

International Nuclear Information System (INIS)

Görling, Martin; Larsson, Mårten; Alvfors, Per

2013-01-01

Highlights: ► Pyrolysis gases can efficiently be upgraded to bio-methane. ► The integration can increase energy efficiency and provide a renewable vehicle fuel. ► The biomass to bio-methane conversion efficiency is 83% (HHV). ► The efficiency is higher compared to bio-methane produced via gasification. ► Competitive alternative to other alternatives of bio-oil upgrading. - Abstract: Bio-methane, a renewable vehicle fuel, is today produced by anaerobic digestion and a 2nd generation production route via gasification is under development. This paper proposes a poly-generation plant that produces bio-methane, bio-char and heat via fast pyrolysis of biomass. The energy and material flows for the fuel synthesis are calculated by process simulation in Aspen Plus®. The production of bio-methane and bio-char amounts to 15.5 MW and 3.7 MW, when the total inputs are 23 MW raw biomass and 1.39 MW electricity respectively (HHV basis). The results indicate an overall efficiency of 84% including high-temperature heat and the biomass to bio-methane yield amounts to 83% after allocation of the biomass input to the final products (HHV basis). The overall energy efficiency is higher for the suggested plant than for the gasification production route and is therefore a competitive route for bio-methane production

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

NARCIS (Netherlands)

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.

2016-01-01

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

Production of phenolic-rich bio-oil from catalytic fast pyrolysis of biomass using magnetic solid base catalyst

International Nuclear Information System (INIS)

Zhang, Zhi-bo; Lu, Qiang; Ye, Xiao-ning; Li, Wen-tao; Hu, Bin; Dong, Chang-qing

2015-01-01

Highlights: • Phenolic-rich bio-oil was selectively produced from catalytic fast pyrolysis of biomass using magnetic solid base catalyst. • The actual yield of twelve major phenolic compounds reached 43.9 mg/g. • The peak area% of all phenolics reached 68.5% at the catalyst-to-biomass ratio of 7. • The potassium phosphate/ferroferric oxide catalyst possessed promising recycling properties. - Abstract: A magnetic solid base catalyst (potassium phosphate/ferroferric oxide) was prepared and used for catalytic fast pyrolysis of poplar wood to selectively produce phenolic-rich bio-oil. Pyrolysis–gas chromatography/mass spectrometry experiments were conducted to investigate the effects of pyrolysis temperature and catalyst-to-biomass ratio on the product distribution. The actual yields of important pyrolytic products were quantitatively determined by the external standard method. Moreover, recycling experiments were performed to determine the re-utilization abilities of the catalyst. The results showed that the catalyst exhibited promising activity to selectively produce phenolic-rich bio-oil, due to its capability of promoting the decomposition of lignin to generate phenolic compounds and meanwhile inhibiting the devolatilization of holocellulose. The maximal phenolic yield was obtained at the pyrolysis temperature of 400 °C and catalyst-to-biomass ratio of 2. The concentration of the phenolic compounds increased monotonically along with the increasing of the catalyst-to-biomass ratio, with the peak area% value increasing from 28.1% in the non-catalytic process to as high as 68.5% at the catalyst-to-biomass ratio of 7. The maximal total actual yield of twelve quantified major phenolic compounds was 43.9 mg/g, compared with the value of 29.0 mg/g in the non-catalytic process. In addition, the catalyst could be easily recovered and possessed promising recycling properties.

Temperature influence on the fast pyrolysis of manure samples: char, bio-oil and gases production

Science.gov (United States)

Fernandez-Lopez, Maria; Anastasakis, Kostas; De Jong, Wiebren; Valverde, Jose Luis; Sanchez-Silva, Luz

2017-11-01

Fast pyrolysis characterization of three dry manure samples was studied using a pyrolyzer. A heating rate of 600°C/s and a holding time of 10 s were selected to reproduce industrial conditions. The effect of the peak pyrolysis temperature (600, 800 and 1000°C) on the pyrolysis product yield and composition was evaluated. Char and bio-oil were gravimetrically quantified. Scanning electron microscopy (SEM) was used to analyse the char structure. H2, CH4, CO and CO2 were measured by means of gas chromatography (GC). A decrease in the char yield and an increase of the gas yield were observed when temperature increased. From 800°C on, it was observed that the char yield of samples Dig R and SW were constant, which indicated that the primary devolatilization reactions stopped. This fact was also corroborated by GC analysis. The bio-oil yield slightly increased with temperature, showing a maximum of 20.7 and 27.8 wt.% for samples Pre and SW, respectively, whereas sample Dig R showed a maximum yield of 16.5 wt.% at 800°C. CO2 and CO were the main released gases whereas H2 and CH4 production increased with temperature. Finally, an increase of char porosity was observed with temperature.

Temperature influence on the fast pyrolysis of manure samples: char, bio-oil and gases production

Directory of Open Access Journals (Sweden)

Fernandez-Lopez Maria

2017-01-01

Full Text Available Fast pyrolysis characterization of three dry manure samples was studied using a pyrolyzer. A heating rate of 600°C/s and a holding time of 10 s were selected to reproduce industrial conditions. The effect of the peak pyrolysis temperature (600, 800 and 1000°C on the pyrolysis product yield and composition was evaluated. Char and bio-oil were gravimetrically quantified. Scanning electron microscopy (SEM was used to analyse the char structure. H2, CH4, CO and CO2 were measured by means of gas chromatography (GC. A decrease in the char yield and an increase of the gas yield were observed when temperature increased. From 800°C on, it was observed that the char yield of samples Dig R and SW were constant, which indicated that the primary devolatilization reactions stopped. This fact was also corroborated by GC analysis. The bio-oil yield slightly increased with temperature, showing a maximum of 20.7 and 27.8 wt.% for samples Pre and SW, respectively, whereas sample Dig R showed a maximum yield of 16.5 wt.% at 800°C. CO2 and CO were the main released gases whereas H2 and CH4 production increased with temperature. Finally, an increase of char porosity was observed with temperature.

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

Science.gov (United States)

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

2017-08-11

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

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

Science.gov (United States)

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

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

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.

Study on the hydrodeoxygenative upgrading of crude bio-oil produced from woody biomass by fast pyrolysis

International Nuclear Information System (INIS)

Kim, Tae-Seung; Oh, Shinyoung; Kim, Jae-Young; Choi, In-Gyu; Choi, Joon Weon

2014-01-01

Crude bio-oil produced from fast pyrolysis of yellow poplar wood was subjected to HDO (hydrodeoxygenation) for the purpose of reducing water content as well as increasing heating value. HDO was performed in an autoclave reactor at three different reaction factors: temperature (250–370 °C), reaction time (40–120 min), and Pd/C catalyst loading (0–6 wt%) under hydrogen atmosphere. After completion of HDO, gas, char, and two immiscible liquid products (light oil and heavy oil) were obtained. Liquid products were less acidic and contained less water than crude bio-oil. Water content of heavy oil was ranged between 0.4 wt% and 1.9 wt%. Heating values of heavy oil were estimated between 28.7 and 37.4 MJ/kg, which was about twice higher than that of crude bio-oil. Elemental analysis revealed that heavy oil had a lower O/C ratio (0.17–0.36) than crude bio-oil (0.71). H/C ratio of heavy oil decreased from 1.50 to 1.32 with an increase of temperature from 250 °C to 350 °C, respectively. - Highlights: • Bio-oil was subjected to hydrodeoxygenation with Pd/C catalyst in supercritical ethanol. • Gas, char and two immiscible liquids (light/heavy oil) were obtained as final products. • Ethanol addition reduced the char formation during hydrodeoxygenation. • The heavy oil was characteristic to less acidic and less water content than bio-oil. • Higher heating value of the heavy oil was measured to 28.7–37.4 MJ/kg

Bio-oil from Flash Pyrolysis of Agricultural Residues

DEFF Research Database (Denmark)

Ibrahim, Norazana

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...

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.

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

Science.gov (United States)

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

2016-03-01

This study investigated fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst. Effects of reaction temperature, CaO/HZSM-5 ratio, and corn stover/scum ratio on co-pyrolysis product fractional yields and selectivity were investigated. Results showed that co-pyrolysis temperature was selected as 550°C, which provides the maximum bio-oil and aromatic yields. Mixed CaO and HZSM-5 catalyst with the weight ratio of 1:4 increased the aromatic yield to 35.77 wt.% of feedstock, which was 17% higher than that with HZSM-5 alone. Scum as the hydrogen donor, had a significant synergistic effect with corn stover to promote the production of bio-oil and aromatic hydrocarbons when the H/C(eff) value exceeded 1. The maximum yield of aromatic hydrocarbons (29.3 wt.%) were obtained when the optimal corn stover to scum ratio was 1:2. Copyright © 2016 Elsevier Ltd. All rights reserved.

Flash pyrolysis properties of algae and lignin residue

DEFF Research Database (Denmark)

Trinh, Ngoc Trung; Jensen, Peter Arendt; Sørensen, Hanne Risbjerg

of macroalgae showed a promising result with on yield of 54 wt% dry ash free basis (daf) and 78% energy recovery in the bio-oil. The physiochemical properties of the bio-oils were characterized with respect to higher heating value, molecular mass distribution, viscosity, pH, density and elemental compositions......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. The product distributions and energy recoveries were measured and compared among these biomasses. The fast pyrolysis...

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.

Study of bio-oil and bio-char production from algae by slow pyrolysis

International Nuclear Information System (INIS)

Chaiwong, K.; Kiatsiriroat, T.; Vorayos, N.; Thararax, C.

2013-01-01

This study examined bio-oil and bio-char fuel produced from Spirulina Sp. by slow pyrolysis. A thermogravimetric analyser (TGA) was used to investigate the pyrolytic characteristics and essential components of algae. It was found that the temperature for the maximum degradation, 322 °C, is lower than that of other biomass. With our fixed-bed reactor, 125 g of dried Spirulina Sp. algae was fed under a nitrogen atmosphere until the temperature reached a set temperature between 450 and 600 °C. It was found that the suitable temperature to obtain bio-char and bio-oil were at approximately 500 and 550 °C respectively. The bio-oil components were identified by a gas chromatography/mass spectrometry (GC–MS). The saturated functional carbon of the bio-oil was in a range of heavy naphtha, kerosene and diesel oil. The energy consumption ratio (ECR) of bio-oil and bio-char was calculated, and the net energy output was positive. The ECR had an average value of 0.49. -- Highlights: •Bio-oil and bio-char fuel produced from Spirulina Sp. by slow pyrolysis. •Suitable temperature to obtained bio-oil and bio-char were at about 550 and 500 °C. •Saturated functional carbon of bio-oil was heavy naphtha, kerosene, diesel oil. •ECR had an average value of 0.49

Biofuel Production from Jatropha Bio-Oil Derived Fast Pyrolysis: Effect and Mechanism of CoMoS Supported on Al2O3

Science.gov (United States)

Rodseanglung, T.; Ratana, T.; Phongaksorn, M.; Tungkamani, S.

2018-03-01

The aims of this research was to understand the CoMo/Al2O3 sulfide catalyst effect to remove oxygen-containing and nitrogen-containing molecules from Jatropha bio-oil derived fast pyrolysis converted to biofuels via hydrotreating process. The activity and selectivity of CoMo/γ-Al2O3 sulfided catalysts in hydrodeoxygenation (HDO) of Jatropha bio-oil derived fast pyrolysis was evaluated in a Parr batch reactor under 50 bar of H2 atmosphere for 2 h at 300 320 and 340 °C. It appeared that the CoMo/Al2O3 sulfide catalyst have high performance in activity for promoting the fatty acid, fatty ester, fatty amide and fatty nitrile compounds were converted to paraffin/olefin (Diesel range), this could be the CUS site on supported Al2O3 catalyst. The difference in selectivity products allowed us to propose a reaction scheme.

Selective pyrolysis of paper mill sludge by using pretreatment processes to enhance the quality of bio-oil and biochar products

International Nuclear Information System (INIS)

Reckamp, Joseph M.; Garrido, Rene A.; Satrio, Justinus A.

2014-01-01

Paper mill sludge (PMS) is a residual biomass that is generated at paper mills in large quantities. Currently, PMS is commonly disposed in landfills, which causes environmental issues through chemical leaching and greenhouse gas production. In this research, we are exploring the potential of fast pyrolysis process for converting PMS into useful bio-oil and biochar products. We demonstrate that by subjecting PMS to a combination of acid hydrolysis and torrefaction pre-treatment processes it is possible to alter the physicochemical properties and composition of the feedstock material. Fast pyrolysis of pretreated PMS produced bio-oil with significantly higher selectivity to levoglucosenone and significantly reduced the amount of ketone, aldehyde, and organic acid components. Pretreatment of PMS with combined 4% mass fraction phosphoric acid hydrolysis and 220 °C torrefaction processed prior to fast pyrolysis resulted in a 17 times increase of relative selectivity towards levoglucosenone in bio-oil product along with a reduction of acids, ketones, and aldehydes combined from 21 % to 11 %. Biochar, produced in higher yield, has characteristics that potentially make the solid byproduct ideal for soil amendment agent or sorbent material. This work reveals a promising process system to convert PMS waste into useful bio-based products. More in-depth research is required to gather more data information for assessing the economic and sustainability aspects of the process. - Highlights: • Acid hydrolysis and torrefaction reduce bio-oil yield, but improve quality. • Dilute acid conditions provide optimal treatment for bio-oil quality and yield. • Pyrolysis of treated PMS produces high selectivity to levoglucosenone formation. • Treated PMS produces bio-oil with reduced acid, ketone, and aldehyde content. • Pyrolysis of treated PMS produces biochar with low volatile matter in high yield

PYROLYSIS OF ISOCHRYSIS MICROALGAE WITH METAL OXIDE CATALYSTS FOR BIO-OIL PRODUCTION

Directory of Open Access Journals (Sweden)

TEVFİK AYSU

2016-12-01

Full Text Available Pyrolysis of Isochrysis microalgae was carried out in a fixed-bed reactor without and with metal oxide catalysts (CeO2, TiO2, Al2O3 at the temperatures of 450, 500 and 550 oC with a constant heating rate of 40 oC/min. The pyrolysis conditions including catalyst and temperature were studied in terms of their effects on the yields of pyrolysis products and quality. The amount of bio-char, bio-oil and gas products was calculated. The composition of the produced bio-oils was determined by Elemental analysis (EA, Fourier transform infrared spectroscopy (FT-IR, proton nuclear magnetic resonance (1H NMR and Gas chromatography/mass spectrometry (GC–MS techniques. As a result of the pyrolysis experiments, it is shown that there have been significant effects of both catalyst and temperature on the conversion of Isochrysis microalgae into solid, liquid (bio-oil and gas products. The highest bio-oil yield (24.30 % including aqueous phase was obtained in the presence of TiO2 (50% as catalyst at 500 °C. 98 different compounds were identified by GC-MS in bio-oils obtained at 500 oC. According to 1H NMR analysis, bio-oils contained ∼60-64 % aliphatic and ∼17-19 % aromatic structural units. EA showed that the bio-oils contained ∼66-69 % C and having 31-34 MJ/kg higher heating values.

Estimation and Comparison of Bio-Oil Components from Different Pyrolysis Conditions

Energy Technology Data Exchange (ETDEWEB)

Lyu, Gaojin [Key Lab of Pulp and Paper Science and Technology of Ministry of Education, Qilu University of Technology, Jinan (China); State Key Lab of Pulp and Paper Engineering, South China University of Technology, Guangzhou (China); Wu, Shubin, E-mail: shubinwu@scut.edu.cn; Zhang, Hongdan [State Key Lab of Pulp and Paper Engineering, South China University of Technology, Guangzhou (China)

2015-06-15

In the case of development and utilization of bio-oils, a quantitative chemical characterization is necessary to evaluate its actual desired characteristics for downstream production. This paper describes an analytical approach for the determination of families of lightweight chemicals from bio-oils by using GC-MS techniques. And on this basis, new explorations in the field of influence factors, such as feedstocks, pyrolysis temperatures, and low-temperature pretreatment, on the composition and products yields of bio-oil were further investigated. Up to 40% (wt.%) of the bio-oil is successfully quantified by the current method. Chemical functionalities in the bio-oil correlate strongly with the original feedstocks because of their different chemical compositions and structure. Pyrolysis temperature plays a vital role in the yields of value-added compounds, both overall and individually. Higher temperature favored the generation of small aldehydes and acids, accompanied by a reduction of phenols. The optimal temperatures for maximum furans and ketones yields were 520 and 550°C, respectively. The low-temperature pretreatment of biomass has a good enrichment for the lightweight components of the bio-oils. In this case, much higher amounts of compounds, such as furans, ketones, and phenols were produced. Such a determination would contribute greatly to a deeper understanding of the chemical efficiency of the pyrolysis reaction and how the bio-oils could be more properly utilized.

Estimation and Comparison of Bio-Oil Components from Different Pyrolysis Conditions

International Nuclear Information System (INIS)

Lyu, Gaojin; Wu, Shubin; Zhang, Hongdan

2015-01-01

In the case of development and utilization of bio-oils, a quantitative chemical characterization is necessary to evaluate its actual desired characteristics for downstream production. This paper describes an analytical approach for the determination of families of lightweight chemicals from bio-oils by using GC-MS techniques. And on this basis, new explorations in the field of influence factors, such as feedstocks, pyrolysis temperatures, and low-temperature pretreatment, on the composition and products yields of bio-oil were further investigated. Up to 40% (wt.%) of the bio-oil is successfully quantified by the current method. Chemical functionalities in the bio-oil correlate strongly with the original feedstocks because of their different chemical compositions and structure. Pyrolysis temperature plays a vital role in the yields of value-added compounds, both overall and individually. Higher temperature favored the generation of small aldehydes and acids, accompanied by a reduction of phenols. The optimal temperatures for maximum furans and ketones yields were 520 and 550°C, respectively. The low-temperature pretreatment of biomass has a good enrichment for the lightweight components of the bio-oils. In this case, much higher amounts of compounds, such as furans, ketones, and phenols were produced. Such a determination would contribute greatly to a deeper understanding of the chemical efficiency of the pyrolysis reaction and how the bio-oils could be more properly utilized.

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

Pyrolysis bio-oil upgrading to renewable fuels.

Science.gov (United States)

2014-01-01

This study aims to upgrade woody biomass pyrolysis bio-oil into transportation fuels by catalytic hydrodeoxygenation : (HDO) using nanospring (NS) supported catalyst via the following research objectives: (1) develop nanospring-based : catalysts (nan...

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.

Upgrading low-boiling-fraction fast pyrolysis bio-oil using supercritical alcohol: Understanding alcohol participation, chemical composition, and energy efficiency

International Nuclear Information System (INIS)

Jo, Heuntae; Prajitno, Hermawan; Zeb, Hassan; Kim, Jaehoon

2017-01-01

Highlights: • Non-catalytic and non-hydrogen based bio-oil upgrading was conducted using scMeOH. • 16–40 wt% alcohols were consumed during the upgrading. • High bio-oil yield of 78.4 wt% and low TAN of 4.0 mg KOH/g were achieved. • Effect of supercritical alcohols, reaction times, temperature and bio-oil concentration was conducted. • scMeOH upgrading has good energy recovery (ER) and energy efficiency (EE) compared with scEtOH and scIPA. - Abstract: Herein, a supercritical methanol (scMeOH) route for efficient upgrading of the low-boiling fraction of fast pyrolysis bio-oil containing a large amount of low-molecular-weight acids and water was investigated. The effects of various reaction parameters, including the temperature, concentration, and time, were explored. The yield of bio-oil and the energy efficiency of the scMeOH upgrading process were determined based on the amount of methanol that participated in the reaction during upgrading and fractionation of the upgraded heavy-fraction bio-oils (UHBOs) and upgraded light-fraction bio-oils (ULBOs). Upgrading at 400 °C with 9.1 wt% bio-oil for 30 min generated a high bio-oil yield of 78.4 wt% with a low total acid number (TAN) of 4.0 mg-KOH/g-oil and a higher heating value of 29.9 MJ kg −1 . The energy recovery (ER) was 94–131% and the energy efficiency (EE) was in the range of 79–109% depending on the calorific values of the ULBOs. Compared with upgrading in supercritical ethanol and supercritical isopropanol, less alcohol participation, a lower TAN, and higher ER and EE were achieved with scMeOH upgrading. Plausible pathways for bio-oil upgrading in supercritical alcohols based on detailed compositional analysis of the UHBO, ULBO, and gaseous products were discussed.

Use of palm oil decanter cake as a new substrate for the production of bio-oil by vacuum pyrolysis

International Nuclear Information System (INIS)

Dewayanto, Nugroho; Isha, Ruzinah; Nordin, Mohd Ridzuan

2014-01-01

Highlights: • Vacuum pyrolysis has been employed to produce bio-oil from palm oil waste. • Effect of the pyrolysis temperature was investigated in this study. • Bio-oil properties of cellulosic and oily based material were determined. • Bio-oil from decanter cake has potential to be used as fuel. - Abstract: The present study was carried out to investigate the potential of palm oil decanter cake (PDC) for bio-oil production at various temperatures by vacuum pyrolysis. PDC was first dried in oven at 105 °C for 24 h to remove moisture and ground to particle size of 0.85–2 mm. Pyrolysis experiments were carried out at 400, 450, 500, 550 and 600 °C, with heating rate of 15 °C/min. The highest yield of bio-oil (22.12 wt%) was obtained at pyrolysis temperature of 500 °C. The chemical characterization of bio-oil was studied using 1 H NMR, FTIR, CHNS analyzer and GC–MS. The other properties like pH, calorific value and thermal volatilization were also determined. The pH value recorded to be 6.38, which is found to be higher as compared to other bio-oils. The calorific value of PDC bio-oil found to be 36.79 MJ/kg, which is slightly lower than that of conventional liquid fuel such as gasoline and diesel fuel. However, the bio-oil obtained from PDC has better fuel characteristics than that of bio-oil derived from palm kernel shell (PKS)

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.

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.

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

Directory of Open Access Journals (Sweden)

Brandon Jeffrey

Full Text Available Fast pyrolysis has been identified as one of the biorenewable conversion platforms that could be a part of an alternative energy future, but it has not yet received the same attention as cellulosic ethanol in the analysis of genetic inheritance within potential feedstocks such as maize. Ten bio-oil compounds were measured via pyrolysis/gas chromatography-mass spectrometry (Py/GC-MS in maize cobs. 184 recombinant inbred lines (RILs of the intermated B73 x Mo17 (IBM Syn4 population were analyzed in two environments, using 1339 markers, for quantitative trait locus (QTL mapping. QTL mapping was performed using composite interval mapping with significance thresholds established by 1000 permutations at α = 0.05. 50 QTL were found in total across those ten traits with R2 values ranging from 1.7 to 5.8%, indicating a complex quantitative inheritance of these traits.

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...... components and molecular mass distribution of the lignin oils. The obtained lignin oil has a very different components composition when compared to a beech wood oil....

Phase separation of bio-oil produced by co-pyrolysis of corn cobs and polypropylene

Science.gov (United States)

Supramono, D.; Julianto; Haqqyana; Setiadi, H.; Nasikin, M.

2017-11-01

In co-pyrolysis of biomass-plastics, bio-oil produced contains both oxygenated and non-oxygenated compounds. High oxygen composition is responsible for instability and low heating value of bio-oil and high acid content for corrosiveness. Aims of the present work are to evaluate possibilities of achieving phase separation between oxygenated and non-oxygenated compounds in bio-oil using a proposed stirred tank reactor and to achieve synergistic effects on bio-oil yield and non-oxygenated compound layer yield. Separation of bio-oil into two layers, i.e. that containing oxygenated compounds (polar phase) and non-oxygenated compounds (non-polar phase) is important to obtain pure non-polar phase ready for the next processing of hydrogenation and used directly as bio-fuel. There has been no research work on co-pyrolysis of biomass-plastic considering possibility of phase separation of bio-oil. The present work is proposing a stirred tank reactor for co-pyrolysis with nitrogen injection, which is capable of tailoring co-pyrolysis conditions leading to low viscosity and viscosity asymmetry, which induce phase separation between polar phase and non-polar phase. The proposed reactor is capable of generating synergistic effect on bio-oil and non-polar yields as the composition of PP in feed is more than 25% weight in which non-polar layers contain only alkanes, alkenes, cycloalkanes and cycloalkenes.

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. .

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.

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

Science.gov (United States)

Aysu, Tevfik; Sanna, Aimaro

2015-10-01

Pyrolysis of Nannochloropsis was carried out in a fixed-bed reactor with newly prepared ceria based catalysts. The effects of pyrolysis parameters such as temperature and catalysts on product yields were investigated. The amount of bio-char, bio-oil and gas products, as well as the compositions of the resulting bio-oils was determined. The results showed that both temperature and catalyst had significant effects on conversion of Nannochloropsis into solid, liquid and gas products. The highest bio-oil yield (23.28 wt%) and deoxygenation effect was obtained in the presence of Ni-Ce/Al2O3 as catalyst at 500°C. Ni-Ce/Al2O3 was able to retain 59% of the alga starting energy in the bio-oil, compared to only 41% in absence of catalyst. Lower content of acids and oxygen in the bio-oil, higher aliphatics (62%), combined with HHV show promise for production of high-quality bio-oil from Nannochloropsis via Ni-Ce/Al2O3 catalytic pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

High selectivity and stability of Mg-doped Al-MCM-41 for in-situ catalytic upgrading fast pyrolysis bio-oil

International Nuclear Information System (INIS)

Karnjanakom, Surachai; Suriya-umporn, Thanyamai; Bayu, Asep; Kongparakul, Suwadee; Samart, Chanatip; Fushimi, Chihiro; Abudula, Abuliti; Guan, Guoqing

2017-01-01

Highlights: • Mg-doped Al-MCM-41 was developed for in-situ catalytic upgrading of bio-oils. • Mg/Al-MCM-41 exhibited high selectivity to aromatic hydrocarbons. • The ratio of produced hydrocarbon reached up to 80% in upgraded bio-oil. • 1 wt.% Mg/Al-MCM-41 showed the highest catalytic activity. • Mg/Al-MCM-41 had stable reusability due to its coking inhabitation ability. - Abstract: In-situ catalytic upgrading of bio-oils derived from the fast pyrolysis of cellulose, lignin or sunflower stalk over Mg-doped Al-MCM-41 was investigated in details. It is found that Mg species with doping amounts ranged between 0.25 and 10 wt.% was well dispersed on Al-MCM-41, and that doping Mg on Al-MCM-41 effectively adjusted the acidity and basicity of the catalysts, resulting in significant improvement of bio-oil quality. Mg/Al-MCM-41 exhibited high selective conversion of bio-oils derived from cellulose, lignin or sunflower stalk to high value-added aromatic hydrocarbons via catalytic cracking, deoxygenation and aromatization. In the upgraded bio-oil, the relative total hydrocarbon amount reached up to approximately ≥80%, which consisted of aromatic hydrocarbon approximately 76% and aliphatic hydrocarbon approximately 4% for all feedstocks. The selectivity to the monocyclic aromatic hydrocarbons (MAHs) such as benzene, toluene and xylenes (BTXs) increased while the coke formed on the catalyst decreased with the increase in Mg doping amount. 1 wt.% Mg/Al-MCM-41 resulted in the highest relative total hydrocarbon amount in the upgraded bio-oil at lower catalytic deoxygenation temperature, and showed stable reusability for at least 5 cycles. It is expected that Mg/Al-MCM-41 can be widely applied for bio-oil upgrading in a practical process.

Pyrolysis of Jatropha curcas pressed cake for bio-oil production in a fixed-bed system

International Nuclear Information System (INIS)

Jourabchi, Seyed Amirmostafa; Gan, Suyin; Ng, Hoon Kiat

2014-01-01

Highlights: • The pyrolysis of Jatropha curcas waste in a fixed-bed rig was studied. • Yield, calorific value, water content and acidity of bio-oil were compared. • Empirical correlations for bio-oil yield and specifications were developed. • Optimisation of bio-oil production based on combined specifications was achieved. - Abstract: This study investigated the effects of pyrolysis parameters on the yield and quality of bio-oil from Jatropha curcas pressed cake. This biomass was pyrolysed in a fixed-bed reactor over a temperature range of 573.15 K to 1073.15 K and a nitrogen linear speed range of 7.8 × 10 −5 m/s to 6.7 × 10 −2 m/s. The heating rate and biomass grain size were 50 K/min and <2 mm, respectively. The bio-oils were tested for the gross calorific value, water content and acidity. The pyrolysis process was simulated using Thermo-Gravimetric Analysis (TGA) and Differential Scanning Calorimeter (DSC) for mass and energy balances analyses. Empirical correlations between the bio-oil specifications and pyrolysis parameters were developed using linear and nonlinear multiple regression methods for process optimisation. At optimum pyrolysis conditions, above 50% of the waste is converted to bio-oil with less than 30% water content, a gross calorific value of 15.12 MJ/kg and a pH of 6.77

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

Science.gov (United States)

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

2013-04-21

Biomass fast pyrolysis is considered as a promising route to produce liquid for the transportation field from a renewable resource. However, the derived bio-oils are mainly oxygenated (45-50%w/w O on a wet basis) and contain almost no hydrocarbons. Therefore, upgrading is necessary to obtain a liquid with lower oxygen content and characterization of oxygenated compounds in these products is essential to assist conversion reactions. For this purpose, comprehensive two-dimensional gas chromatography (GC × GC) can be investigated. Oxygen speciation in such matrices is hampered by the large diversity of oxygenated families and the complexity of the hydrocarbon matrix. Moreover, response factors must be taken into account for oxygenate quantification as the Flame Ionisation Detector (FID) response varies when a molecule contains heteroatoms. To conclude, no distillation cuts were accessible and the analysis had to cover a large range of boiling points (30-630 °C). To take up this analytical challenge, a thorough optimization approach was developed. In fact, four GC × GC column sets were investigated to separate oxygenated compounds from the hydrocarbon matrix. Both model mixtures and the upgraded biomass flash pyrolysis oil were injected using GC × GC-FID to reach a suitable chromatographic separation. The advantages and drawbacks of each column combination for oxygen speciation in upgraded bio-oils are highlighted in this study. Among the four sets, an original polar × semi-polar column combination was selected and enabled the identification by GC × GC-ToF/MS of more than 40 compounds belonging to eight chemical families: ketones, furans, alcohols, phenols, carboxylic acids, guaiacols, anisols, and esters. For quantification purpose, the GC × GC-FID chromatogram was divided into more than 60 blobs corresponding to the previously identified analyte and hydrocarbon zones. A database associating each blob to a molecule and its specific response factor (determined

Ultra-high performance supercritical fluid chromatography hyphenated to atmospheric pressure chemical ionization high resolution mass spectrometry for the characterization of fast pyrolysis bio-oils.

Science.gov (United States)

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

2018-06-01

Extensive characterization of complex mixtures requires the combination of powerful analytical techniques. A Supercritical Fluid Chromatography (SFC) method was previously developed, for the specific case of fast pyrolysis bio oils, as an alternative to gas chromatography (GC and GC × GC) or liquid chromatography (LC and LC × LC), both separation methods being generally used prior to mass spectrometry (MS) for the characterization of such complex matrices. In this study we investigated the potential of SFC hyphenated to high resolution mass spectrometry (SFC-HRMS) for this characterization using Negative ion Atmospheric Pressure Chemical ionization ((-)APCI) for the ionization source. The interface between SFC and (-)APCI/HRMS was optimized from a mix of model compounds with the objective of maximizing the signal to noise ratio. The main studied parameters included both make-up flow-rate and make-up composition. A methodology for the treatment of APCI/HRMS data is proposed. This latter allowed for the identification of molecular formulae. Both SFC-APCI/HRMS method and data processing method were applied to a mixture of 36 model compounds, first analyzed alone and then spiked in a bio-oil. In both cases, 19 compounds could be detected. Among them 9 could be detected in a fast pyrolysis bio-oil by targeted analysis. The whole procedure was applied to the characterization of a bio-oil using helpful representations such as mass-plots, van Krevelen diagrams and heteroatom class distributions. Finally the results were compared with those obtained with a Fourier Transform ion-cyclotron resonance mass spectrometer (FT-ICR/MS). Copyright © 2018 Elsevier B.V. All rights reserved.

Bio-oil production from cotton stalk

International Nuclear Information System (INIS)

Zheng Jilu; Yi Weiming; Wang Nana

2008-01-01

Cotton stalk was fast pyrolyzed at temperatures between 480 deg. C and 530 deg. C in a fluidized bed, and the main product of bio-oil is obtained. The experimental result shows that the highest bio-oil yield of 55 wt% was obtained at 510 deg. C for cotton stalk. The chemical composition of the bio-oil acquired was analyzed by GC-MS, and its heat value, stability, miscibility and corrosion characteristics were determined. These results showed that the bio-oil obtained can be directly used as a fuel oil for combustion in a boiler or a furnace without any upgrading. Alternatively, the fuel can be refined to be used by vehicles. Furthermore, the energy performance of the pyrolysis process was analyzed. In the pyrolysis system used in our experiment, some improvements to former pyrolysis systems are done. Two screw feeders were used to prevent jamming the feeding system, and the condenser is equipped with some nozzles and a heat exchanger to cool quickly the cleaned hot gas into bio-oil

Fast pyrolysis of lignin, macroalgae and sewage sludge

Energy Technology Data Exchange (ETDEWEB)

Trinh, N.T.

2013-04-15

Non-conventional biomass feedstock may also be applicable for fast pyrolysis processes. Among the forms of non-conventional biomasses, macroalgae, lignin (industrial residue) and sewage sludge may be attractive materials due to their low price, non-competitiveness with food crops and the possible utilization of solid wastes. Besides, a fast pyrolysis process can be used as a process to densify the biomass and produce bioslurry, a mixture of bio-oil and pyrolytic char. The bioslurry is found to be a possible feedstock for pressurized gasification plants. Thus, the aims of this project are to investigate fast pyrolysis properties of lignin, sewage sludge and macroalgae on a lab scale PCR and characterize their bio-oil properties. Bioslurry properties with respect to use as a feedstock for pressurized gasification is also investigated. Lignin and sewage sludge PCR pyrolysis provided bio-oil yields of 47 and 54 wt% daf, and oil energy recovery of 45 and 50 %, respectively. While the macroalgae PCR pyrolysis showed promising results with an organic oil yield of 65 wt% daf and an oil energy recovery of 76 %. The HHV of the lignin, sewage sludge and macroalgae oils were 29.7, 25.7 and 25.5 MJ/kg db respectively, and that are higher than that of typical bioiv oil from conventional biomasses (23-24 MJ/kg db). Almost all metals feedstock contents were contained in the chars at temperatures of 550 - 575 deg. C for lignin, sewage sludge and macroalgae PCR pyrolysis. Due to high feedstock nitrogen and sulfur contents, also a high level of nitrogen and sulfur of macroalgae and sewage sludge oils were observed compared to conventional bio-oil and this may limit their further industrial applications. The lignin char had a high proportion of small size particles, a HHV of 21 MJ/kg db and were almost free of chloride and sulfur, thus it is considered as a promising fuel for gasification or combustion; whereas macroalgae and sewage sludge chars containing high amounts of

Hydrodeoxygenation of Pyrolysis Bio-Oil Over Ni Impregnated Mesoporous Materials.

Science.gov (United States)

Lee, In-Gu; Lee, Heejin; Kang, Bo Sung; Kim, Young-Min; Kim, Sang Chai; Jung, Sang-Chul; Ko, Chang Hyun; Park, Young-Kwon

2018-02-01

The catalytic hydrodeoxygenation (HDO) of bio-oil over Ni-supported mesoporous materials was performed using a high pressure autoclave reactor. The actual pyrolysis oil of cork oak wood was used as a sample, and Ni/Al-SBA-15 and Ni/Al-MSU-F were used as catalysts. In addition, supercritical ethanol was added as solvent. Both Ni-supported mesoporous catalysts showed efficient HDO reaction ability. A higher heating value and pH of bio-oil were achieved by the HDO reaction over both catalysts and upgraded bio-oil had a lower viscosity. Compared to Ni/Al-MSU-F, Ni/Al- SBA-15 produced more upgraded bio-oil with a lower oxygen content and higher heating value via a catalytic HDO process.

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.

Torrefied biomass as feed for fast pyrolysis : An experimental study and chain analysis

NARCIS (Netherlands)

Louwes, Alexander Charnchai; Basile, Lucia; Yukananto, Riza; Bhagwandas, Jina; Bramer, Eduard A.; Brem, Gerrit

2017-01-01

A torrefaction pre-treatment could enhance the fast pyrolysis process to produce bio-oil by decreasing the required energy for grinding biomass particles and by improving bio-oil characteristics so they resemble more those of fossil fuels. To evaluate this hypothesis, this work compares fast

THE HISTORY OF RESEARCH AND DEVELOPMENT OF FAST PYROLYSIS PLANT FOR BIO-OIL PRODUCTION AT THE FACULTY OF AGRICULTURAL ENGINEERING OF UNICAMP / HISTÓRICO DA PESQUISA E DESENVOLVIMENTO DA PLANTA DE PIRÓLISE RÁPIDA PARA PRODUÇAO DE BIO-ÓLEO DA FACULDADE DE E

Directory of Open Access Journals (Sweden)

LUIS A. B. CORTEZ

2009-11-01

Full Text Available This article is dedicated to describe the fast pyrolysis plant of biomass PPR-200 settled at UNICAMP School of Agricultural Engineering (FEAGRI. This fast pyrolysis plant, the first in Brazil to produce oil with fluidized bed reactor , began operating in 1998 with studies in a reactor for gasification, adapted to obtain bio-oil. Currently, PPR-200 operates with a 200 kg h-1 biomass capacity, and is used to conduct exploratory testing with various vegetable raw materials, such as sugar cane trash and bagasse, elephant grass, sawdust from wood, rice straw, coffee straw, orange bagasse, etc.. Around 15% of biomass is burnt to provide heat to the process. The remainder turns into the following products: bio-oil (20-40%, fine charcoal (20-30%, extract acid (10-15% and pyrolysis gas (15-35%. The pyrolysis gas is composed mainly by CH4, the H2, CO and CO2.Keywords: Biomass, bioenergy, reactor, fluidized bed.

Hydrogen production via catalytic steam reforming of fast pyrolysis oil fractions

International Nuclear Information System (INIS)

Wang, D.; Czernik, S.; Montane, D.; Mann, M.; Chornet, E.

1997-01-01

Hydrogen is the prototype of the environmentally cleanest fuel of interest for power generation using fuel cells, and as a co-adjuvant or autonomous transportation fuel in internal combustion engines. The conversion of biomass to hydrogen can be carried out through two distinct thermochemical strategies: (a) gasification followed by shift conversion; (b) catalytic steam reforming and shift conversion of specific fractions derived from fast pyrolysis and aqueous/steam processes of biomass. This paper shows that fast pyrolysis of biomass results in a bio-oil that can be adequately fractionated into valuable co-products leaving as by-product an aqueous fraction containing soluble organics (a mixture of alcohols, aldehydes and acids). This fraction can be converted to hydrogen by catalytic steam reforming followed by a shift conversion step. The methods used, the yields obtained and their economic significance will be discussed. (author)

Bio-flex obtained from pyrolysis of biomass as fuel; Bio-flex obtido da pirolise de biomassa como combustivel

Energy Technology Data Exchange (ETDEWEB)

Mesa Perez, Juan Miguel; Viltre Rodriguez, Roberto Alfonso; Marin Mesa, Henry Ramon [Bioware Tecnologia, Campinas, SP (Brazil); Rocha, Jose Dilcio [Universidade Estadual de Campinas (NIPE/UNICAMP), SP (Brazil). Nucleo Interdisciplinar de Planejamento Energetico; Samaniego, Manuel Raul Pelaez [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Planejamento de Sistemas Energeticos; Cortez, Luis Augusto Barbosa [Universidade Estadual de Campinas (FEAGRI/UNICAMP), SP (Brazil). Fac. de Engenharia Agricola

2006-07-01

This paper describes the BIOWARE experience in the bio fuel production from biomass residues. Fast pyrolysis of a mixture of sugar cane trash and elephant grass carried out in a fluidized bed reactor with capacity of 200 kg/h dry feed (12% w/w). The co-products particulate charcoal, acid extract, and bio-oil were obtained. The fast pyrolysis pilot plant PPR-200 belonged to UNICAMP and is operated by BIOWARE personnel. This paper presents the chemical rote to bio-flex production (a kind of bio diesel from acid esterification) from pyrolytic carboxylic acids. Both ethanol and methanol were used as reactant but higher yields were found with methanol. (author)

Hydrotreatment of bio-oil distillates produced from pyrolysis and hydrothermal liquefaction of duckweed: A comparison study.

Science.gov (United States)

Wang, Feng; Tian, Ye; Zhang, Cai-Cai; Xu, Yu-Ping; Duan, Pei-Gao

2018-09-15

A comprehensive comparison of hydrothermal liquefaction (HTL) to the pyrolysis of duckweed was conducted to determine the yields and components of the crude bio-oils and their distillates. The upgrading behaviors of the distillates were thoroughly investigated with the use of used engine oil as a solvent. With all other variables fixed, HTL produced crude bio-oil with a lower H/C ratio (1.28 ± 0.03) than pyrolysis did (1.45 ± 0.04). However, its distillates had a higher H/C ratio (1.60 ± 0.05) and total yield (66.1 ± 2.0 wt%) than pyrolysis (1.46 ± 0.04 and 47.2 ± 1.4 wt%, respectively). Phenolics and nitrogenous heterocycles constituted relatively major proportions of the two crude bio-oils and most of their distillates. Obvious differences in molecular composition between the two crude bio-oils and their distillates were ascribed to the distinct impacts of HTL and pyrolysis and were affected by the distillate temperature. Co-hydrotreating with used engine oil (UEO) provided the upgraded bio-oils much higher H/C ratios (~1.78 ± 0.05) and higher heating values (~45.5 ± 1.4 MJ·kg -1 ), as well as much lower contents of N, O and S compared to their initial distillates. Aromatics and alkanes constituted a large proportion in most of upgraded bio-oils. N removal from the pyrolysis distillates was easier than from the HTL distillates. Distinct differences in yields and molecular compositions for the upgraded bio-oils were also attributed to the different influences associated with the two conversion routes. Copyright © 2018 Elsevier B.V. All rights reserved.

Influence of reaction conditions on fast pyrolysis of macroalge

International Nuclear Information System (INIS)

Bae, Yoon Ju; Kim, Jung Hwan; Cho, Hye Jung; Ko, Jeong Huy; Heo, Hyeon Su; Park, Hye Jin; Park, Young Kwon

2010-01-01

Full text: The importance of renewable energy sources has increased rapidly due to the high international crude oil prices and environmental concerns over fossil fuel use. Recently, there has been a growing interest in aquatic biomass, especially marine macro algae, and a number of studies have been initiated to evaluate its potential for bio-energy. This paper reports a fast pyrolysis of macro algae under different reaction conditions such as pyrolysis temperature, particle size and sample quantity. Various macro algae such as Undaria pinnatifida, Laminaria japonica and Porphyra tenera were fast pyro lysed at temperatures between 300-600 degree Celsius in a batch reactor and the main product of bio-oil was obtained. The optimal reaction temperature for the production of bio-oil was 500 degree Celsius. At this temperature, the maximum bio-oil yields were 40.4 wt % ( by Undaria pinnatifida), 37.6 wt % (by Laminaria japonica) and 47.4 wt % (by Porphyra tenera), respectively. In particular, after pre-treatment with 2.0M HCl solution, the product yield of bio-oil was increased in macro algae, Undaria pinnatifida. The pyroylsis gases were analyzed by using GC-TCD and GC-FID and qualitative analyses of bio-oil were performed using GC-MS. The maximum yield of bio-oil, Undaria pinnatifida, Laminaria japonica and Porphyra tenera, was obtained at 500 degree Celsius (40.4 wt %, 37.6 wt % and 47.4 wt %, respectively). (author)

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

Science.gov (United States)

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

2018-05-18

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

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

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. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

Sensöz, Sevgi; Angin, Dilek

2008-09-01

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

Bio-oils from biomass slow pyrolysis: a chemical and toxicological screening.

Science.gov (United States)

Cordella, Mauro; Torri, Cristian; Adamiano, Alessio; Fabbri, Daniele; Barontini, Federica; Cozzani, Valerio

2012-09-15

Bio-oils were produced from bench-scale slow-pyrolysis of three different biomass samples (corn stalks, poplar and switchgrass). Experimental protocols were developed and applied in order to screen their chemical composition. Several hazardous compounds were detected in the bio-oil samples analysed, including phenols, furans and polycyclic aromatic hydrocarbons. A procedure was outlined and applied to the assessment of toxicological and carcinogenic hazards of the bio-oils. The following hazardous properties were considered: acute toxicity; ecotoxicity; chronic toxicity; carcinogenicity. Parameters related to these properties were quantified for each component identified in the bio-oils and overall values were estimated for the bio-oils. The hazard screening carried out for the three bio-oils considered suggested that: (i) hazards to human health could be associated with chronic exposures to the bio-oils; (ii) acute toxic effects on humans and eco-toxic effects on aquatic ecosystems could also be possible in the case of loss of containment; and (iii) bio-oils may present a marginal potential carcinogenicity. The approach outlined allows the collection of screening information on the potential hazards posed by the bio-oils. This can be particularly useful when limited time and analytical resources reduce the possibility to obtain detailed specific experimental data. Copyright © 2012 Elsevier B.V. All rights reserved.

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

2017-11-01

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.

Fast pyrolysis of sugarcane and cassava residues in a free-fall reactor

International Nuclear Information System (INIS)

Pattiya, Adisak; Sukkasi, Sittha; Goodwin, Vituruch

2012-01-01

Fast pyrolysis of agricultural residues from sugarcane and cassava plantations was carried out in a laboratory-scale free-fall reactor unit. The objectives of this work were to investigate the effects of biomass types and pyroysis conditions, such as reactor temperature, condensation temperature, nitrogen flow rate and run duration, on pyrolysis product distribution, as well as to study the basic properties of the products. The results showed that all of the parameters affected the product distribution. The optimum reactor temperatures for maximising bio-oil yield were in the range of 350–450 °C. About 70 wt% of bio-oil yield could be obtained by pyrolysis of cassava stalk at a reactor temperature of 450 °C and a primary condensation temperature of 10 °C. It was also found that the minimum flow rate of nitrogen for obtaining high bio-oil yield was 1.5 l/min. The product characterisation showed that the bio-oil and char produced from the agricultural residues with the free-fall reactor unit were to a certain extent similar to those produced from different types of biomass with different types of pyrolysis reactor configurations. -- Highlights: ► Fast pyrolysis of sugarcane and cassava agricultural residues was carried out in a laboratory-scale free-fall reactor unit. ► The effects of process parameters on product yields were investigated. ► The process parameters included reactor temperature, condensation temperature, nitrogen flow rate and run duration. ► Basic properties of pyrolysis products were examined.

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

Science.gov (United States)

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

2014-11-01

The influence of KOH addition and air pretreatment on co-pyrolysis (600 °C) of a mixture of bio-oil and biomass (aspen wood) was investigated with the goal of increasing biochar yield. The bio-oil was produced as a byproduct of the pyrolysis of biomass and recycled in subsequent runs. Co-pyrolysis of the biomass with the recycled bio-oil resulted in a 16% mass increase in produced biochar. The yields were further increased by either air pretreatment or KOH addition prior to co-pyrolysis. Air pretreatment at 220 °C for 3 h resulted in the highest mass increase (32%) compared to the base case of pyrolysis of biomass only. No synergistic benefit was observed by combining KOH addition with air pretreatment. In fact, KOH catalyzed reactions that increased the bed temperature resulting in carbon loss via formation of CO and CO2. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

Fast oxidative pyrolysis of sugar cane straw in a fluidized bed reactor

International Nuclear Information System (INIS)

Mesa-Pérez, Juan Miguel; Rocha, José Dilcio; Barbosa-Cortez, Luis Augusto; Penedo-Medina, Margarita; Luengo, Carlos Alberto; Cascarosa, Esther

2013-01-01

This study focuses on the technical viability evaluation of the fast pyrolysis of sugar cane straw for its energy use. By means of this thermochemical process, the sugar cane straw is converted into bio-fuels (biochar, bio-oil) and non-condensable gases. The bio-fuels obtained could be used as fuel or as raw material in the chemical industry. The fast pyrolysis of sugar cane straw has been developed in a fluidized bed reactor. In order to improve this process to obtain high bio-oil yield, the influence of the operational conditions (equivalence ratio and temperature) on the product yields and on their characteristics was evaluated. The product yields of bio-oil and char were up to 35.5 wt.% and 48.2 wt.% respectively. The maximum bio-oil yield was achieved at temperature and equivalence ratio conditions of 470 °C and 0.14. The bio-oil obtained has low oxygen content (38.48 wt.% dry basis), very low water content, and a lower heating value of 22.95 MJ/kg. The gas chromatographic analyses allowed the identification of oxygenated compounds and heterocyclic aromatic hydrocarbons. The bio-oil pH ranged between 3.14 and 3.57 due to the presence of acid organic compounds. The char obtained has a high fixed carbon and volatile matter content. Its HHV value is 13.54 MJ/kg. -- Highlights: • Pyrolysis of sugar cane straw was studied in a fluidized bed reactor. • The product yields were evaluated. • The composition of the liquid and solid products obtained was analyzed. • This is an environmentally friendly use for this waste

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

The transport phase of pyrolytic oil exiting a fast fluidized bed reactor

Science.gov (United States)

Daugaard, Daren Einar

An unresolved and debated aspect in the fast pyrolysis of biomass is whether the bio-oil exits as a vapor or as an aerosol from the pyrolytic reactor. The determination of the bio-oil transport phase will have direct and significant impact on the design of fast pyrolysis systems. Optimization of both the removal of particulate matter and collection of bio-oil will require this information. In addition, the success of catalytic reforming of bio-oil to high-value chemicals will depend upon this transport phase. A variety of experimental techniques were used to identify the transport phase. Some tests were as simple as examining the catch of an inline filter while others attempted to deduce whether vapor or aerosol predominated by examining the pressure drop across a flow restriction. In supplementary testing, the effect of char on aerosol formation and the potential impact of cracking during direct contact filtering are evaluated. The study indicates that for pyrolysis of red oak approximately 90 wt-% of the collected bio-oil existed as a liquid aerosol. Conversely, the pyrolysis of corn starch produced bio-oil predominately in the vapor phase at the exit of the reactor. Furthermore, it was determined that the addition of char promotes the production of aerosols during pyrolysis of corn starch. Direct contact filtering of the product stream did not collect any liquids and the bio-oil yield was not significantly reduced indicating measurable cracking or coking did not occur.

Pyrolysis kinetics of spent lark mushroom substrate and characterization of bio-oil obtained from the substrate

International Nuclear Information System (INIS)

Jiang, Haifeng; Cheng, Zhiqiang; Zhao, Tianqi; Liu, Mengzhu; Zhang, Mingyue; Li, Jianing; Hu, Meijuan; Zhang, Li; Li, Junfeng

2014-01-01

Highlights: • Pyrolysis behavior of spent lark mushroom substrate is investigated. • Significant pyrolysis stage occurs at the range of 232–382 °C. • Kinetics reveals the influence of heating rate on pyrolysis process. • The maximum bio-oil yield is found at 470 °C. • The characterization shows obtained oil can be utilized as a potential resource. - Abstract: In our work, thermal behavior and kinetic characteristics of spent lark mushroom substrate were evaluated to elaborate the thermal decomposition mechanisms and explore the influence of heating rate by using thermogravimetric analyzer and Coats–Redfern method. The study of pyrolysis temperature of raw material was also operated at the range of 410–530 °C, under the feeding rate 0.36 g/min, and the nitrogen flow 16 L/h. The results showed that the maximum bio-oil yield was obtained at 470 °C with the yield of 14.4 wt.%. The analysis of Fourier transform infrared spectrometer and gas chromatography coupled with mass selective detector indicated that the target liquid production was consisted of phenols, hydrocarbons and other components. Simultaneously, the low oxygen and high hydrogen content in bio-oil was also determined by elemental analysis. Based on the above-mentioned results, we demonstrated that the bio-oil obtained from the substrate had high utilization value as a potential energy resource

Catalytic pyrolysis of microalgae to high-quality liquid bio-fuels

International Nuclear Information System (INIS)

Babich, I.V.; Hulst, M. van der; Lefferts, L.; Moulijn, J.A.; O'Connor, P.; Seshan, K.

2011-01-01

The pyrolytic conversion of chlorella algae to liquid fuel precursor in presence of a catalyst (Na 2 CO 3 ) has been studied. Thermal decomposition studies of the algae samples were performed using TGA coupled with MS. Liquid oil samples were collected from pyrolysis experiments in a fixed-bed reactor and characterized for water content and heating value. The oil composition was analyzed by GC-MS. Pretreatment of chlorella with Na 2 CO 3 influences the primary conversion of chlorella by shifting the decomposition temperature to a lower value. In the presence of Na 2 CO 3 , gas yield increased and liquid yield decreased when compared with non-catalytic pyrolysis at the same temperatures. However, pyrolysis oil from catalytic runs carries higher heating value and lower acidity. Lower content of acids in the bio-oil, higher aromatics, combined with higher heating value show promise for production of high-quality bio-oil from algae via catalytic pyrolysis, resulting in energy recovery in bio-oil of 40%. -- Highlights: → The pyrolytic catalytic conversion of chlorella algae to liquid fuel precursor. → Na 2 CO 3 as a catalyst for the primary conversion of chlorella. → Pyrolysis oil from catalytic runs carries higher heating value and lower acidity. → High-quality bio-oil from algae via catalytic pyrolysis with energy recovery in bio-oil of 40%.

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

Characteristics of bio-oil from the pyrolysis of palm kernel shell in a newly developed two-stage pyrolyzer

International Nuclear Information System (INIS)

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

2016-01-01

Pyrolysis of palm kernel shell was performed using a two-stage pyrolyzer consisting of an auger reactor and a fluidized bed reactor within the auger reactor temperature range of ∼290–380 °C at the fluidized bed reactor temperature of ∼520 °C, and with a variable residence time of the feed material in the auger reactor. The highest bio-oil yield of the two-stage pyrolysis was ∼56 wt%. The bio-oil derived from the auger reactor contained degradation products of the hemicelluloses of PKS, such as acetic acid, and furfural, whereas the fluidized bed reactor produced a bio-oil with high concentrations of acetic acid and phenol. The auger reactor temperature and the residence time of PKS in the auger reactor had an influence on the acetic acid concentration in the bio-oil, while their changes did not induce an observable trend on the phenol concentration in the bio-oil derived from the fluidized bed reactor. The maximum concentrations of acetic acid and phenol in bio-oil were ∼78 and 12 wt% dry basis, respectively. As a result, it was possible for the two-stage pyrolyzer to separately produce two different bio-oils in one operation without any costly fractionation process of bio-oils. - Highlights: • The two-stage pyrolyzer is composed of an auger and a fluidized bed reactor. • The two-stage pyrolyzer produced two different bio-oils in a single operation. • The maximum bio-oil yield of the two-stage pyrolysis was ∼56 wt%. • The maximum concentration of acetic acid in bio-oil was ∼78 wt% dry basis. • The maximum concentration of phenol in bio-oil was ∼12 wt% dry basis.

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.

BioOil presents: Free-flowing alternative to traditional biomass energy generation

Energy Technology Data Exchange (ETDEWEB)

McChesney, S.

2003-12-01

A new technology, called fast pyrolysis, is described. Fast pyrolysis is a process for converting biomass collected from agricultural and forest residues into an organic liquid fuel, called BioOil, that's easily transported, stored and handled. BioOil's principal virtue is that it can be used to generate carbon-neutral, cost-effective process heat and electricity; it also disposes of organic waste, and creates new jobs and industries. As an indication of interest in BioOil, two recent developments are cited as worthy of note: an award of $23 million for biomass research jointly by the USDA and the USDOE and a commitment of $30 million by the Government of Canada to support the development and demonstration of bio-based systems and technologies. (The Canadian investment is part of the $1 billion commitment toward implementation of the Climate Change Program for Canada). The fast pyrolysis process is carbon dioxide neutral, i.e. when biomass is converted into thermal energy, the carbon dioxide that is released is equal to the amount of carbon dioxide that went into growing the biomass. The process is particularly appealing to energy companies in areas with large forestry or agricultural potential. In Canada, DynaMotive Energy Systems Corporation is the most advanced in developing and commercializing environmentally friendly fuels produced from biomass; the company is also a world leader in fast pyrolysis technology. Ontario Power Generation is cooperating with DynaMotive on a project to produce BioOil from residue supplied by Erie Flooring and Wood Products. The 2.5 megawatt gas turbine that will combust the bio-oil and generate electricity will be supplied by the Magellan Aerospace Corporation. Beyond meeting the energy requirements of Erie Flooring and Wood Products, the project will also contribute about 1.5 megawatts of power to OPG's green energy portfolio in 2004. It is expected that the example of a commercial project of this scale, will serve

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.)

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

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...... between fast pyrolysis of wheat straw at different reactor temperatures and the short-term degradability of biochar in soil. After 115 days incubation 3–12% of the added biochar-C had been emitted as CO2. On average, 90% of the total biochar-C loss occurred within the first 20 days of the experiment......, 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...

Two-step microalgal biodiesel production using acidic catalyst generated from pyrolysis-derived bio-char

International Nuclear Information System (INIS)

Dong, Tao; Gao, Difeng; Miao, Chao; Yu, Xiaochen; Degan, Charles; Garcia-Pérez, Manuel; Rasco, Barbara; Sablani, Shyam S.; Chen, Shulin

2015-01-01

Highlights: • Highly active catalyst was prepared using bio-char co-produced in Auger pyrolysis. • Catalyst inhibitors in crude oil were effectively removed by a practical refinery process. • Free fatty acids (FFA) content in refined microalgal oil was reduced to less than 0.5%. • A total fatty acid methyl ester (FAME) yield of 99% was obtained via a two-step process. • The inexpensive bio-char catalyst is superior to Amberlyst-15 in pre-esterification. - Abstract: An efficient process for biodiesel production from fast-refined microalgal oil was demonstrated. A low cost catalyst prepared from pyrolysis-derived bio-char, was applied in pre-esterification to reduce free fatty acid (FFA) content. Results showed that the bio-char catalyst was highly active in esterification; however, the performance of the catalyst significantly reduced when crude microalgal oil was used as feedstock. To solve the problem caused by catalyst-fouling, a fast and scalable crude oil refinery procedure was carried out to remove chlorophyll and phospholipids that might degrade the catalyst and the quality of biodiesel. The activity and reusability of bio-char catalyst were remarkably improved in the fast-refined oil. FFA content in the refined microalgal oil was reduced to less than 0.5% after pre-esterification. The bio-char catalyst could be reused for 10 cycles without dramatic loss in activity. The pre-esterification fits the first-order kinetic reaction with activation energy of 42.16 kJ/mol. The activity of bio-char catalyst was superior to commercial Amberlyst-15 under the same reaction condition. A total fatty acid methyl ester (FAME, namely biodiesel) yield of 99% was obtained following the second-step CaO-catalyzed transesterification. The cost-effective bio-char catalyst has great potential for biodiesel production using feedstocks having high FFA content.

Upgrading Fast Pyrolysis Oil via Hydrodeoxygenation and Thermal Treatment: Effects of Catalytic Glycerol Pretreatment

NARCIS (Netherlands)

Reyhanitash, Ehsan; Tymchyshyn, M.; Yuan, Zhongshun; Albion, K.; van Rossum, G.; Xu, C.

2014-01-01

The effects of stabilizing fast pyrolysis oil (PO) with glycerol via catalytic glycerol pretreatment on upgrading via hydrodeoxygenation (HDO) or thermal treatment (TT) were studied. Nonstabilized (original) fast pyrolysis oil was also upgraded via HDO or TT to obtain benchmarks. Generally, HDO

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

An overview of empty fruit bunch from oil palm as feedstock for bio-oil production

International Nuclear Information System (INIS)

Chang, Siu Hua

2014-01-01

Empty fruit bunch (EFB) from oil palm is one of the potential biomass to produce biofuels like bio-oil due to its abundant supply and favorable physicochemical characteristics. Confirming the assertion, this paper presents an overview of EFB as a feedstock for bio-oil production. The fundamental characteristics of EFB in terms of proximate analysis, ultimate analysis and chemical composition, as well as the recent advances in EFB conversion processes for bio-oil production like pyrolysis and solvolysis are outlined and discussed. A comparison of properties in terms of proximate analysis, ultimate analysis and fuel properties between the bio-oil from EFB and petroleum fuel oil is included. The major challenges and future prospects towards the utilization of EFB as a useful resource for bio-oil production are also addressed. - Highlights: • Palm EFB has high heating value and low greenhouse gas emissions during combustion. • Conversion of EFB to bio-oil is mainly by fast pyrolysis without and with catalyst. • Bio-oil from EFB is lower in heating value, heavier and more acidic than fuel oil. • The viscosity of bio-oil from EFB is between those of light and heavy fuel oils. • The flash and pour points of bio-oil from EFB are close to those of light fuel oil

Steam reforming of bio-oil from coconut shell pyrolysis over Fe/olivine catalyst

International Nuclear Information System (INIS)

Quan, Cui; Xu, Shaoping; Zhou, Congcong

2017-01-01

Highlights: • Steam reforming of the actual bio-oil was investigated with Fe/olivine catalyst. • Most of phenols in bio-oil were converted into gas products. • A carbon conversion of 97.2% was obtained under optimized conditions. - Abstract: Catalytic steam reforming of coconut shell pyrolysis bio-oil over Fe/olivine catalyst was conducted in a fixed-bed quartz reactor. The effects of calcination temperature, iron loading, reaction temperature, steam to carbon ratio (S/C), bio-oil weight hourly space velocity (W b HSV) on gas composition and carbon conversion were investigated. The results indicate that Fe/olivine has good activity for steam reforming of bio-oil, the couple Fe 2+/3+ /Fe 2+ may be sufficiently efficient for C–C, C–O and C–H breaking. After steam reforming, most of the phenolics in pyrolysis oil are converted into light molecular compounds such as H 2 , CO, CO 2 , and CH 4 . The H 2 concentration and carbon conversion were enhanced by increasing reaction temperature from 750 to 800 °C and the S/C from 1.5 to 2, but decreased with increasing calcination temperature. In the W b HSV range of 0.5–0.6, the hydrogen concentration decreased obviously, whereas it decreased slightly by further increasing W b HSV. The highest hydrogen concentration of 47.6 vol% was obtained among the catalysts tested, and the best carbon conversion was 97.2% over 10% Fe/olivine catalyst under the reforming conditions of temperature = 800 °C, W b HSV = 0.5, S/C = 2.

Catalytic cracking of fast and tail gas reactive pyrolysis bio-oils over HZSM-5

Science.gov (United States)

While hydrodeoxygenation (HDO) of pyrolysis oil is well understood as an upgrading method, the high processing pressures associated with it alone justify the exploration of alternative upgrading solutions, especially those that could adapt pyrolysis oils into the existing refinery infrastructure. Ca...

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

Science.gov (United States)

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

2015-02-01

Liquefaction bio-oil (LBO) produced with ethanol (or acetone) as the solvent and pyrolysis bio-oil (PBO) produced at 550°C (or 850°C) from sewage sludge (SS) were produced, and were characterized and evaluated in terms of their heavy metal (HM) composition. The total concentration, speciation and leaching characteristic of HMs (Cu, Cr, Pb, Zn, Cd, and Ni) in both LBO and PBO were investigated. The total concentration and exchangeable fraction of Zn and Ni in bio-oils were at surprisingly high levels. Quantitative risk assessment of HM in bio-oils was performed by the method of risk assessment code (RAC), potential ecological risk index (PERI) and geo-accumulation index (GAI). Ni in bio-oil produced by pyrolysis at 850°C (PBO850) and Zn in bio-oil by liquefaction at 360°C with ethanol as solvent (LBO-360E) were evaluated to possess very high risk to the environment according to RAC. Additionally, Cd in PBO850 and LBO-360E were evaluated by PERI to have very high risk and high risk, respectively, while Cd in all bio-oils was assessed moderately contaminated according to GAI. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

KAUST Repository

Imran, Ali; Bramer, Eddy 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

Catalytic Fast Pyrolysis of Alcell Lignin with Nano-NiO

Directory of Open Access Journals (Sweden)

Jiao Chen

2015-11-01

Full Text Available Catalytic fast pyrolysis of Alcell lignin with various additive ratios (5%, 10%, and 15%, mass ratio of nano-NiO was investigated using a horizontal pyrolyzer. Characterization methods, including Fourier transform infrared spectroscopy (FTIR, gas chromatography (GC, gas chromatography coupled with mass spectrometry (GC/MS, and elemental analysis, were utilized to identify the catalytic fast pyrolysis products. The results indicated that the nano-NiO catalyst had remarkable effects on the yield and quality of these products. The formation of gases, especially CO, CO2, and CH4, were greatly promoted when the additive ratio increased, while the formation of bio-char was clearly inhibited. However, when the additive ratio was 10%, the maximum yield of bio-oil (53.09 wt.% was obtained, and the corresponding maximum higher heating value (HHV was 25.33 MJ/kg. Furthermore, nano-NiO caused a large variation in the species of the compounds in bio-oil. Operating with the optimal nano-NiO additive ratio (10%, the carbon conversion rate was 65.50%, and the energy conversion rate was 74.53%.

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

Fast microwave assisted pyrolysis of biomass using microwave absorbent.

Science.gov (United States)

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

2014-03-01

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

Ni-Based Catalysts for the Hydrotreatment of Fast Pyrolysis Oil

NARCIS (Netherlands)

Ardiyanti, A. R.; Bykova, M. V.; Khromova, S. A.; Yin, W.; Venderbosch, R. H.; Yakovlev, V. A.; Heeres, Hero

Catalytic hydrotreatment is an attractive technology to convert fast pyrolysis oil to stabilized oil products for co processing in conventional crude oil refinery units. We report here the use of novel bimetallic NiCu- and NiPd-based (Picula) catalysts characterized by a high Ni content (29-58 wt %)

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

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.

Comparative techno-economic analysis of biohydrogen production via bio-oil gasification and bio-oil reforming

International Nuclear Information System (INIS)

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

2013-01-01

This paper evaluates the economic feasibility of biohydrogen production via two bio-oil processing pathways: bio-oil gasification and bio-oil reforming. Both pathways employ fast pyrolysis to produce bio-oil from biomass stock. The two pathways are modeled using Aspen Plus ® for a 2000 t d −1 facility. Equipment sizing and cost calculations are based on Aspen Economic Evaluation® software. Biohydrogen production capacity at the facility is 147 t d −1 for the bio-oil gasification pathway and 160 t d −1 for the bio-oil reforming pathway. The biomass-to-fuel energy efficiencies are 47% and 84% for the bio-oil gasification and bio-oil reforming pathways, respectively. Total capital investment (TCI) is 435 million dollars for the bio-oil gasification pathway and is 333 million dollars for the bio-oil reforming pathway. Internal rates of return (IRR) are 8.4% and 18.6% for facilities employing the bio-oil gasification and bio-oil reforming pathways, respectively. Sensitivity analysis demonstrates that biohydrogen price, biohydrogen yield, fixed capital investment (FCI), bio-oil yield, and biomass cost have the greatest impacts on facility IRR. Monte-Carlo analysis shows that bio-oil reforming is more economically attractive than bio-oil gasification for biohydrogen production. -- Highlights: ► Biohydrogen production via bio-oil reforming has higher energy efficiency compared to gasification. ► Hydrogen price, fixed capital cost, and feedstock cost most strongly affect IRR. ► Lower risk investment is biohydrogen production via bio-oil reforming

Synthesis and tribological studies of nanoparticle additives for pyrolysis bio-oil formulated as a diesel fuel

International Nuclear Information System (INIS)

Xu, Yufu; Peng, Yubin; Zheng, Xiaojing; Dearn, Karl D.; Xu, Hongming; Hu, Xianguo

2015-01-01

The tribological behaviour of pyrolysis bio-oil with a synthesized nano-Lanthanum oxide (La 2 O 3 ) additive was evaluated using a point contact four ball tribometer under different frictional conditions. Results were compared against a micro (μ)-La 2 O 3 additive and an un-additised bio-oil as a control. The results show that nano-La 2 O 3 impregnated bio-oil had better tribological properties than the control groups. Under the operating loads, the optimum nanoparticle concentration within the bio-oil was investigated. At these levels, the combined action of adsorbed bio-oil films on the worn surfaces and the bearing effects of the nano-La 2 O 3 minimized friction and wear. The tribo-mechanisms were ascribed to adhesive wear as a result of lubrication starvation under high loads, and abrasive wear at high rotational speeds as a result of combined deformation and aggregation of the nano-La 2 O 3 particles. - Highlights: • The tribological properties of pyrolysis bio-oil with (μ & n) La 2 O 3 were assessed. • Nano-La 2 O 3 was synthesized with diameters of approximately 20–1000 nm. • Bio-oil w. 1% nano-La 2 O 3 was the optimum additive & concentration for tribological properties. • 1% nano-La 2 O 3 reduced corrosive wear with stable lubrication film for test conditions. • Wear mechanisms were predominately adhesive for higher loads and abrasive for higher speeds

Influence of polystyrene addition to cellulose on chemical structure and properties of bio-oil obtained during pyrolysis

International Nuclear Information System (INIS)

Rutkowski, Piotr; Kubacki, Andrzej

2006-01-01

The cellulose (C), polystyrene (PS) and cellulose/polystyrene (C-PS) mixtures (3:1, 1:1, 1:3 w/w) were subjected to a pyrolysis process to produce bio-oil. The pyrolytic oil yield was in the range of 45.5-94.8 wt% depending on the composition of the sample. Pyrolysis of polystyrene gives the highest oil yield, whereas for cellulose, the yield of liquid products was the lowest. The basic physicochemical properties of oils are strongly influenced by the original material and do not change additively. The polystyrene addition to cellulose clearly improves the quality of the bio-oil, resulting in decreases in acid number, pour point and density. The change of color is not so distinct. The FT-IR analysis of the oils showed that the oxygen functionalities and hydrocarbons contents highly depend on the composition of the cellulose/polystyrene mixture. The fractionation of bio-oils by column chromatography using hexane and benzene was followed by GC-MS analyses. Different classes of organic compounds were identified, i.e., carboxylic acids, phenols, aldehydes, ketones, esters, ethers and unsaturated linear and cyclic hydrocarbons. The proportion of hydrocarbons increases with a decrease of the cellulose/polystyrene ratio. The obtained results indicate that during pyrolysis, not only does decomposition of cellulose and polystyrene occur, but also, reactions between products from C and PS take place. That was proved by the presence of compounds identified only in the bio-oils obtained from C-PS compositions

Fast pyrolysis of hardwood residues using a fixed bed drop-type pyrolyzer

International Nuclear Information System (INIS)

Mazlan, Mohammad Amir Firdaus; Uemura, Yoshimitsu; Osman, Noridah B.; Yusup, Suzana

2015-01-01

Highlights: • Pyrolysis of rubber and Meranti wood was conducted by using a drop-type pyrolyzer. • As temperature increase, char yield decrease, but bio-oil and gas yield increase. • Maximum pyrolysis temperature for pyrolysis of RWS is 550 °C and 600 °C for MWS. • Calorific value of bio-char is very high and potential to be used as a solid fuel. • CO and CO 2 are the major gas components in the non-condensable gases by-product. - Abstract: In this research, rubber wood sawdust (RWS) and Meranti wood sawdust (MWS) were pyrolyzed in a fixed bed drop-type pyrolyzer under an inert condition. The first part of the study is to determine the influence of pyrolysis temperature (450, 500, 550, 600, 650 °C) on the yield of pyrolysis products. Pyrolysis of these different residues generate an almost identical maximum amount of bio-oil close to 33 wt.%, but at different maximum temperature (550 °C for pyrolysis of RWS and 600 °C for pyrolysis of MWS). To evaluate the effect of biomass type on the composition and characterization of pyrolysis products, the second part involves the analyses of pyrolysis products from the maximum pyrolysis temperature. Acetic acid, tetrahydrofuran, and benzene were the main bio-oil components. The bio-oil contained high percentage of oxygen and hydrogen, indicating high water content in the bio-oil. High amount of water in bio-oil significantly reduced its calorific value. Under extensive heating, particle size of the bio-char from SEM images decreased due to breakage and shrinkage mechanisms. The major components of non-condensable gases were CO and CO 2

Production and detailed characterization of bio-oil from fast pyrolysis of palm kernel shell

International Nuclear Information System (INIS)

Asadullah, Mohammad; Ab Rasid, Nurul Suhada; Kadir, Sharifah Aishah Syed A.; Azdarpour, Amin

2013-01-01

Bio-oil has been produced from palm kernel shell in a fluidized bed reactor. The process conditions were optimized and the detailed characteristics of bio-oil were carried out. The higher feeding rate and higher gas flow rate attributed to higher bio-oil yield. The maximum mass fraction of biomass (57%) converted to bio-oil at 550 °C when 2 L min −1 of gas and 10 g min −1 of biomass were fed. The bio-oil produced up to 500 °C existed in two distinct phases, while it formed one homogeneous phase when it was produced above 500 °C. The higher heating value of bio-oil produced at 550 °C was found to be 23.48 MJ kg −1 . As GC–MS data shows, the area ratio of phenol is the maximum among the area ratio of identified compounds in 550 °C bio-oil. The UV–Fluorescence absorption, which is the indication of aromatic content, is also the highest in 550 °C bio-oil. -- Highlights: • Maximum 56 wt% yield of bio-oil was obtained at 550 °C from palm kernel shell. • Two layer of bio-oil was observed up to 500 °C, while it was one layer above 500 °C. • Bio-oil from palm kernel shell provides more than 40% area ratio of phenol in GC–MS analysis. • The calorific value of palm kernel shell bio-oil is higher than other bio-oil

Nano-catalysts for upgrading bio-oil: Catalytic decarboxylation and hydrodeoxygenation

Science.gov (United States)

Uemura, Yoshimitsu; Tran, Nga T. T.; Naqvi, Salman Raza; Nishiyama, Norikazu

2017-09-01

Bio-oil is a mixture of oxygenated chemicals produced by fast pyrolysis of lignocellulose, and has attracted much attention recently because the raw material is renewable. Primarily, bio-oil can be used as a replacement of heavy oil. But it is not highly recommended due to bio-oil's inferior properties: high acidity and short shelf life. Upgrading of bio-oil is therefore one of the important technologies nowadays, and is categorized into the two: (A) decrarboxylation/decarbonylation by solid acid catalysts and (B) hydrodeoxygenation (HDO) by metallic catalysts. In our research group, decarboxylation of bio-oil by zeolites and HDO of guaiacol (a model compound of bio-oil) have been investigated. In this paper, recent developments of these upgrading reactions in our research group will be introduced.

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

International Nuclear Information System (INIS)

Bruun, Esben W.; Hauggaard-Nielsen, Henrik; Ibrahim, Norazana; Egsgaard, Helge; Ambus, Per; Jensen, Peter A.; Dam-Johansen, Kim

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 between fast pyrolysis of wheat straw at different reactor temperatures and the short-term degradability of biochar in soil. After 115 days incubation 3-12% of the added biochar-C had been emitted as CO 2 . On average, 90% of the total biochar-C loss occurred within the first 20 days of the experiment, 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 pyrolysis process may result in incomplete conversion of biomass due to limitations to heat transfer and kinetics. In our case chemical analysis of the biochars revealed unconverted cellulosic and hemicellulosic fractions, which in turn were found to be proportional with the short-term biochar degradation 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 CO 2 neutral bio-oil is the other factor to optimize when adjusting the pyrolysis temperature settings to give the overall greatest climate change mitigation effect.

Flash pyrolysis fuel oil: BIO-POK

Energy Technology Data Exchange (ETDEWEB)

Gust, S. [Neste Oy, Porvoo (Finland)

1995-12-31

Flash pyrolysis oil from Ensyn Tech., Canada and Union Fenosa, Spain was combusted with simple pressure atomisation equipment commonly used with light fuel oils in intermediate size (0.1-1 MW) boilers. With a number of modifications to the combustion system, carbon monoxide (CO) and nitrous oxide (NO{sub x}) could be reduced to acceptable levels: CO < 30 ppm and NO{sub x} < 140 ppm. Particulate emissions which were initially very high (Bacharach 4-5) were reduced (Bach. 2-3) by system changes but are still higher than from light fuel oil (Bach. <1). The modifications to the combustion system were: acid resistant progressive cavity pump, higher oil preheat temperature and higher oil pressure than for light fuel oils, refractory section between burner and boiler warmed up to at least 800 deg C. In addition, it was necessary to store pyrolysis oil samples under inert conditions to prevent oxidation and to rinse nozzles with alcohol after shutdown to prevent coking. The complexity and cost of these system modifications are considered to be too great for current grades of flash pyrolysis oil to be sold as a light fuel oil replacement. Improvements to fuel quality will be necessary. The main improvements are lowering of viscosity and improving of stability

Flash pyrolysis fuel oil: BIO-POK

Energy Technology Data Exchange (ETDEWEB)

Gust, S [Neste Oy, Porvoo (Finland)

1996-12-31

Flash pyrolysis oil from Ensyn Tech., Canada and Union Fenosa, Spain was combusted with simple pressure atomisation equipment commonly used with light fuel oils in intermediate size (0.1-1 MW) boilers. With a number of modifications to the combustion system, carbon monoxide (CO) and nitrous oxide (NO{sub x}) could be reduced to acceptable levels: CO < 30 ppm and NO{sub x} < 140 ppm. Particulate emissions which were initially very high (Bacharach 4-5) were reduced (Bach. 2-3) by system changes but are still higher than from light fuel oil (Bach. <1). The modifications to the combustion system were: acid resistant progressive cavity pump, higher oil preheat temperature and higher oil pressure than for light fuel oils, refractory section between burner and boiler warmed up to at least 800 deg C. In addition, it was necessary to store pyrolysis oil samples under inert conditions to prevent oxidation and to rinse nozzles with alcohol after shutdown to prevent coking. The complexity and cost of these system modifications are considered to be too great for current grades of flash pyrolysis oil to be sold as a light fuel oil replacement. Improvements to fuel quality will be necessary. The main improvements are lowering of viscosity and improving of stability

CFD modeling of space-time evolution of fast pyrolysis products in a bench-scale fluidized-bed reactor

International Nuclear Information System (INIS)

Boateng, A.A.; Mtui, P.L.

2012-01-01

A model for the evolution of pyrolysis products in a fluidized bed has been developed. In this study the unsteady constitutive transport equations for inert gas flow and decomposition kinetics were modeled using the commercial computational fluid dynamics (CFD) software FLUENT-12. The Eulerarian-Eulerian multiphase model system described herein is a fluidized bed of sand externally heated to a predetermined temperature prior to introduction of agricultural biomass. We predict the spontaneous emergence of pyrolysis vapors, char and non-condensable (permanent) gases and confirm the observation that the kinetics are fast and that bio-oil vapor evolution is accomplished in a few seconds, and occupying two-thirds of the spatial volume of the reactor as widely reported in the open literature. The model could be advantageous in the virtual design of fast pyrolysis reactors and their optimization to meet economic scales required for distributed or satellite units. - Highlights: ► We model the evolution of pyrolysis products in a fluidized bed via CFD. ► We predict the spontaneous emergence of pyrolysis products. ► We confirm the experimental observation that the kinetics are fast. ► And that bio-oil vapor evolution is accomplished in a few seconds. ► The model is advantageous in the virtual design of fast pyrolysis reactors.

Exergy analysis of synthetic biofuel production via fast pyrolysis and hydroupgrading

International Nuclear Information System (INIS)

Peters, Jens F.; Petrakopoulou, Fontina; Dufour, Javier

2015-01-01

This paper presents the first assessment of the exergetic performance of a biorefinery process based on catalytic hydroupgrading of bio-oil from fast pyrolysis. Lignocellulosic biomass is converted into bio-oil through fast pyrolysis, which is then upgraded to synthetic fuels in a catalytic hydrotreating process. The biorefinery process is simulated numerically using commercial software and analyzed using exergetic analysis. Exergy balances are defined for each component of the plant and the exergetic efficiencies and exergy destruction rates are calculated at the component, section and plant level, identifying thermodynamic inefficiencies and revealing the potential for further improvement of the process. The overall biofuel process results in an exergetic efficiency of 60.1%, while the exergetic efficiency of the upgrading process in the biorefinery alone is 77.7%. Within the biorefinery, the steam reforming reactor is the main source of inefficiencies, followed by the two hydrotreating reactors. In spite of the high operating pressures in the hydrotreating section, the compressors have little impact on the total exergy destruction. Compared to competing lignocellulosic biofuel processes, like gasification with Fischer–Tropsch synthesis or lignocellulosic ethanol processes, the examined system achieves a significantly higher exergetic efficiency. - Highlights: • Exergetic analysis of a biorefinery for bio-oil hydroupgrading. • Detailed simulation model using 83 model compounds. • Exergy destruction quantified in each component of the plant. • Exergetic efficiency and potential for improvement determined on component level. • Highest exergy destruction in the pyrolysis plant and the steam reformer

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)

Biocrude oils from the fast pyrolysis of poultry litter and hardwood

International Nuclear Information System (INIS)

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

2010-01-01

The safe and economical disposal of poultry litter is becoming a major problem for the USA poultry industry. Current disposal methods such as land application and feeding to cattle are now under pressure because of pollution of water resources due to leaching, runoffs and concern for mad cow disease contamination of the food chain. Incineration or combustion is potentially applicable to large scale operations, but for small scale growers and EPA non-attainment areas, this is not a suitable option because of the high cost of operation. Thus, there is a need for developing appropriate technologies to dispose poultry litter. Poultry litters from broiler chicken and turkey houses, as well as bedding material were converted into biocrude oil in a fast pyrolysis fluidized bed reactor. The biocrude oil yields were relatively low ranging from 36 wt% to 50 wt% depending on the age and bedding material content of the litter. The bedding material (which was mostly hardwood shavings) biocrude oil yield was 63 wt%. The higher heating value (HHV) of the poultry litter biocrude oils ranged from 26 MJ/kg to 29 MJ/kg while that of the bedding material was 24 MJ/kg. The oils had relatively high nitrogen content ranging from 4 wt% to 8 wt%, very low sulfur (<1 wt%) content and high viscosity. The viscosities of the oils appeared to be a function of both the source of litter and the pyrolysis temperature. The biochar yield ranged from 27 wt% to 40 wt% depending on the source, age and composition of the poultry litter. The biochar ash content ranged from 24 wt% to 54 wt% and was very rich in inorganic components such as potassium and phosphorous.

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. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

Understanding the fast pyrolysis of lignin.

Science.gov (United States)

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

2011-11-18

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

Bio oil from pyrolysis of cashew nut shell-characterisation and related properties

International Nuclear Information System (INIS)

Das, Piyali; Sreelatha, T.; Ganesh, Anuradda

2004-01-01

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 1 HNMR, 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

Catalytic flash pyrolysis of oil-impregnated-wood and jatropha cake using sodium based catalysts

KAUST Repository

Imran, Ali

2015-11-24

Catalytic pyrolysis of wood with impregnated vegetable oil was investigated and compared with catalytic pyrolysis of jatropha cake making use of sodium based catalysts to produce a high quality bio-oil. The catalytic pyrolysis was carried out in two modes: in-situ catalytic pyrolysis and post treatment of the pyrolysis vapors. The in-situ catalytic pyrolysis was carried out in an entrained flow reactor system using a premixed feedstock of Na2CO3 and biomass and post treatment of biomass pyrolysis vapor was conducted in a downstream fixed bed reactor of Na2CO3/γ-Al2O3. Results have shown that both Na2CO3 and Na2CO3/γ-Al2O3 can be used for the production of a high quality bio-oil from catalytic pyrolysis of oil-impregnated-wood and jatropha cake. The catalytic bio-oil had very low oxygen content, water content as low as 1wt.%, a neutral pH, and a high calorific value upto 41.8MJ/kg. The bio-oil consisted of high value chemical compounds mainly hydrocarbons and undesired compounds in the bio-oil were either completely removed or considerably reduced. Increasing the triglycerides content (vegetable oil) in the wood enhanced the formation of hydrocarbons in the bio-oil. Post treatment of the pyrolysis vapor over a fixed bed of Na2CO3/γ-Al2O3 produced superior quality bio-oil compared to in-situ catalytic pyrolysis with Na2CO3. This high quality bio-oil may be used as a precursor in a fractionating process for the production of alternative fuels. © 2015 Elsevier B.V.

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.

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 [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Meyer, Pimphan [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Snowden-Swan, Lesley [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Padmaperuma, Asanga [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Tan, Eric [National Renewable Energy Lab. (NREL), Golden, CO (United States); Dutta, Abhijit [National Renewable Energy Lab. (NREL), Golden, CO (United States); Jacobson, Jacob [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cafferty, Kara [Idaho National Lab. (INL), Idaho Falls, ID (United States)

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.

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. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Meyer, Pimphan A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Snowden-Swan, Lesley J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Padmaperuma, Asanga B. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Tan, Eric [National Renewable Energy Lab. (NREL), Golden, CO (United States); Dutta, Abhijit [National Renewable Energy Lab. (NREL), Golden, CO (United States); Jacobson, Jacob [Idaho National Lab. (INL), Idaho Falls, ID (United States); Cafferty, Kara [Idaho National Lab. (INL), Idaho Falls, ID (United States)

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.

Bio-Oil Analysis Laboratory Procedures | Bioenergy | NREL

Science.gov (United States)

Bio-Oil Analysis Laboratory Procedures Bio-Oil Analysis Laboratory Procedures NREL develops laboratory analytical procedures (LAPs) for the analysis of raw and upgraded pyrolysis bio-oils. These standard procedures have been validated and allow for reliable bio-oil analysis. Procedures Determination

Effects of the cellulose, xylan and lignin constituents on biomass pyrolysis characteristics and bio-oil composition using the Simplex Lattice Mixture Design method

International Nuclear Information System (INIS)

Fan, Yongsheng; Cai, Yixi; Li, Xiaohua; Jiao, Lihua; Xia, Jisheng; Deng, Xiuli

2017-01-01

Highlights: • Simplex Lattice Mixture Design was firstly applied to study biomass pyrolysis process. • Interactions between the constituents had effects on the biomass pyrolysis behavior. • Biomass pyrolysis behavior can be predicted based on the ratios of three constituents. • Bio-oil composition was affected by the constituents and their pyrolysis products. - Abstract: In order to clarify the relationships between biomass pyrolysis mechanism and its main constituents. The effects of main constituents on biomass pyrolysis characteristics were firstly determined by thermo-gravimetric analysis based on the Simplex Lattice Mixture Design to investigate that whether the prediction of the pyrolysis behavior of a certain lignocellulosic biomass is possible when its main constituent contents are known. The results showed that there are constituent interactions in the pyrolysis process, which can be intuitively reflected through the change laws of kinetics parameters. The mathematical models for calculating kinetics values were established, and the models were proved to be valid for predicting lignocellulosic biomass pyrolysis behavior. In addition, the effects of biomass constituents on bio-oil compositions were explored by subsequent vacuum pyrolysis experiments. The xylan pyrolysis had a certain inhibitory effect on the pyrolysis of cellulose, and the pyrolysis products of lignin might promote the further decomposition of sugars from cellulose pyrolysis, while the interaction between xylan and lignin had a little effect on the bio-oil composition.

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.

The lignin pyrolysis composition and pyrolysis products of palm kernel shell, wheat straw, and pine sawdust

International Nuclear Information System (INIS)

Chang, Guozhang; Huang, Yanqin; Xie, Jianjun; Yang, Huikai; Liu, Huacai; Yin, Xiuli; Wu, Chuangzhi

2016-01-01

Highlights: • The primarily pyrolysis composition of PKS lignin was p-hydroxyphenyl unit. • Higher phenol yield and lower gas energy yield were obtained from PKS pyrolysis. • PKS produced more bio-oil and biochar than WS and PS from pyrolysis at 650–850 °C. • PKS-char had poorer gasification reactivity due to higher ordering carbon degree. - Abstract: The lignin monomer composition of palm kernel shell (PKS) was characterized using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and the characteristics and distributions of products obtained from PKS pyrolysis were investigated using Py-GC/MS, GC, and a specially designed pyrolysis apparatus. The gasification reactivity of PKS biochar was also characterized using thermogravimetry (TG) and Raman spectroscopy. All the results were compared with those obtained from wheat straw (WS) and pine sawdust (PS). The results showed that PKS lignin is primarily composed of p-hydroxyphenyl structural units, while WS and PS lignins are mainly made up of guaiacyl units. Both the mass and energy yields of non-condensable gases from PKS pyrolysis were lower than those obtained from WS and PS pyrolysis at 650–850 °C, owing to the lower volatile content (75.21%) and lack of methoxy groups in PKS. Compared with WS and PS, higher bio-oil productivity was observed during PKS pyrolysis. Phenols were the main component of PKS bio-oil from pyrolysis at 500 °C, and the phenol content of PKS bio-oil (13.49%) was higher than in WS bio-oil (1.62%) and PS bio-oil (0.55%). A higher yield of biochar (on an ash-free basis) was also obtained from PKS pyrolysis. Because of its greater relative degree of ordered carbon, PKS biochar exhibited lower in situ reactivity during CO_2 or H_2O gasification than WS and PS biochars. A longer residence time and addition of steam were found to be beneficial during PKS biochar gasification.

Total recovery of nitrogen and phosphorus from three wetland plants by fast pyrolysis technology.

Science.gov (United States)

Liu, Wu-Jun; Zeng, Fan-Xin; Jiang, Hong; Yu, Han-Qing

2011-02-01

Fast pyrolysis of three wetland plants (Alligator weed, Oenanthe javanica and Typha angustifolia) in a vertical drop fixed bed reactor was investigated in this study. The experiments were carried out at different pyrolysis temperatures, and the maximum bio-oil yields achieved were 42.3%, 40.2% and 43.6% for Alligator weed, Oenanthe javanica and Typha angustifolia, respectively. The elemental composition of the bio-oil and char were analyzed, and the results show that a low temperature was appropriate for the nitrogen and phosphorus enrichment in char. GC-MS analysis shows that nitrogenous compounds, phenols and oxygenates were the main categories in the bio-oil. A series of leaching tests were carried out to examine the recovery of the nitrogen and phosphorus in the char, and the results indicate that significant fractions of nitrogen and phosphorus could be recovered by leaching process. Copyright © 2010 Elsevier Ltd. All rights reserved.

Bio-oil production via co-pyrolysis of almond shell as biomass and high density polyethylene

International Nuclear Information System (INIS)

Önal, Eylem; Uzun, Başak Burcu; Pütün, Ayşe Eren

2014-01-01

Highlights: • We investigate to see the effect of HDPE addition on thermal decomposition of lignocellulosic materials. • Increasing the proportion of HDPE in mixtures increases the oil yields. • After co-pyrolysis applied, obtained oil is more stable due to having lower oxygen content and higher heating value. • The addition of HDPE to aS has a positive effect on fuel properties of obtained oil. - Abstract: Biomass from almond shell (aS) was co-pyrolyzed with high density polyethylene (HDPE) polymer to investigate the synergistic effects on the product yields and compositions. The pyrolysis temperature was selected as 500 °C, based on results of TGA-DTG. Co-pyrolysis of HDPE-biomass mixtures were pyrolysed with various proportions such as 1:0, 1:1, 1:2, 2:1 and 0:1. The yield of liquids produced during co-pyrolysis enhanced 23%, as the weight ratio of HDPE in the mixture was doubled. Obtained bio-oils were analyzed with using column chromatography, 1 H NMR, GC/MS, and FT-IR. According to analyses results, produced liquids by co-pyrolysis had higher carbon (26% higher) and hydrogen contents (78% higher), lower oxygen content (%86 less) with a higher heating value (38% higher) than those of biomass oil

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

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

Immediate catalytic upgrading of soybean shell bio-oil

International Nuclear Information System (INIS)

Bertero, Melisa; Sedran, Ulises

2016-01-01

The pyrolysis of soybean shell and the immediate catalytic upgrading of the bio-oil over an equilibrium FCC catalyst was studied in order to define its potential as a source for fuels and chemicals. The experiments of pyrolysis and immediate catalytic upgrading were performed at 550 °C during 7 min with different catalysts to oil relationships in an integrated fixed bed pyrolysis-conversion reactor. The results were compared under the same conditions against those from pine sawdust, which is a biomass source commonly used for the production of bio-oil. In the pyrolysis the pine sawdust produced more liquids (61.4%wt.) than the soybean shell (54.7%wt.). When the catalyst was presented, the yield of hydrocarbons increased, particularly in the case of soybean shell, which was four time higher than in the pyrolysis. The bio-oil from soybean shell produced less coke (between 3.1 and 4.3%wt.) in its immediate catalytic upgrading than that from pine sawdust (between 5 and 5.8%wt.), due to its lower content of phenolic and other high molecular weight compounds (three and five times less, respectively). Moreover, soybean shell showed a higher selectivity to hydrocarbons in the gasoline range, with more olefins and less aromatic than pine sawdust. - Highlights: • Soybean shell is a possible source of fuels with benefits as compared to pine sawdust. • Bio-oils upgraded over FCC catalyst in an integrated pyrolysis-conversion reactor. • Pine sawdust bio-oil had more phenols than soybean shell bio-oil. • Soybean shell bio-oil produced more hydrocarbons in gasoline range and less coke.

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.

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...

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.

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 (LC 50 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.

Bio-oil and bio-char production from biomass and their structural analyses

International Nuclear Information System (INIS)

Kilic, Murat; Özsin, Gamzenur; Pütün, Ayşe E.; Pütün, Ersan

2015-01-01

Energy demand is increasing day by day because of the rapid developments in the population, industrialization and urbanisation. Since, fossil fuels will be at the verge of getting extinct, researches are mostly focused on the renewable sources, such as biomass, in recent years. This paper provides an environmentally friendly process to convert waste biomass samples to bio-oil and bio-char by pyrolysis. For this purpose, pyrolysis characteristics of pomegranate peels under inert atmosphere were studied by using both TGA to analysis decomposition behaviour and a batch reactor to investigate product yields and properties. The properties of bio-oil and bio-char were investigated by different analytical techniques such as GC-MS, FT-IR, SEM, He pycnometry and elemental analysis. As a consequence, it is possible to obtain bio-oil, which has similar properties like petroleum hydrocarbons, and to obtain bio-char, which can be further used as a solid fuel or a carbonaceous adsorbent material via pyrolysis process. (full text)

Insecticidal activity of bio-oils and biochar as pyrolysis products and their combination with microbial agents against Agrotis ipsilon (Lepidoptera: Noctuidae)

Science.gov (United States)

Pyrolysis technology for producing biochar and bio-oils can be used as a potential alternative to make biopesticides, which are urgently needed in integrated pest management (IPM). Insecticidal activity of three components of bio-oils: aqueous, organic and their mixture, was evaluated individually a...

Characterization of Catalytic Fast Pyrolysis Oils: The Importance of Solvent Selection for Analytical Method Development

Energy Technology Data Exchange (ETDEWEB)

Ferrell, Jack R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Ware, Anne E [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2018-02-25

Two catalytic fast pyrolysis (CFP) oils (bottom/heavy fraction) were analyzed in various solvents that are used in common analytical methods (nuclear magnetic resonance - NMR, gas chromatography - GC, gel permeation chromatography - GPC, thermogravimetric analysis - TGA) for oil characterization and speciation. A more accurate analysis of the CFP oils can be obtained by identification and exploitation of solvent miscibility characteristics. Acetone and tetrahydrofuran can be used to completely solubilize CFP oils for analysis by GC and tetrahydrofuran can be used for traditional organic GPC analysis of the oils. DMSO-d6 can be used to solubilize CFP oils for analysis by 13C NMR. The fractionation of oils into solvents that did not completely solubilize the whole oils showed that miscibility can be related to the oil properties. This allows for solvent selection based on physico-chemical properties of the oils. However, based on semi-quantitative comparisons of the GC chromatograms, the organic solvent fractionation schemes did not speciate the oils based on specific analyte type. On the other hand, chlorinated solvents did fractionate the oils based on analyte size to a certain degree. Unfortunately, like raw pyrolysis oil, the matrix of the CFP oils is complicated and is not amenable to simple liquid-liquid extraction (LLE) or solvent fractionation to separate the oils based on the chemical and/or physical properties of individual components. For reliable analyses, for each analytical method used, it is critical that the bio-oil sample is both completely soluble and also not likely to react with the chosen solvent. The adoption of the standardized solvent selection protocols presented here will allow for greater reproducibility of analysis across different users and facilities.

Fixed-bed hydrogen pyrolysis of rapeseed: product yields and compositions

International Nuclear Information System (INIS)

Onay, O.; Kockar, O.M.; Gaines, A.F.; Snape, C.E.

2006-01-01

The fixed-bed hydro pyrolysis tests have been conducted on a sample of rapeseed to investigate the effect of hydro pyrolysis on the yields and chemical structures of bio-oils, with a view to improving overall product quality. A ammonium dioxydithiomolybdenate catalyst has been used in some tests to further increase conversion. The maximum bio-oil yield of 84% was obtained in hydrogen atmosphere (with catalyst) at hydrogen pressure of 15 MPa, hydrogen flow rate of 10 dm 3 min -1 , hydro pyrolysis temperature of 520 degree C, and heating rate of 5 o Cmin -1 . Then this bio-oil was characterized by elemental analysis and some spectroscopic and chromatographic techniques. And finally, this bio-oil yield and chemical composition compared with oil obtained from fast pyrolysis condition

Upgrading pyrolysis bio-oil to biofuel over bifunctional Co-Zn/HZSM-5 catalyst in supercritical methanol

International Nuclear Information System (INIS)

Cheng, Shouyun; Wei, Lin; Julson, James; Muthukumarappan, Kasiviswanathan; Kharel, Parashu Ram

2017-01-01

Highlights: • Integration of Co-Zn/HZSM-5 and supercritical methanol was used for bio-oil hydrodeoxygenation. • Co-Zn/HZSM-5 exhibited higher effectiveness than Co/HZSM-5 or Zn/HZSM-5. • 15%Co5%Zn/HZSM-5 produced biofuel with the highest hydrocarbons content at 35.33%. • Loading of Co and/or Zn did not change crystalline structure of HZSM-5. • Hydrogenation and esterification are main reactions in bio-oil hydrodeoxygenation. - Abstract: The role of catalyst is essential in processes of upgrading biomass pyrolysis bio-oil into hydrocarbon biofuel. While the majority of heterogeneous catalytic processes are conducted in the presence of gas (nearly ideal) or liquid phase, a growing number of processes are utilizing supercritical fluids (SCFs) as reaction media. Although hydrodeoxygenation (HDO) is proven a promising process for pyrolysis bio-oil upgrading to hydrocarbon biofuel, catalyst efficiency remains a challenge. Integrating heterogeneous catalysts with SCFs in a bio-oil HDO process was investigated in this study. Bifunctional Co-Zn/HZSM-5 catalysts were firstly used to upgrade bio-oil to biofuel in supercritical methanol. The loading of Co and Zn did not change HZSM-5 crystalline structure. Physicochemical properties of biofuel produced by Co and/or Zn loaded HZSM-5 catalysts such as water content, total acid number, viscosity and higher heating value improved. Bimetallic Co-Zn/HZSM-5 catalysts showed enhanced reactions of decarboxylation and decarbonylation that resulted in higher yields of CO and CO 2 . Bimetallic Co-Zn/HZSM-5 catalysts were more effective for bio-oil HDO than monometallic Co/HZSM-5 or Zn/HZSM-5 catalyst , which was attributed to the synergistic effect of Co and Zn on HZSM-5 support. Bimetallic Co-Zn/HZSM-5 catalysts increased biofuel yields and hydrocarbons contents in biofuels in comparison with monometallic Co/HZSM-5 and Zn/HZSM-5 catalysts. 5%Co15%Zn/HZSM-5 catalyst generated the highest biofuel yield at 22.13 wt.%, and 15%Co5

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

Energy Technology Data Exchange (ETDEWEB)

Abdullah, Nurhayati; Sulaiman, Fauziah; Taib, Rahmad Mohd [School of Physics, Universiti Sains Malaysia, 11800 USM Pulau Pinang (Malaysia); Miskam, Muhamad Azman [Science and Engineering Research Centre, Universiti Sains Malaysia, 14300 Nibong Tebal, Pulau Pinang (Malaysia)

2015-04-24

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

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.

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

Science.gov (United States)

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

2018-05-01

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

Electrocatalytic upgrading of biomass pyrolysis oils to chemical and fuel

Science.gov (United States)

Lam, Chun Ho

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

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.

Gasoline from biomass through refinery-friendly carbohydrate-based bio-oil produced by ketalization.

Science.gov (United States)

Batalha, Nuno; da Silva, Alessandra V; de Souza, Matheus O; da Costa, Bruna M C; Gomes, Elisa S; Silva, Thiago C; Barros, Thalita G; Gonçalves, Maria L A; Caramão, Elina B; dos Santos, Luciana R M; Almeida, Marlon B B; de Souza, Rodrigo O M A; Lam, Yiu L; Carvalho, Nakédia M F; Miranda, Leandro S M; Pereira, Marcelo M

2014-06-01

The introduction of biomass-derived compounds as an alternative feed into the refinery structure that already exists can potentially converge energy uses with ecological sustainability. Herein, we present an approach to produce a bio-oil based on carbohydrate-derived isopropylidene ketals obtained by reaction with acetone under acidic conditions directly from second-generation biomass. The obtained bio-oil showed a greater chemical inertness and miscibility with gasoil than typical bio-oil from fast pyrolysis. Catalytic upgrading of the bio-oil over zeolites (USY and Beta) yielded gasoline with a high octane number. Moreover, the co-processing of gasoil and bio-oil improved the gasoline yield and quality compared to pure gasoil and also reduced the amount of oxygenated compounds and coke compared with pure bio-oil, which demonstrates a synergistic effect. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Utilization possibilities of palm shell as a source of biomass energy in Malaysia by producing bio-oil in pyrolysis process

International Nuclear Information System (INIS)

Abnisa, Faisal; Daud, W.M.A. Wan; Husin, W.N.W.; Sahu, J.N.

2011-01-01

Agriculture residues such as palm shell are one of the biomass categories that can be utilized for conversion to bio-oil by using pyrolysis process. Palm shells were pyrolyzed in a fluidized-bed reactor at 400, 500, 600, 700 and 800 o C with N 2 as carrier gas at flow rate 1, 2, 3, 4 and 5 L/min. The objective of the present work is to determine the effects of temperature, flow rate of N 2 , particle size and reaction time on the optimization of production of renewable bio-oil from palm shell. According to this study the maximum yield of bio-oil (47.3 wt%) can be obtained, working at the medium level for the operation temperature (500 o C) and 2 L/min of N 2 flow rate at 60 min reaction time. Temperature is the most important factor, having a significant positive effect on yield product of bio-oil. The oil was characterized by Fourier Transform infra-red (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC-MS) techniques. -- Highlights: → This study reports the results of experimental investing of conversion palm shell into bio-oil by using pyrolysis and to find the optimum condition to produce the highest yield of bio-oil. → Several parameters which have effect to the process such as temperature, N 2 flow rate, reaction time and particle size is will be investigated in this study. → The outcome of this result will be important for abatement and control of increasingly waste palm shell storage problems any energy source to the world.

Fast pyrolysis of Miscanthus sinensis in fluidized bed reactors: Characteristics of product yields and biocrude oil quality

International Nuclear Information System (INIS)

Bok, Jin Pil; Choi, Hang Seok; Choi, Joon Weon; Choi, Yeon Seok

2013-01-01

In the present work, fast pyrolysis of Miscanthus sinensis was performed and the product yields and properties of the resulting biocrude oil were determined for varying reactor configurations and pyrolysis temperatures. Two types of reactors (rectangular and cylindrical fluidized beds) were adopted, and pyrolysis temperature was increased from 400 °C to 550 °C. Based on the results, it was found that the reaction temperature greatly influenced the product yield and the characteristics of biocrude oil. The highest yield of biocrude oil for the rectangular reactor was 48.9 wt.%, produced at 500 °C, and the highest yield for the cylindrical reactor was 50.01 wt.%, produced at 450 °C. Additionally, the biocrude oil yield in the rectangular reactor sharply decreased when reaction temperature was increased to 550 °C, while only a slight decrease was observed in the cylindrical reactor. From GC/MS analysis, biocrude oil was found to contain various chemical components, such as nonaromatic ketones, furans, sugars, lignin-derived phenols, guaiacols and syringols. In particular, the sugar content of the biocrude oil produced in rectangular reactor (2.11–9.35 wt.%) was generally lower than that produced in the cylindrical reactor (7.93–10.79 wt.%). - Highlights: • Fast pyrolysis of Miscanthus sinensis was performed in two fluidized bed reactors to obtain biocrude oil. • The yield and characteristics of the biocrude oil were scrutinized with changing reaction temperature and reactor type. • The reaction temperature was found to be the most influencing parameter for the fast pyrolysis reaction. • The different heating rate caused by reactor type has an effect on the final product yield and characteristics

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

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

Science.gov (United States)

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

2013-01-01

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

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

Bio-oil fueled diesel power plant; Biooeljyllae toimiva dieselvoimala

Energy Technology Data Exchange (ETDEWEB)

Vuorinen, A [Modigen Oy, Helsinki (Finland)

1996-12-31

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

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

Optimum conditions for maximising pyrolysis liquids of oil palm empty fruit bunches

International Nuclear Information System (INIS)

Sulaiman, F.; Abdullah, N.

2011-01-01

As production of palm oil is expanding, a more efficient use of oil palm biomass to obtain more energy from oil palm plantations is investigated. The work was carried out on a fluidised bed bench scale fast pyrolysis unit, with the objective of determining the important conditions and key variables which are required to maximise the liquid yield and its quality. The investigation on the impact of reactor temperature, varying residence time by changing the nitrogen flow rate and combined impact of ash content and particle size on the product yields is presented. The properties of the liquid product were analysed and compared with wood derived bio-oil and petroleum fuels. It was found that in all cases the liquid product separated into two phases presenting difficulties for fuel applications, which are critically discussed. Potential solutions are also proposed which include upgrading of the liquid for fuel applications and other useful applications. -- Highlights: → Fibre analysis, proximate analysis and elemental analysis were carried out in this work. → Thermal degradation behaviour of EFB using thermogravimetry and differential thermogravimetry curves is in good agreement with other studies. → Maximum yield for liquids was determined to be around 55% at reactor temperature, 450 o C utilising residence time of 1.03 s → The low organic yield obtained for highest ash content of size below 150 μm is not due to low closure. → The phase separated liquid produced would present a challenging fuel due to its high viscosity and high water content.

Understanding the Behavior of the Oligomeric Fractions During Pyrolysis Oils Upgrading

Science.gov (United States)

Stankovikj, Filip

Fast pyrolysis oils represent most viable renewable sources for production of fuels and chemicals, and they could supplement significant portion of the depleting fossil fuels in near future. Progress on their utilization is impeded by their thermal and storage instability, lack of understanding of their complex composition and behavior during upgrading, including the poorly described water soluble fraction (WS). This work offers two new methodologies for simplified, and sensible description of the pyrolysis oils in terms of functional groups and chemical macro-families, augments our understanding of the composition of the WS, and the behavior of the heavy non-volatile fraction during pyrolysis oils stabilization. The concept of analyzing the volatile and non-volatile fraction in terms of functional groups has been introduced, and the quantification power of spectroscopic techniques (FTIR, 1H-NMR, UV fluorescence) for phenols, carbonyl and carboxyl groups was shown. The FT-ICR-MS van Krevelen diagram revealed the importance of dehydration reactions in pyrolysis oils and the presence of "pyrolytic humins" was hypothesized. For the first time the WS was analyzed with plethora of analytical techniques. This lead to proposition of a new characterization scheme based on functional groups, describing 90-100 wt.% of the bio-oils. The structure of idealized "pyrolytic humin" was further described as a random combination of 3-8 units of dehydrated sugars, coniferyl-type phenols, furans, and carboxylic acids attached on a 2,5-dioxo-6-hydroxyhexanal (DHH) backbone rich in carbonyl groups. TG-FTIR studies resulted in defining rules for fitting pyrolysis oils' DTG curves and assignment of TG residue. This second method is reliable for estimation of water content, light volatiles, WS and WIS. Finally, stabilization of two oils was analyzed through the prism of functional groups. Carbonyl and hydroxyl groups interconverted. The first attempt to follow silent 31P-NMR oxygen was

Biomass catalytic fast pyrolysis over hierarchical ZSM-5 and Beta zeolites modified with Mg and Zn oxides

Czech Academy of Sciences Publication Activity Database

Hernando, H.; Moreno, I.; Fermoso, J.; Ochoa-Hernández, Cristina; Pizarro, P.; Coronado, J. M.; Čejka, Jiří; Serrano, D. P.

2017-01-01

Roč. 7, č. 3 (2017), s. 289-304 ISSN 2190-6815 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : catalytic fast pyrolysis * hierarchial zeolite * bio -oil upgrading Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

Biomass catalytic fast pyrolysis over hierarchical ZSM-5 and Beta zeolites modified with Mg and Zn oxides

Czech Academy of Sciences Publication Activity Database

Hernando, H.; Moreno, I.; Fermoso, J.; Ochoa-Hernández, Cristina; Pizarro, P.; Coronado, J. M.; Čejka, Jiří; Serrano, D. P.

2017-01-01

Roč. 7, č. 3 (2017), s. 289-304 ISSN 2190-6815 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : catalytic fast pyrolysis * hierarchial zeolite * bio-oil upgrading Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

Flash pyrolysis fuel oil: bio-pok

Energy Technology Data Exchange (ETDEWEB)

Gust, S [Neste Oy, Porvoo (Finland)

1997-12-01

Samples of flash pyrolysis liquid produced by Union Fenosa, Spain from pine and straw and samples produced by Ensyn of Canada from mixed hardwoods were combusted with simple pressure atomization equipment commonly used with light fuel oils in intermediate size (0.1-1 MW) boilers. With a number of modifications to the combustion system, carbon monoxide (CO) and nitrous oxide (NO{sub x}) could be reduced to acceptable levels: CO < 30 ppm and NO{sub x} < 140 ppm. Particulate emissions which were initially very high (Bacharach 4-5) were reduced (Bach. 2-3) by system improvements but are still higher than from light fuel oil (Bach. <1). The modifications to the combustion system were: refractory section between burner and boiler, acid resistant progressive cavity pump, higher liquid preheat temperature and higher pressure than for light fuel oils. The main problems with pyrolysis liquids concerns their instability or reactivity. At temperatures above 100 deg C they begin to coke, their viscosity increases during storage and oxygen from air causes skin formation. This requires that special handling procedures are developed for fuel storage, delivery and combustion systems. (orig.)

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

Science.gov (United States)

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

2014-08-01

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

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.

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.

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.

Catalytic flash pyrolysis of oil-impregnated-wood and jatropha cake using sodium based catalysts

NARCIS (Netherlands)

Ali Imran, A.; Bramer, Eduard A.; Seshan, Kulathuiyer; Brem, Gerrit

2016-01-01

Catalytic pyrolysis of wood with impregnated vegetable oil was investigated and compared with catalytic pyrolysis of jatropha cake making use of sodium based catalysts to produce a high quality bio-oil. The catalytic pyrolysis was carried out in two modes: in-situ catalytic pyrolysis and post

Catalytic partial oxidation of pyrolysis oils

Science.gov (United States)

Rennard, David Carl

2009-12-01

details the catalytic partial oxidation of glycerol without preheat: droplets of glycerol are sprayed directly onto the top of the catalyst bed, where they react autothermally with contact times on the order of tau ≈ 30 ms. The reactive flash volatilization of glycerol results in equilibrium syngas production over Rh-Ce catalysts. In addition, water can be added to the liquid glycerol, resulting in true autothermal reforming. This highly efficient process can increase H2 yields and alter the H2 to CO ratio, allowing for flexibility in syngas quality depending on the purpose. Chapter 5 details the results of a time on stream experiment, in which optimal syngas conditions are chosen. Although conversion is 100% for 450 hours, these experiments demonstrate the deactivation of the catalyst over time. Deactivation is exhibited by decreases in H2 and CO 2 production accompanied by a steady increase in CO and temperature. These results are explained as a loss of water-gas shift equilibration. SEM images suggest catalyst sintering may play a role; EDS indicates the presence of impurities on the catalyst. In addition, the instability of quartz in the reactor is demonstrated by etching, resulting in a hole in the reactor tube at the end of the experiment. These results suggest prevaporization may be desirable in this application, and that quartz is not a suitable material for the reactive flash volatilization of oxygenated fuels. In Chapter 6, pyrolysis oil samples from three sources - poplar, pine, and hardwoods - are explored in the context of catalytic partial oxidation. Lessons derived from the tests with model compounds are applied to reactor design, resulting in the reactive flash vaporization of bio oils. Syngas is successfully produced, though deactivation due to coke and ash deposition keeps H2 below equlibrium. Coke formation is observed on the reactor walls, but is avoided between the fuel injection site and catalyst by increasing the proximity of these in the reactor

Catalytic flash pyrolysis of oil-impregnated-wood and jatropha cake using sodium based catalysts

KAUST Repository

Imran, Ali; Bramer, Eddy A.; Seshan, Kulathuiyer; Brem, Gerrit

2015-01-01

Catalytic pyrolysis of wood with impregnated vegetable oil was investigated and compared with catalytic pyrolysis of jatropha cake making use of sodium based catalysts to produce a high quality bio-oil. The catalytic pyrolysis was carried out in two

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.

Experimental investigation of flash pyrolysis oil droplet combustion

DEFF Research Database (Denmark)

Ibrahim, Norazana; Jensen, Peter A.; Dam-Johansen, Kim

2013-01-01

at a temperature ranging between 1000 and 1400°C with an initial gas velocity of 1.6 m/s and oxygen concentration of 3%. The evolution of combustion of bio-oil droplets was recorded by a digital video camera. It was observed that the combustion behaviour of pyrolysis oil droplet differ from the heavy oil in terms......The aim of this work is to investigate and compare the combustion behaviour of a single droplet of pyrolysis oil derived from wheat straw and heavy fossil oil in a single droplet combustion chamber. The initial oil droplet diameters were in between 500 μm to 2500 μm. The experiments were performed...

The characteristics of palm oil plantation solid biomass wastes as raw material for bio oil

Science.gov (United States)

Yanti, RN; Hambali, E.; Pari, G.; Suryani, A.

2018-03-01

Indonesia is the largest palm oil plantations estate in the world. It reached 11,30 million hectares in 2015 and increased up to 11,67 million hectares in 2016. The advancement of technology recent, the solid waste of palm oil plantation can be re-produced become bio oil through pyrolysis hydrothermal process and utilized for biofuel. The purpose of this research was to analyze the characteristics of feedstock of bio oil of solid waste of palm oil plantations estate. The feedstock used was derived from solid waste of palm oil plantations in Riau Province. Characteristic analysis of waste oil included chemical compound content (cellulose, hemicellulose, lignin), ultimate analysis (C, H, N, O, S) to know height heating value (HHV). The result of analysis of chemical content showed that solid waste of palm cellulose 31,33 – 66,36 %, hemicellulose 7,54 – 17,94 %, lignin 21,43 - 43,1. The HHV of hydrothermal pyrolysis feedstock was 15,18 kJ/gram - 19,57 kJ/gram. Generally, the solid waste of palm oil plantations estate containing lignocellulose can be utilized as bio oil through hydrothermal pyrolysis. The CG-MS analysis of bio oil indicated hydrocarbon contents such as pentadecane, octadecane, hexadecane and benzene.

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).

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

Decarbonisation of olefin processes using biomass pyrolysis oil

International Nuclear Information System (INIS)

Sharifzadeh, M.; Wang, L.; Shah, N.

2015-01-01

Highlights: • Decarbonization of olefin processes using biomass pyrolysis oil was proposed. • The decarbonization is based on integrated catalytic processing of bio-oil. • The retrofitted process features significant economic and environmental advantages. - Abstract: An imperative step toward decarbonisation of current industrial processes is to substitute their petroleum-derived feedstocks with biomass and biomass-derived feedstocks. For decarbonisation of the petrochemical industry, integrated catalytic processing of biomass pyrolysis oil (also known as bio-oil) is an enabling technology. This is because, under certain conditions, the reaction products form a mixture consisting of olefins and aromatics, which are very similar to the products of naphtha hydro-cracking in the conventional olefin processes. These synergies suggest that the catalytic bio-oil upgrading reactors can be seamlessly integrated to the subsequent separation network with minimal retrofitting costs. In addition, the integrated catalytic processing provides a high degree of flexibility for optimization of different products in response to market fluctuations. With the aim of assessing the techno-economic viability of this pathway, five scenarios in which different fractions of bio-oil (water soluble/water insoluble) were processed with different degrees of hydrogenation were studied in the present research. The results showed that such a retrofit is not only economically viable, but also provides a high degree of flexibility to the process, and contributes to decarbonisation of olefin infrastructures. Up to 44% reductions in greenhouse gas emissions were observed in several scenarios. In addition, it was shown that hydrogen prices lower than 6 $/kg will result in bio-based chemicals which are cheaper than equivalent petrochemicals. Alternatively, for higher hydrogen prices, it is possible to reform the water insoluble phase of bio-oil and produce bio-based chemicals, cheaper than

Application of Gamma Radiation on Bio-oil Produced from Pyrolysis of Soybean Cake

International Nuclear Information System (INIS)

Pichestapong, P.; Injarean, U.; Prapakornrattana, P.; Charoen, K.

2014-01-01

Soybean cake residue from soy milk making can be pyrolysed to produce pyrolysis liquid or bio-oil which has potency to be used as liquid fuel. Pyrolysis of soybean cake residue with the application of gamma irradiation was investigated in a batch reactor at 450°C for 1.5 hr under nitrogen flow 250 cc/min. Feed of soybean cake residue was exposed to gamma radiation at the doses of 200 to 1,000 kGy before pyrolysing. It was found that pyrolysis liquid yield increased significantly by 12.9 to 19.3 % at the irradiation doses of 400 kGy and higher. The increment was mainly due to the increasing of aqueous phase in the pyrolysis liquid. The heating value of organic phase in the pyrolysis liquid was 7,890 kcal/kg. The organic phase from the unexposed feed was also irradiated at 20-100 kGy. The viscosity of irradiated organic phase was found to increase with the increasing irradiation dose. Irradiated organic phase was distilled at temperatures 200 and 250°C. It was found that the first distilled fraction (<200°C) corresponding to gasoline fraction increased with the increasing irradiation dose while the second distilled fraction (200-250°C) corresponding to kerosene fraction seems to decrease. The composition of organic phase was also determined by GC-MS.

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

Science.gov (United States)

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

2018-01-01

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

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.

Pyrolysis Recovery of Waste Shipping Oil Using Microwave Heating

Directory of Open Access Journals (Sweden)

Wan Adibah Wan Mahari

2016-09-01

Full Text Available This study investigated the use of microwave pyrolysis as a recovery method for waste shipping oil. The influence of different process temperatures on the yield and composition of the pyrolysis products was investigated. The use of microwave heating provided a fast heating rate (40 °C/min to heat the waste oil at 600 °C. The waste oil was pyrolyzed and decomposed to form products dominated by pyrolysis oil (up to 66 wt. % and smaller amounts of pyrolysis gases (24 wt. % and char residue (10 wt. %. The pyrolysis oil contained light C9–C30 hydrocarbons and was detected to have a calorific value of 47–48 MJ/kg which is close to those traditional liquid fuels derived from fossil fuel. The results show that microwave pyrolysis of waste shipping oil generated an oil product that could be used as a potential fuel.

Characterization of fly ash from bio and municipal waste

DEFF Research Database (Denmark)

Lima, Ana T.; Ottosen, Lisbeth M.; Pedersen, Anne Juul

2008-01-01

the co-combustion of wood and oil. The focus is laid on differences in ash characteristics and on the mobility of Cd and Cr. These two heavy metals are chosen because Cd is the problematic heavy metal in bio ashes and Cr is problematic in many ash stabilization methods (in the Cr(VI) state). Based...

The feasibility of bio-oil production and application on the basis of the rotating cone technology

International Nuclear Information System (INIS)

Gansekoele, E.; Wagenaar, B.M.

2001-07-01

The overall objective of the project on the title subject is to scale up the novel, rotating cone technology for flash pyrolysis of biomass and examine the related bio-energy system by application of bio-oil from several feedstocks in engines and combustion chambers. The specific objectives are: (1) To identify and characterize biomass feedstocks suitable for conversion to bio-oil by means of flash pyrolysis in a rotating cone reactor; (2) To scale-up the rotating cone reactor to a commercial size (200 kg biomass per hour); (3) To optimize the process with respect to quality and yield of the bio-oil in various test runs; (4) To produce bio-oil from various feedstocks in long lasting production runs; (5) To characterize the bio-oil and test it in properly adapted diesel engines and furnaces; and (6) To estimate the market potential for bio-oil and the economic feasibility of the technology. The objectives of the partners are: (1) to establish the most cost effective pre-treatment procedures to produce proper biomass feedstock for the pyrolysis process. In addition, 25 tons of pretreated biomass feedstock was prepared (CIEMAT, Spain); (2) design of the rotating cone pyrolysis plant at a biomass throughput of 200 kg/h, optimization of the pilot plant, and carrying out long duration runs (BTG, Netherlands); (3) development and construction of the flash pyrolysis pilot plant (KARA, Netherlands); and (4) investigation of the application of bio-oil in a combustion chamber, in a gas turbine and a diesel engine with respect to performance, efficiencies and emissions ( Rostock University, Germany). This report comprises the research results of all the partners for the whole chain: from biomass pre-treatment to bio-oil production and application. The different subjects are Biomass pre-treatment, Development of the 200 kg/h pyrolysis plant, Bio-oil application, and Economics and market potential of bio-oil application. refs

Optimization and characterization studies on bio-oil production from palm shell by pyrolysis using response surface methodology

International Nuclear Information System (INIS)

Abnisa, Faisal; Wan Daud, W.M.A.; Sahu, J.N.

2011-01-01

In this work palm shell waste was pyrolyzed to produces bio-oil. The effects of several parameters on the pyrolysis efficiency were tested to identify the optimal bio-oil production conditions. The tested parameters include temperature, N 2 flow rate, feed-stock particle size, and reaction time. The experiments were conducted using a fix-bed reactor. The efficient response surface methodology (RSM), with a central composite design (CCD), were used for modeling and optimization the process parameters. The results showed that the second-order polynomial equation explains adequately the non-linear nature of the modeled response. An R 2 value of 0.9337 indicates a sufficient adjustment of the model with the experimental data. The optimal conditions found to be at the temperature of 500 o C, N 2 flow rate of 2 L/min, particle size of 2 mm and reaction time of 60 min and yield of bio-oil was approximately obtained 46.4 wt %. In addition, Fourier Transform infra-red (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC-MS) were used to characterize the gained bio-oil under the optimum condition. -- Highlights: → The RSM, with a CCD, was used for modeling and optimization for bio-oil synthesis. → The obtained model explains adequately the non-linear nature. → An R 2 value of 0.9337 ensures a sufficient adjustment of the model. → It explains the importance of the experimental factors, their interactions.

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.

Regional differences in the economic feasibility of advanced biorefineries: Fast pyrolysis and hydroprocessing

International Nuclear Information System (INIS)

Brown, Tristan R.; Thilakaratne, Rajeeva; Brown, Robert C.; Hu, Guiping

2013-01-01

This analysis identifies the sensitivity of the fast pyrolysis and hydroprocessing pathway to facility location. The economic feasibility of a 2000 metric ton per day fast pyrolysis and hydroprocessing biorefinery is quantified based on 30 different state-specific facility locations within the United States. We calculate the 20-year internal rate of return (IRR) and net present value (NPV) for each location scenario as a function of state- and region-specific factors. This analysis demonstrates that biorefinery IRR and NPV are very sensitive to bio-oil yield, feedstock cost, location capital cost factor, and transportation fuel market value. The IRRs and NPVs generated for each scenario vary widely as a result, ranging from a low of 7.4% and −$79.5 million in Illinois to a high of 17.2% and $165.5 million in Georgia. The results indicate that the economic feasibility of the fast pyrolysis and hydroprocessing pathway is strongly influenced by facility location within the United States. This result could have important implications for cellulosic biofuel commercialization under the revised Renewable Fuel Standard. - Highlights: ► We model the production of biofuel via fast pyrolysis and hydroprocessing of biomass. ► We compile regional- and state-specific factors for 30 different US state scenarios. ► We quantify facility economic feasibility under each state scenario. ► Facility economic feasibility is strongly influenced by facility location

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-12-01

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

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. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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

2016-01-01

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

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

Science.gov (United States)

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

Fast pyrolysis of biomass in the rotating cone reactor. Reactor development and operation. Final report

International Nuclear Information System (INIS)

Gansekoele, E.; Wagenaar, B.M.

2001-07-01

This report describes the design and characteristics of BTGs pyrolysis plant with a biomass throughput capacity of 50 kg per hour. The pilot plant has been developed for 2 reasons: to produce modest quantities of bio-oil for application purposes, and to generate know-how for the development of a larger 200 kg/hr pilot plant. The design of the 50 kg/hr plant continues the development line which started in 1995 when a similar unit was delivered to China. Major design improvements of the current pyrolysis unit are that it can be operated in a continuous mode and utilizes the combustion heat of the produced char to heat the pyrolysis process. A measurement program has meanwhile been executed as a means to characterize the pyrolysis plant. Results of the characterization study were the following: the pilot plant produces approx. 35 liters of bio-oil per hour and thus achieves a maximum oil yield of 70 weight percent. The bio-oil yield of the plant was inversely proportional with the reactor temperature and inversely proportional with the gas phase residence time. As a result of the pilot plant operation, a few tons of bio-oil have been produced; alongside with a bulk of know-how. All know-how has successfully been utilized in the development of the 200 kg per hour facility

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.

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

Science.gov (United States)

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

2018-03-01

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

Oxidative pyrolysis of kraft lignin in a bubbling fluidized bed reactor with air

International Nuclear Information System (INIS)

Li, Dongbing; Briens, Cedric; Berruti, Franco

2015-01-01

Fast pyrolysis of kraft lignin with partial (air) oxidation was studied in a bubbling fluidized bed reactor at reaction temperatures of 773 and 823 K. The bio-oil vapors were fractionated using a series of three condensers maintained at desired temperatures, providing a dry bio-oil with less than 1% water and over 96% of the total bio-oil energy. Oxygen feed was varied to study its effect on yield, composition, and energy recovery in the gas, char and oil products. The addition of oxygen to the pyrolysis process increased the production of gases such as CO and CO 2 . It also changed the dry bio-oil properties, reducing its heating value, increasing its oxygen content, reducing its average molecular weight and tar concentration, while increasing its phenolics concentration. The lower reaction temperature of 773 K was preferred for both dry bio-oil yield and quality. Autothermal operation of the pyrolysis process was achieved with an oxygen feed of 72 or 54 g per kg of biomass at the reaction temperatures of 773 and 823 K, respectively. Autothermal operation reduced both yield and total energy content of the dry bio-oil, with relative reductions of 24 and 20% for the yield, 28 and 23% for the energy content, at 773 and 823 K. - Highlights: • Autothermal pyrolysis of Kraft lignin is possible with introduction of air. • Under autothermal conditions, 24% of the dry bio-oil chemicals are lost at 773 K. • Partial oxidation helps produce more simple phenols and less pyrolytic lignin. • Bio-oil from lignin pyrolysis has a very high phenolics concentration

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.

The role of phenols from bagasse vacuum pyrolysis bio-oil in cupper sulfured ore flotation

Directory of Open Access Journals (Sweden)

L. E. Brossard

2008-12-01

Full Text Available Vacuum pyrolysis bagasse bio-oil collected in a series of sequential fractions was analyzed for total percentage of phenols and levoglucosan components. It was established that the ratio total phenols- to-levoglucosan could be used as an indicator of the performance of alkaline solutions of bio-oil fractions (SABO when they are used as foaming agents to benefit flotation of sulfured cupper minerals. A high total phenol-to-levoglucosan ratio results in high percentages of Cu in cupper flotation concentrates, L Cu. A closer look at the role of individual phenols reveals that p-cresol is the main phenol, although not the only one, responsible for the observed behavior. Additionally it was noted that rather high doses of these foaming agents must be used to obtain desirable results in flotation processes. A production cost estimate allows consideration of SABO as an alternative to others commercial foaming agents, especially if an optimization study reduces doses of SABO.

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.

Lamellar and pillared ZSM-5 zeolites modified with MgO and ZnO for catalytic fast-pyrolysis of eucalyptus woodchips

Czech Academy of Sciences Publication Activity Database

Fermoso, J.; Hernando, H.; Jana, P.; Moreno, I.; Přech, Jan; Ochoa-Hernández, Cristina; Pizzaro, P.; Coronado, J. M.; Čejka, Jiří

2016-01-01

Roč. 277, č. 1 (2016), s. 171-181 ISSN 0920-5861 R&D Projects: GA ČR(CZ) GAP106/12/0189 EU Projects: European Commission(XE) 604307 - CASCATBEL Institutional support: RVO:61388955 Keywords : lignocellulosic biomass * catalytic fast-pyrolysis * bio-oil Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.636, year: 2016

Combustion Characterization of Individual Bio-oil Droplets

DEFF Research Database (Denmark)

Hansen, Brian Brun; Jensen, Peter Arendt

2015-01-01

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...

Supply chain design under uncertainty for advanced biofuel production based on bio-oil gasification

International Nuclear Information System (INIS)

Li, Qi; Hu, Guiping

2014-01-01

An advanced biofuels supply chain is proposed to reduce biomass transportation costs and take advantage of the economics of scale for a gasification facility. In this supply chain, biomass is converted to bio-oil at widely distributed small-scale fast pyrolysis plants, and after bio-oil gasification, the syngas is upgraded to transportation fuels at a centralized biorefinery. A two-stage stochastic programming is formulated to maximize biofuel producers' annual profit considering uncertainties in the supply chain for this pathway. The first stage makes the capital investment decisions including the locations and capacities of the decentralized fast pyrolysis plants as well as the centralized biorefinery, while the second stage determines the biomass and biofuels flows. A case study based on Iowa in the U.S. illustrates that it is economically feasible to meet desired demand using corn stover as the biomass feedstock. The results show that the locations of fast pyrolysis plants are sensitive to uncertainties while the capacity levels are insensitive. The stochastic model outperforms the deterministic model in the stochastic environment, especially when there is insufficient biomass. Also, farmers' participation can have a significant impact on the profitability and robustness of this supply chain. - Highlights: • Decentralized supply chain design for advanced biofuel production is considered. • A two-stage stochastic programming is formulated to consider uncertainties. • Farmers' participation has a significant impact on the biofuel supply chain design

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

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.

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

Production of biodiesel from Parinari polyandra B. seed oil using bio ...

African Journals Online (AJOL)

Two agricultural residues, cocoa pod ash (CPA) and rice husk ash (RHA), were investigated as bio-based catalysts for the transesterification of Parinari polyandra seeds oil and the results obtained using these bio-based catalysts were compared with potassium hydroxide which is a conventional catalyst. Oil was extracted ...

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.

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

Directory of Open Access Journals (Sweden)

Yong Cui

2017-06-01

Full Text Available 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.

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).

A kinetic reaction model for biomass pyrolysis processes in Aspen Plus

International Nuclear Information System (INIS)

Peters, Jens F.; Banks, Scott W.; Bridgwater, Anthony V.; Dufour, Javier

2017-01-01

Highlights: • Predictive kinetic reaction model applicable to any lignocellulosic feedstock. • Calculates pyrolysis yields and product composition as function of reactor conditions. • Detailed modelling of product composition (33 model compounds for the bio-oil). • Good agreement with literature regarding yield curves and product composition. • Successful validation with pyrolysis experiments in bench scale fast pyrolysis rig. - Abstract: This paper presents a novel kinetic reaction model for biomass pyrolysis processes. The model is based on the three main building blocks of lignocellulosic biomass, cellulose, hemicellulose and lignin and can be readily implemented in Aspen Plus and easily adapted to other process simulation software packages. It uses a set of 149 individual reactions that represent the volatilization, decomposition and recomposition processes of biomass pyrolysis. A linear regression algorithm accounts for the secondary pyrolysis reactions, thus allowing the calculation of slow and intermediate pyrolysis reactions. The bio-oil is modelled with a high level of detail, using up to 33 model compounds, which allows for a comprehensive estimation of the properties of the bio-oil and the prediction of further upgrading reactions. After showing good agreement with existing literature data, our own pyrolysis experiments are reported for validating the reaction model. A beech wood feedstock is subjected to pyrolysis under well-defined conditions at different temperatures and the product yields and compositions are determined. Reproducing the experimental pyrolysis runs with the simulation model, a high coincidence is found for the obtained fraction yields (bio-oil, char and gas), for the water content and for the elemental composition of the pyrolysis products. The kinetic reaction model is found to be suited for predicting pyrolysis yields and product composition for any lignocellulosic biomass feedstock under typical pyrolysis conditions

Detailed characterization of bio-oil from pyrolysis of non-edible seed-cakes by Fourier Transform Infrared Spectroscopy (FTIR) and gas chromatography mass spectrometry (GC-MS) techniques.

Science.gov (United States)

Sugumaran, Vatsala; Prakash, Shanti; Ramu, Emmandi; Arora, Ajay Kumar; Bansal, Veena; Kagdiyal, Vivekanand; Saxena, Deepak

2017-07-15

Bio-oil obtained from pyrolysis is highly complicated mixture with valued chemicals. In order to reduce the complexity for unambiguous characterization of components present in bio-oil, solvent extractions using different solvents with increasing polarity have been adopted. The fractions have been analyzed by Fourier transform infrared (FTIR) spectroscopy for identifying the functional groups and Gas chromatography-mass spectrometry (GC-MS), for detailed characterization of components present in various fractions, thereby providing in-depth information at molecular level of various components in bio-oil. This paper reveals the potential of the analytical techniques in identification and brings out the similarities as well as differences in the components present in the bio-oil obtained from two non-edible oil seed-cakes, viz., Jatropha and Karanjia. Copyright © 2017 Elsevier B.V. All rights reserved.

Opportunities for biomass-derived 'bio-oil' in European heat and power markets

International Nuclear Information System (INIS)

Brammer, J.G.; Lauer, M.; Bridgwater, A.V.

2006-01-01

Bio-oil (biomass fast pyrolysis) systems for heat, power or CHP production are nearing demonstration status. Their commercial attractiveness will depend on many factors, and will vary with the application, the scale, and importantly the location and its associated economic and logistical factors. The objective of this work, carried out as part of an EC-ALTENER project, was to evaluate the opportunities for bio-oil in the heat and power markets of Europe. Bio-oil applications were compared with conventional (fossil) alternatives for the same heat and power duty. The evaluation was carried out by a quantitative assessment of the economic competitiveness of standard applications in 14 European countries. Location-specific data were collected, and combined with technology-specific data obtained from earlier work. A competitiveness factor (c F ) was derived which represents the total annual cost of a conventional alternative relative to a bio-oil application. The results showed a wide variation across Europe. A total of six countries had at least one bio-oil application which was economically competitive. Heat-only applications were found to be the most economically competitive, followed by CHP applications, with electricity-only applications only very rarely competitive. For a given technology, the larger the scale, the better the competitiveness

Opportunities for biomass-derived 'bio-oil' in European heat and power markets

International Nuclear Information System (INIS)

Brammer, J.G.; Bridgwater, A.V.

2006-01-01

Bio-oil (biomass fast pyrolysis) systems for heat, power or CHP production are nearing demonstration status. Their commercial attractiveness will depend on many factors, and will vary with the application, the scale, and importantly the location and its associated economic and logistical factors. The objective of this work, carried out as part of an EC-ALTENER project, was to evaluate the opportunities for bio-oil in the heat and power markets of Europe. Bio-oil applications were compared with conventional (fossil) alternatives for the same heat and power duty. The evaluation was carried out by a quantitative assessment of the economic competitiveness of standard applications in 14 European countries. Location-specific data were collected, and combined with technology-specific data obtained from earlier work. A competitiveness factor (c F ) was derived which represents the total annual cost of a conventional alternative relative to a bio-oil application. The results showed a wide variation across Europe. A total of six countries had at least one bio-oil application which was economically competitive. Heat-only applications were found to be the most economically competitive, followed by CHP applications, with electricity-only applications only very rarely competitive. For a given technology, the larger the scale, the better the competitiveness. (author)

Pyrolysis of marine biomass to produce bio-oil and its upgrading using a novel multi-metal catalyst prepared from the spent car catalytic converter.

Science.gov (United States)

Sabegh, Mahzad Yaghmaei; Norouzi, Omid; Jafarian, Sajedeh; Khosh, Akram Ghanbari; Tavasoli, Ahmad

2018-02-01

In order to reduce the economic and environmental consequences caused by spent car catalyst, we herein report for the first time a novel promising multi-metal catalyst prepared from spent car catalytic converters to upgrade the pyrolysis bio-oils. The physico-chemical properties of prepared catalyst were characterized by XRD, EDS, FESEM, and FT-IR analyses. The thermal stability of the multi-metal catalyst was studied with TGA. To investigate the activity of the catalyst, Conversion of Cladophora glomerata (C. glomerata) into bio-products was carried out via a fixed bed reactor with and without catalyst at the temperature of 500°C. Although the catalyst didn't catalyze the gasification reaction, bio-oil was upgraded over the catalyst. The main effect of the catalyst on the bio-oil components is deoxygenating of nitrogen compounds and promotion the ketonization reaction, which converts acid to ketone and declines the corrosive nature of bio-oil. Copyright © 2017. Published by Elsevier Ltd.

Fast pyrolysis of lignin, macroalgae and sewage sludge

DEFF Research Database (Denmark)

Trinh, Ngoc Trung

effect on the product distributions of the lignin and sewage sludge PCR pyrolysis, as well as their bio-oil properties with respect to molecular mass distribution, identified GC-MS component compositions, water-insoluble fraction, viscosity, and HHV. A maximum of organic oil yields of lignin and sewage...... samples of wood, char and grinded char with respect to phase transitions, rheological properties, elemental composition, and energy density were investigated. Also pumping properties were investigated at temperatures of 25, 40 and 60 ºC and the solids loading of 0 - 20 wt%. The bioslurries obtained...... of the condenser nozzle and high rotor speed for obtaining high bio-oil. The recognized limitations lead to that the old PCR set-up cannot be safely scaled up and perform well in a continuous mode. Thus a new set-up with significant modifications of reactor and bio-condenser has been manufactured to overcome...

The scope for generating bio-oils with relatively low oxygen contents via hydropyrolysis

Energy Technology Data Exchange (ETDEWEB)

Rocha, J.D. [Strathclyde Univ., Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry; Universidade Estadual de Campinas (Brazil). Dept. Fisica Aplicada; Luengo, C.A. [Universidade Estadual de Campinas (Brazil). Dept. Fisica Aplicada; Snape, C.E. [Strathclyde Univ., Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry

1999-07-01

The primary oils obtained in high yields from fast (fluidised-bed) pyrolysis of biomass generally have high oxygen contents (ca. 40% w/w). The scope for using pyrolysis under hydrogen pressure (hydropyrolysis), to give oils with much lower oxygen contents compared to normal pyrolysis has been investigated. Fixed-bed hydropyrolysis tests have been conducted on cellulose, sugar cane bagasse and eucalyptus wood using hydrogen pressures up to 10 MPa, with heating rates of 5 and 300{sup o}C min{sup -1}. A colloidal FeS catalyst was used in some tests (Fe loading of 5%, w/w) to increase overall conversions. Further, the attractive option of using a two-stage reactor in which the primary oil vapors are passed though a bed of hydrotreating catalyst is also described. Raising the hydrogen pressure from atmospheric to 10 MPa reduced the oxygen content of the primary oil by over 10% to below 20% w/w. The addition of a dispersed iron sulphide catalyst gave conversions close to 100% for all three biomass samples investigated at 10 MPa under conditions in the fixed-bed reactor where significant diffusional resistances existed and reduced the oxygen content of the bio-oil by a further 10%. Although NMR indicated that the oils became increasingly aromatic as more oxygen was removed, the increase in hydrogen pressure decreased the extent of overall aromatisation that occurs primarily due to the lower char yields obtained. In two-stage tests for cellulose, using a commercial sulphided Ni/Mo {gamma}-Al{sub 2}O{sub 3} catalyst at 400{sup o}C, increasing the hydrogen pressure from 2.5 to 10 MPa decreased the oxygen content of the oil by over 20% to 10% w/w. The H/C ratios were higher and O/C ratios smaller for the two-stage bio-oils compared to their single stage counterparts. However, the differences in the O/C ratios between the single and two-stage bio-oils increase with pressure. (author)

Understanding the Impacts of AFEX™ Pretreatment and Densification on the Fast Pyrolysis of Corn Stover, Prairie Cord Grass, and Switchgrass.

Science.gov (United States)

Sundaram, Vijay; Muthukumarappan, Kasiviswanathan; Gent, Stephen

2017-03-01

Lignocellulosic feedstocks corn stover, prairie cord grass, and switchgrass were subjected to ammonia fiber expansion (AFEX™) pretreatment and densified using extrusion pelleting and ComPAKco densification technique. The effects of AFEX™ pretreatment and densification were studied on the fast pyrolysis product yields. Feedstocks were milled in a hammer mill using three different screen sizes (2, 4, and 8 mm) and were subjected to AFEX™ pretreatment. The untreated and AFEX™-pretreated feedstocks were moisture adjusted at three levels (5, 10, and 15 % wb) and were extruded using a lab-scale single screw extruder. The barrel temperature of the extruder was maintained at 75, 100, and 125 °C. Durability of the extruded pellets made from AFEX™-pretreated corn stover, prairie cord grass, and switchgrass varied from 94.5 to 99.2, 94.3 to 98.7, and 90.1 to 97.5 %, respectively. Results of the thermogravimetric analysis showed the decrease in the decomposition temperature of the all the feedstocks after AFEX™ pretreatment indicating the increase in thermal stability. Loose and densified feedstocks were subjected to fast pyrolysis in a lab-scale reactor, and the yields (bio-oil and bio-char) were measured. Bio-char obtained from the AFEX™-pretreated feedstocks exhibited increased bulk and particle density compared to the untreated feedstocks. The properties of the bio-oil were statistically similar for the untreated, AFEX™-pretreated, and AFEX™-pretreated densified feedstocks. Based on the bio-char and bio-oil yields, the AFEX™-pretreated feedstocks and the densified AFEX™-pretreated feedstocks (pellets and PAKs) exhibited similar behavior. Hence, it can be concluded that densifying the AFEX™-pretreated feedstocks could be a viable option in the biomass-processing depots to reduce the transportation costs and the logistical impediments without affecting the product yields.

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

Pyrolysis Characteristics of Corn Stalk with Solid Heat Carrier

Directory of Open Access Journals (Sweden)

Min Guo

2015-05-01

Full Text Available Pyrolysis of corn stalk with a solid heat carrier was studied under temperatures ranging from 430 to 620 °C. The solid heat carrier used was high-temperature ash from a CFB boiler. The yields of three products and their characteristics were investigated. Moreover, the distributions of sulfur and nitrogen in the products were determined. The results indicate that with increasing temperature, the char yield decreased, gas yield increased, and calorific value of the gas increased from 10.13 to 16.65 MJ/m3. The yield of bio-oil reached a maximum, 14.24 wt.%, at 510 °C. Light-oil in the bio-oil accounted for more than 69.12 wt.%. The elemental composition of the char and char ash were analyzed. The distribution of sulfur and nitrogen in the char decreased to 60.44 and 46.52 wt.%, respectively, depending on the raw materials used. These results provide basic data for the possible industrial application of corn stalk.

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

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...

Catalytic upgrading of biomass pyrolysis vapours using Faujasite zeolite catalysts

NARCIS (Netherlands)

Nguyen, T.S.; Zabeti, M.; Lefferts, Leonardus; Brem, Gerrit; Seshan, Kulathuiyer

2012-01-01

Bio-oil produced via fast pyrolysis of biomass has the potential to be processed in a FCC (fluid catalytic cracking) unit to generate liquid fuel. However, this oil requires a significant upgrade to become an acceptable feedstock for refinery plants due to its high oxygen content. One promising

Production and characterization of Lemna minor bio-char and its catalytic application for biogas reforming

International Nuclear Information System (INIS)

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

2012-01-01

Pyrolysis of fast-growing aquatic biomass - Lemna minor (commonly known as duckweed) with the emphasis on production, characterization and catalytic application of bio-char is reported in this paper. The yield of bio-char was determined as a function of L. minor pyrolysis temperature and sweep gas flow rate. It was found that the pore development during L. minor pyrolysis was not significant and the changes in the reaction conditions (temperature and sweep gas flow rate) did not alter markedly the textural characteristics and BET surface area of the bio-char produced. Thermogravimetric/differential thermogravimetric (TG/DTG) analyses of L. minor and different bio-char samples in inert (helium) and oxidative (air) media showed substantial differences in their TG/DTG patterns. A comparison of scanning electron micrographs (SEM) of L. minor, bio-char and ash indicated that the basic structural features of L. minor remained intact and were not affected by thermolysis. The inorganic ash content of L. minor derived bio-char is significantly higher than that of typical terrestrial (plant) biomass. The energy dispersive spectroscopic (EDS) analysis of L. minor ash showed that it mostly consisted of silica, and small quantities of Na, K and Ca compounds. The treatment of bio-char with CO 2 at 800 °C increased its BET surface area. It was found that CO 2 -treated bio-char exhibited appreciable initial catalytic activity in biogas reforming. -- Highlights: ► New data on characterization of bio-chars derived from Lemna minor are presented. ► Effect of pyrolysis operational parameters on bio-char properties is determined. ► Basic skeletal structure of Lemna minor leaflets does not change during pyrolysis. ► Bio-chars show an appreciable initial catalytic activity for biogas reforming.

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).

Behenic acid pyrolysis to produce diesel-like hydrocarbons

International Nuclear Information System (INIS)

Xu, Zhi-Xiang; Liu, Peng; Xu, Gui-Sheng; He, Zhi-Xia; Ji, Heng-Song; Wang, Qian

2017-01-01

Highlights: • Behenic acid is a suitable bio-renewable resource to produce bio-fuel oil using catalytic cracking. • Little fraction of aromatic compounds presented in bio-fuel oil. • Carbon chain of fatty acid was cracked to form short carbon chain carboxyl firstly. • ESI FT-ICR MS experiment was an effective method to analyze bio-fuel oil heavy compounds. - Abstract: In order to obtain diesel-like bio-fuel oil, behenic acid was selected to carry out fast pyrolysis. The decomposition temperature of behenic acid was in the range of 250–450 °C at 20 k/min according to TG experiment. The bio-fuel oil mainly contained alkane, alkene and fatty acid. Components of products were C_1_3–C_2_0 hydrocarbon. Little fraction of aromatic compounds was found in bio-fuel oil. According to ESI FT-ICR MS analysis results, the oxygen containing compounds in bio-fuel oil were mainly O_2–O_4 classes, with the O_3 being the major class. According to GC–MS and ESI FT-ICR MS results, it was found that the carbon chain of behenic acid was cracked to form short carbon chain carboxyl firstly. And then decarboxylation reaction carried out. In other means carboxyl groups were more stable than carbon chain of fatty acid. The probable mechanism of O_4 species was free radical reaction. The recommended pyrolysis path was also proposed. Diesel-like bio-fuel oil can be obtained using behenic acid catalytic cracking.

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

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)

1996-12-31

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

Fast pyrolysis of linseed. Product yields and compositions

Energy Technology Data Exchange (ETDEWEB)

Acikgoz, C.; Onay, O.; Kockar, O.M. [Department of Chemical Engineering, Faculty of Engineering and Architecture, Iki Eylul Campus, Anadolu University, Eskisehir 26470 (Turkey)

2004-06-01

Fixed-bed fast pyrolysis experiments have been conducted on a sample of linseed (Linum usitatissimum L.) to determine particularly the effect of pyrolysis temperature, heating rate, particle size and sweep gas flow rate on the pyrolysis product yields and their compositions. The maximum oil yield of 57.7wt.% was obtained at a final pyrolysis temperature of 550C, particle size range 0.6mmpyrolysis products were characterised by elemental analysis and various chromatographic and spectroscopic techniques. Chromatographic and spectroscopic studies on oil showed that it can be used as a renewable fuel and chemical feedstock, with a calorific value of 38.45MJ/kg and empirical formula of CH{sub 1.64}O{sub 0.11}N{sub 0.03}.

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. Copyright © 2014 Elsevier Ltd. All rights reserved.

Analytical characterization of products obtained from slow pyrolysis of Calophyllum inophyllum seed cake: study on performance and emission characteristics of direct injection diesel engine fuelled with bio-oil blends.

Science.gov (United States)

Rajamohan, Sakthivel; Kasimani, Ramesh

2018-04-01

This paper aims to analyse the characteristics and properties of the fractions obtained from slow pyrolysis of non-edible seed cake of Calophyllum inophyllum (CI). The gas, bio-oil and biochar obtained from the pyrolysis carried out at 500 °C in a fixed bed batch type reactor at a heating rate of 30 °C/min were characterized by various analytical techniques. Owing to the high volatile content of CI biomass (72.61%), it was selected as the raw material in this present investigation. GC-MS and FT-IR analysis of bio-oil showed the presence of higher amount of oxygenated compounds, phenol derivatives, esters, acid and furans. The physicochemical properties of the bio-oil were tested as per ASTM norms which imply that bio-oil is a highly viscous liquid with lower heating value as compared to that of diesel fuel. The chemical composition of evolved gas was analysed by using GC testing which revealed the presence of combustible components. The FT-IR characterization of biochar showed the presence of aliphatic and aromatic hydrocarbons whereas the elevated amount of carbon in biochar indicates its potential to be used as solid fuel. The performance and emission characteristics of CI engine were assessed with different CI bio-oil blends and compared with baseline diesel fuel. The results showed that addition of bio-oil leads to decreased brake thermal efficiency and increased brake specific energy consumption. Meanwhile, increase in blend ratio reduces harmful pollutants such as oxides of nitrogen and smoke in the exhaust. From the engine testing, it is suggested to employ 20% of CI bio-oil blends in CI engine to obtain better operation.

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. Copyright © 2013 Elsevier Ltd. All rights reserved.

Pyrolysis of oil palm mesocarp fiber and palm frond in a slow-heating fixed-bed reactor: A comparative study.

Science.gov (United States)

Kabir, G; Mohd Din, A T; Hameed, B H

2017-10-01

Oil palm mesocarp fiber (OPMF) and palm frond (PF) were respectively devolatilized by pyrolysis to OPMF-oil and PF-oil bio-oils and biochars, OPMF-char and PF-char in a slow-heating fixed-bed reactor. In particular, the OPMF-oil and PF-oil were produced to a maximum yield of 48wt% and 47wt% bio-oils at 550°C and 600°C, respectively. The high heating values (HHVs) of OPMF-oil and PF-oil were respectively found to be 23MJ/kg and 21MJ/kg, whereas 24.84MJ/kg and 24.15MJ/kg were for the corresponding biochar. The HHVs of the bio-oils and biochars are associated with low O/C ratios to be higher than those of the corresponding biomass. The Fourier transform infrared spectra and peak area ratios highlighted the effect of pyrolysis temperatures on the bio-oil compositions. The bio-oils are pervaded with numerous oxygenated carbonyl and aromatic compounds as suitable feedstocks for renewable fuels and chemicals. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Compatibility Assessment of Fuel System Infrastructure Plastics with Bio-oil and Diesel Fuel

Energy Technology Data Exchange (ETDEWEB)

Kass, Michael D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Fuels, Engines and Emissions Research Center; Janke, Christopher James [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Fuels, Engines and Emissions Research Center; Connatser, Raynella M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Fuels, Engines and Emissions Research Center; Lewis, Samuel Arthur [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Fuels, Engines and Emissions Research Center; Keiser, James R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Fuels, Engines and Emissions Research Center; Gaston, Katherine [National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center

2017-12-05

We report that bio-oil derived via fast pyrolysis is being developed as a renewable fuel option for petroleum distillates. The compatibility of neat bio-oil with 18 plastic types was evaluated using neat diesel fuel as the baseline. The plastic materials included polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyoxymethylene (POM), POM copolymer, high density polyethylene (HDPE), polybutylene terephthalate (PBT), polypropylene (PP), polyethylene terephthalate glycol (PETG), polythiourea (PTU), four nylon grades, and four thermosetting resins. Specimens of each material were immersed in the test fuels for a period of 16 weeks to achieve full saturation. Except for PP and HDPE, the plastic materials underwent higher volume expansion in bio-oil than in the baseline diesel (which was negligible in most cases). This volume increase corresponds to the higher polarity of the bio-oil. PPS, PET, and PTFE were unaffected by bio-oil exposure, but modest swelling (between 2 and 5%) occurred for the two acetals (POM and POM copolymer), Nylon-12, PBT, PETG, and the four resin grades. More moderate swelling (8–15%) was noted for Nylon-6, Nylon-6/6, and Nylon-11, and excessive swell (>40%) occurred for PTU. The nonpolar nature of PP and HDPE matches that of diesel, leading to higher solubility (swell) in this fuel type. Finally, the relatively low volume expansion following exposure indicates that many of the existing infrastructure plastics (excluding PTU) should be suitable for use with bio-oil.

Conventional and microwave pyrolysis of a macroalgae waste from the Agar-Agar industry. Prospects for bio-fuel production.

Science.gov (United States)

Ferrera-Lorenzo, N; Fuente, E; Bermúdez, J M; Suárez-Ruiz, I; Ruiz, B

2014-01-01

A comparative study of the pyrolysis of a macroalgae industrial solid waste (algae meal) in an electrical conventional furnace and in a microwave furnace has been carried out. It was found that the chars obtained from both pyrolyses are similar and show good properties for performing as a solid bio-fuel and as a precursor of activated carbon. Bio-oils from conventional pyrolysis have a greater number of phenolic, pyrrole and alkane compounds whereas benzene and pyridine compounds are more predominant in microwave pyrolysis with a major presence of light compounds. The bio-gas fraction from microwave pyrolysis presents a much higher syngas content (H2+CO), and a lower CO2 and CH4 proportion than that obtained by conventional pyrolysis. Yields are similar for both treatments with a slightly higher gas yield in the case of microwave pyrolysis due to the fact that microwave heating favors heterogeneous reactions between the gases and the char. Copyright © 2013 Elsevier Ltd. All rights reserved.

Co pyrolysis of biomass and PP

International Nuclear Information System (INIS)

Heo, Hyeon Su; Kim, Jung Hwan; Cho, Hye Jung; Ko, Jeong Huy; Park, Hye Jin; Bae, Yoon Ju; Park, Young Kwon

2010-01-01

Full text: While bio-oil has received considerable attention both as a source of energy and as an organic feedstock, its stability as fuel is very low due to high oxygen content. Therefore, there are many efforts to upgrade it. Among them, co pyrolysis with polyolefin can be a method to obtain stable bio-oil. Because polyolefins contain higher hydrogen and carbon content than biomass and no oxygen, plastic/ biomass co pyrolysis may upgrade the bio-oil properties by increasing the carbon and hydrogen contents while reducing oxygen content. In this study, wood biomass was mixed with PP and then co pyrolysis was carried out in a batch reactor. The produced oil and gas was analyzed using GC and GC-MS. Also elemental analysis was performed to know the hydrogen, carbon and oxygen content of bio-oil. The effect of various reaction conditions on bio-oil properties were presented in detail. (author)

Air Permitting Implications of a Biorefinery Producing Raw Bio-Oil in Comparison with Producing Gasoline and Diesel Blendstocks

Energy Technology Data Exchange (ETDEWEB)

Bhatt, Arpit H [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Zhang, Yi Min [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2018-02-01

A biorefinery, considered a chemical process plant under the Clean Air Act permitting program, could be classified as a major or minor source based on the size of the facility and magnitude of regulated pollutants emitted. Our previous analysis indicates that a biorefinery using fast pyrolysis conversion process to produce finished gasoline and diesel blendstocks with a capacity of processing 2,000 dry metric tons of biomass per day would likely be classified as a major source because several regulated pollutants (such as particulate matter, sulfur dioxide, nitrogen oxide) are estimated to exceed the 100 tons per year (tpy) major source threshold, applicable to chemical process plants. Being subject to a major source classification could pose additional challenges associated with obtaining an air permit in a timely manner before the biorefinery can start its construction. Recent developments propose an alternative approach to utilize bio-oil produced via the fast pyrolysis conversion process by shipping it to an existing petroleum refinery, where the raw bio-oil can be blended with petroleum-based feedstocks (e.g., vacuum gas oil) to produce gasoline and diesel blendstocks with renewable content. Without having to hydro-treat raw bio-oil, a biorefinery is likely to reduce its potential-to-emit to below the 100 tpy major source threshold, and therefore expedite its permitting process. We compare the PTE estimates for the two biorefinery designs with and without hydrotreating of bio-oils and examine the air permitting implications on potential air permit classification and discuss the best available control technology requirements for the major source biorefinery utilizing hydrotreating operation. Our analysis is expected to provide useful information to new biofuel project developers to identify opportunities to overcome challenges associated with air permitting.

Techno-economic performance analysis of bio-oil based Fischer-Tropsch and CHP synthesis platform

International Nuclear Information System (INIS)

Ng, Kok Siew; Sadhukhan, Jhuma

2011-01-01

The techno-economic potential of the UK poplar wood and imported oil palm empty fruit bunch derived bio-oil integrated gasification and Fischer-Tropsch (BOIG-FT) systems for the generation of transportation fuels and combined heat and power (CHP) was investigated. The bio-oil was represented in terms of main chemical constituents, i.e. acetic acid, acetol and guaiacol. The compositional model of bio-oil was validated based on its performance through a gasification process. Given the availability of large scale gasification and FT technologies and logistic constraints in transporting biomass in large quantities, distributed bio-oil generations using biomass pyrolysis and centralised bio-oil processing in BOIG-FT system are technically more feasible. Heat integration heuristics and composite curve analysis were employed for once-through and full conversion configurations, and for a range of economies of scale, 1 MW, 675 MW and 1350 MW LHV of bio-oil. The economic competitiveness increases with increasing scale. A cost of production of FT liquids of 78.7 Euro/MWh was obtained based on 80.12 Euro/MWh of electricity, 75 Euro/t of bio-oil and 116.3 million Euro/y of annualised capital cost. -- Highlights: → Biomass to liquid process and gas to liquid process synthesis. → Biorefinery economic analysis. → Pyrolysis oil to biofuel. → Gasification and Fischer-Tropsch. → Process integration, pinch analysis and energy efficiency.

Attrition-free pyrolysis to produce bio-oil and char.

Science.gov (United States)

Mauviel, Guillain; Guillain, Mauviel; Kies, Fairouz; Fairouz, Kies; René, Mar Sans; Mar, Sans Rene; Ferrer, Monique; Monique, Ferrer; Lédé, Jacques; Jacques, Lédé

2009-12-01

Experiments are performed on a laboratory scale setup where beech wood chips are heated by gas convection and walls radiation. This study shows that it is possible to obtain high bio-oil and char yields with relatively low external heat transfer coefficients. The main advantage of this convection/radiation heat transfer mode compared to solid-solid collisions, applied in fluidized bed or twin screw reactors, is the reduction of solid attrition (char and sand). Thus tricky gas-solid separation through hot cyclones and/or hot filters could be avoided or reduced. It should be possible to recover directly bio-oil with less char particles and char free of sand dust. These qualities would allow easier use of these bio-products in different applications.

Chemical and physical characterisation of biomass-based pyrolysis oils. Literature view

Energy Technology Data Exchange (ETDEWEB)

Fagernaes, L [VTT Energy, Espoo (Finland). Energy Production Technologies

1996-12-31

Biomass-based pyrolysis oils are complex mixtures of mainly organic compounds and water. The determination of their physical and chemical properties and chemical composition is a challenge for researchers. Characterisation of biomass pyrolysis oils has been studied at many universities in North America and Europe in the 1980s and 1990s. The existing literature on the analytical methods used for these oils is reviewed in this report. For characterising the chemical composition, the bio-oils have first been mainly fractionated into different classes. Solvent extraction and adsorption chromatography are the most general methods used. In adsorption chromatography, the oils have been fractionated into different hydrocarbon and polar fractions. The fractions obtained have been analysed with various chromatographic and spectroscopic methods. Gas chromatography/mass spectrometry (GC/MS) technique is the analytical method most widely used and well adaptable for the fractions. For high-molecular-mass and highly polar compounds liquid chromatographic (LC) techniques as well as infrared (FT-IR) and nuclear magnetic resonance (1H NMR and 13C NMR) spectroscopies are more suitable due to the low volatility of pyrolysis oils. For whole pyrolysis oils, LC techniques, primarily size exclusion chromatography and FT-IR and FT-NMR spectroscopies have proved to be useful methods

Chemical and physical characterisation of biomass-based pyrolysis oils. Literature view

Energy Technology Data Exchange (ETDEWEB)

Fagernaes, L. [VTT Energy, Espoo (Finland). Energy Production Technologies

1995-12-31

Biomass-based pyrolysis oils are complex mixtures of mainly organic compounds and water. The determination of their physical and chemical properties and chemical composition is a challenge for researchers. Characterisation of biomass pyrolysis oils has been studied at many universities in North America and Europe in the 1980s and 1990s. The existing literature on the analytical methods used for these oils is reviewed in this report. For characterising the chemical composition, the bio-oils have first been mainly fractionated into different classes. Solvent extraction and adsorption chromatography are the most general methods used. In adsorption chromatography, the oils have been fractionated into different hydrocarbon and polar fractions. The fractions obtained have been analysed with various chromatographic and spectroscopic methods. Gas chromatography/mass spectrometry (GC/MS) technique is the analytical method most widely used and well adaptable for the fractions. For high-molecular-mass and highly polar compounds liquid chromatographic (LC) techniques as well as infrared (FT-IR) and nuclear magnetic resonance (1H NMR and 13C NMR) spectroscopies are more suitable due to the low volatility of pyrolysis oils. For whole pyrolysis oils, LC techniques, primarily size exclusion chromatography and FT-IR and FT-NMR spectroscopies have proved to be useful methods

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...

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

Science.gov (United States)

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

2018-06-01

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

Fast pyrolysis of corn stover using ZnCl2: Effect of washing treatment on the furfural yield and solvent extraction of furfural

International Nuclear Information System (INIS)

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

2015-01-01

To produce a bio-oil having a high concentration of furfural, corn stover was fast-pyrolyzed using ZnCl 2 in a fluidized bed reactor at 330–430 °C. The effects of various parameters such as reaction temperature, water- and acid-washing prior to pyrolysis, and ZnCl 2 content on the product and furfural yields were investigated. Moreover, solvent extraction was conducted using toluene at different mass ratios of bio-oil/toluene to recover furfural from the obtained bio-oil. The maximum yield of bio-oil was 59 wt%. The bio-oil mainly comprised acetic acid, α-hydroxyketones, and furfural. The maximum furfural yield was 11.5 wt% when the feed material was water-washed, impregnated with 18.5 wt% ZnCl 2 , and pyrolyzed. Although acid-washing removed alkali and alkaline earth metals much more efficiently than water-washing, water-washing was better than acid-washing for the furfural production. Toluene extraction was very effective to recover furfural from bio-oil. The maximum recovery rate (82%) was achieved at a bio-oil/toluene ratio of 1:4. - Highlights: • Corn stover pretreated and impregnated with ZnCl 2 was successfully pyrolyzed. • Furfural was recovered from bio-oil by extraction using toluene. • Water-washing was better than acid-washing for the furfural production. • The highest furfural yield was 11.5 wt% of the product. • The highest furfural recovery rate was 82%

Pyrolysis oil as diesel fuel

Energy Technology Data Exchange (ETDEWEB)

Gros, S [Wartsila Diesel International Ltd., Vaasa (Finland). Diesel Technology

1997-12-31

Wood waste pyrolysis oil is an attractive fuel alternative for diesel engine operation. The main benefit is the sustainability of the fuel. No fossil reserves are consumed. The fact that wood waste pyrolysis oil does not contribute to CO{sub 2} emissions is of utmost importance. This means that power plants utilising pyrolysis oil do not cause additional global warming. Equally important is the reduced sulphur emissions that this fuel alternative implies. The sulphur content of pyrolysis oil is extremely low. The high water content and low heating value are also expected to result in very low NO{sub x} emissions. Utilisation of wood waste pyrolysis oil in diesel engines, however, involves a lot of challenges and problems to be solved. The low heating value requires a new injection system with high capacity. The corrosive characteristics of the fluid also underline the need for new injection equipment materials. Wood waste pyrolysis oil contains solid particles which can clog filters and cause abrasive wear. Wood waste pyrolysis oil has proven to have extremely bad ignition properties. The development of a reliable injection system which is able to cope with such a fuel involves a lot of optimisation tests, redesign and innovative solutions. Successful single-cylinder tests have already been performed and they have verified that diesel operation on wood pyrolysis oil is technically possible. (orig.)

Pyrolysis oil as diesel fuel

Energy Technology Data Exchange (ETDEWEB)

Gros, S. [Wartsila Diesel International Ltd., Vaasa (Finland). Diesel Technology

1996-12-31

Wood waste pyrolysis oil is an attractive fuel alternative for diesel engine operation. The main benefit is the sustainability of the fuel. No fossil reserves are consumed. The fact that wood waste pyrolysis oil does not contribute to CO{sub 2} emissions is of utmost importance. This means that power plants utilising pyrolysis oil do not cause additional global warming. Equally important is the reduced sulphur emissions that this fuel alternative implies. The sulphur content of pyrolysis oil is extremely low. The high water content and low heating value are also expected to result in very low NO{sub x} emissions. Utilisation of wood waste pyrolysis oil in diesel engines, however, involves a lot of challenges and problems to be solved. The low heating value requires a new injection system with high capacity. The corrosive characteristics of the fluid also underline the need for new injection equipment materials. Wood waste pyrolysis oil contains solid particles which can clog filters and cause abrasive wear. Wood waste pyrolysis oil has proven to have extremely bad ignition properties. The development of a reliable injection system which is able to cope with such a fuel involves a lot of optimisation tests, redesign and innovative solutions. Successful single-cylinder tests have already been performed and they have verified that diesel operation on wood pyrolysis oil is technically possible. (orig.)

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

Science.gov (United States)

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

2016-05-01

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

EFFECT OF AQUEOUS PRETREATMENT ON PYROLYSIS CHARACTERISTICS OF NAPIER GRASS

Directory of Open Access Journals (Sweden)

ISAH YAKUB MOHAMMED

2015-11-01

Full Text Available Effect of non-catalytic aqueous pretretment on pyrolysis characteristics of Napier grass was investigated using thermogravimetric analyser. Increasing pretreatment severity (0.0-2.0 improved pyrolysis process. The residual mass at the end of pyrolysis for the pretreated sample was about 50% less compared to the untreated sample. Kinetics of the process was evaluated using order based model and both pretreated and untreated samples followed first order reaction. The activation energy of the pretreated samples was similar and higher than that of the raw sample which was attributed to faster rate of decomposition due removal of hetromaterials (ash, extractives and some hemicellulose in the pretreatment stage. Finally, this pretreatment method has demonstrated effectiveness for the removal of pyrolysis retardants and will improve the quantity and quality of bio-oil yield.

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...

Catalytic biomass pyrolysis process

Science.gov (United States)

Dayton, David C.; Gupta, Raghubir P.; Turk, Brian S.; Kataria, Atish; Shen, Jian-Ping

2018-04-17

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

A comparison of pipeline versus truck transport of bio-oil.

Science.gov (United States)

Pootakham, Thanyakarn; Kumar, Amit

2010-01-01

Biomass-based energy and fuels are receiving attention because they are considered carbon neutral; i.e. the amount of CO(2) released during combustion of this biomass is nearly the same as that taken up by the plants during their growth. Bio-oil is a dark viscous liquid consisting of hydrocarbons. These are produced by fast pyrolysis of biomass. "As-is" biomass material has a low energy density (MJ m(-3)), hence, the cost of transporting this energy is high. Bio-oil has a high energy density as compared to "as-is" biomass material, consequently it helps in reducing the cost of energy transport. This study compares the life cycle assessment of transportation of bio-oil by pipeline with that by truck. The scope of the work includes the transportation of bio-oil by truck or pipeline from a centralized plant (supplied with forest biomass) to an end-user. Two cases are studied for pipeline transport of bio-oil: the first case considers a coal-based electricity supply for pumping the bio-oil through a pipeline; the second case considers an electricity supply from a renewable resource. The two cases of pipeline transport are compared to two cases of truck transport (truck trailer and super B-train truck). The life cycle greenhouse gas (GHG) emissions from the pipeline transport of bio-oil for the two cases of electricity supply are 345 and 17 g of CO(2) m(-3) km(-1), respectively. Similar values for transport by trailer (capacity - 30 m(3)) and super B-train truck (capacity - 60 m(3)) are 89 and 60 g of CO(2) m(-3) km(-1), respectively. Energy input for bio-oil transport is 3.95 MJ m(-3) km(-1) by pipeline, 2.59 MJ m(-3) km(-1) by truck and 1.66 MJ m(-3) km(-1) by super B-train truck. The results show that GHG emissions in pipeline transport are largely dependent on the source of electricity (higher for coal-based electricity). Substituting 250 m(3) day(-1) of pipeline-transported bio-oil for coal-based electricity can mitigate about 5.1 million tonnes of CO(2) per year

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

Catalytic cracking of bio-oil to organic liquid product (OLP).

Science.gov (United States)

Hew, K L; Tamidi, A M; Yusup, S; Lee, K T; Ahmad, M M

2010-11-01

The main objective of this paper is to find the optimum operating condition to upgrade the EFB-derived pyrolysis oil (bio-oil) to liquid fuel, mainly gasoline using Taguchi Method. From the analysis that has been done, it is found that the optimum operating condition for heterogeneous catalytic cracking process is at 400 degrees C, 15min of reaction time using 30g of catalyst weight where operating at this condition produced the highest yield of gasoline fraction which is 91.67 wt.%. This observation proves that EFB-derived pyrolysis oil could be upgraded via heterogeneous catalytic cracking to produce gasoline.

Controllable production of liquid and solid biofuels by doping-free, microwave-assisted, pressurised pyrolysis of hemicellulose

International Nuclear Information System (INIS)

Li, T.; Remón, J.; Shuttleworth, P.S.; Jiang, Z.; Fan, J.; Clark, J.H.; Budarin, V.L.

2017-01-01

Highlights: • Microwave pyrolysis of xylan in the absence of any external microwave absorber. • High energy-efficient and controllable production of biochar and bio-oil from xylan. • Water in liquid phase is needed for fast microwave pyrolysis. • Production of bio-oil and bio-char with HHVs 52% and 19% greater than that of xylan. - Abstract: Batch, pressurised microwave-assisted pyrolysis of hemicellulose in the absence of any external microwave absorber was found to be a promising route for the production of bio-based chemicals and biofuels. The experiments were conducted in a 10 mL batch reactor using a fixed power of 200 W employing different initial masses of xylan (0.1–0.7 g) for a maximum time, temperature and pressure of 10 min, 250 °C and 200 psi, respectively. The gas, bio-oil and solid (char) yields varied by 16–40%, 2–21% and 40–82%, respectively. Char production is preferential using a low amount of xylan (<0.25 g), while bio-oil production is favoured using a high amount of xylan (0.25–0.7 g). The effect of the sample mass is accounted for by the different physical state of the volatiles released during pyrolysis depending on the pressure attained during the experiment. This permits the process to be easily customised for the selective production of liquid (bio-oil) or solid (bio-char). Regarding the bio-oil, it is composed of a mixture of platform chemicals such as aldehydes, alkenes, phenols, polyaromatic hydrocarbons (PAHC), cyclic ketones and furans, with the composition varying depending on the initial mass of xylan. The char had a higher proportion of C together with a lower proportion of O than the original feedstock. Energy efficiencies of 100 and 26% were achieved for char and bio-oil production, respectively; thus leading to an increase in the HHV of the products (with respect to the original feedstock) of 52% for char and 19% for bio-oil.

Production of bio-oil from underutilized forest biomass using an auger reactor

Science.gov (United States)

H. Ravindran; S. Thangalzhy-Gopakumar; S. Adhikari; O. Fasina; M. Tu; B. Via; E. Carter; S. Taylor

2015-01-01

Conversion of underutilized forest biomass to bio-oil could be a niche market for energy production. In this work, bio-oil was produced from underutilized forest biomass at selected temperatures between 425–500°C using an auger reactor. Physical properties of bio-oil, such as pH, density, heating value, ash, and water, were analyzed and compared with an ASTM standard...

Integrated biomass pyrolysis with organic Rankine cycle for power generation

Science.gov (United States)

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

2018-02-01

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

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. Published by Elsevier Ltd.

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

OpenAIRE

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 during hydrotreatment is desirable to reduce the formation of by-products such as char and gaseous components. This paper deals with the catalytic hydrotreatment of representative model components for t...

Pyrolysis oil from carbonaceous solid wastes in Malaysia

International Nuclear Information System (INIS)

Islam, M.N.; Jamil, M.K.; Ani, F.N.; Zailani, R.

2000-01-01

The agro-industrial sector of Malaysia produces a huge amount of oil palm and paddy rice. These generate a significant amount of renewable biomass solid wastes in the forms of oil palm shell and rice husk. Apart from this a huge quantity of scrap tyre is generated from the country's faster increasing usage of transportation vehicles like motorcycle, car, bus and lorries. These wastes are producing pollution and disposal problems affecting the environment. Besides energy is not recovered efficiently from these waste resources. From the elemental composition and thermogravimetric analysis (TGA) studies of the wastes, it appeared that the wastes could be used for pyrolysis liquid oil production. Pyrolysis at present is deemed to be a potential method for the conversion of carbonaceous solid wastes into upgraded liquid products which can either be tried for liquid fuel or value-added chemical. A fluidized bed bench scale fast pyrolysis system was employed for this thermochemical conversion process of solid wastes. Silica sand was used as fluidized bed material and nitrogen gas as the fluidising medium. The products obtained were liquid oil, solid char and gas. The liquid oil and solid char were collected separately while the gas was flared. The maximum liquid product yield was found to vary with feedstock material fluidized bed temperature. The maximum liquid product yield was found to be 58, 53 and 40 wt. % of biomass fed at fluidized bed temperature at 500, 525 and 450 0 C respectively for oil palm shell, scrap tyre and rice husk. The solid char yield was 25, 36 and 53 wt. % of biomass fed at the condition of maximum liquid product yield for oil palm shell, scrap tyre and rice husk respectively. The oil products were subjected to FTIR, GC and GC/MS analysis for their group composition and detailed chemical compositions. The pyrolysis oil from scrap tyre was found to contain highest percentage of pure hydrocarbons (25 wt. % of total feed) with esters and oxygenated

Development of advanced technologies for biomass pyrolysis

Science.gov (United States)

Xu, Ran

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

Catalytic Flash Pyrolysis of Biomass Using Different Types of Zeolite and Online Vapor Fractionation

KAUST Repository

Imran, Ali

2016-03-11

Bio-oil produced from conventional flash pyrolysis has poor quality and requires expensive upgrading before it can be used as a transportation fuel. In this work, a high quality bio-oil has been produced using a novel approach where flash pyrolysis, catalysis and fractionation of pyrolysis vapors using two stage condensation are combined in a single process unit. A bench scale unit of 1 kg/h feedstock capacity is used for catalytic pyrolysis in an entrained down-flow reactor system equipped with two-staged condensation of the pyrolysis vapor. Zeolite-based catalysts are investigated to study the effect of varying acidities of faujasite Y zeolites, zeolite structures (ZSM5), different catalyst to biomass ratios and different catalytic pyrolysis temperatures. Low catalyst/biomass ratios did not show any significant improvements in the bio-oil quality, while high catalyst/biomass ratios showed an effective deoxygenation of the bio-oil. The application of zeolites decreased the organic liquid yield due to the increased production of non-condensables, primarily hydrocarbons. The catalytically produced bio-oil was less viscous and zeolites were effective at cracking heavy molecular weight compounds in the bio-oil. Acidic zeolites, H-Y and H-ZSM5, increased the desirable chemical compounds in the bio-oil such as phenols, furans and hydrocarbon, and reduced the undesired compounds such as acids. On the other hand reducing the acidity of zeolites reduced some of the undesired compounds in the bio-oil such as ketones and aldehydes. The performance of H-Y was superior to that of the rest of zeolites studied: bio-oil of high chemical and calorific value was produced with a high organic liquid yield and low oxygen content. H-ZSM5 was a close competitor to H-Y in performance but with a lower yield of bio-oil. Online fractionation of catalytic pyrolysis vapors was employed by controlling the condenser temperature and proved to be a successful process parameter to tailor the

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

International Nuclear Information System (INIS)

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

2016-01-01

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.

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.

Bio-oil hydrodeoxygenation catalysts produced using strong electrostatic adsorption

Science.gov (United States)

We synthesized hydrothermally stable metal catalysts with controlled particle size and distribution, with the goal of determining which catalyst(s) can selectively catalyze the production of aromatics from bio-oil (from pyrolysis of biomass). Both precious and base transition metal catalysts (Ru, Pt...

Model-free pyrolysis kinetics of sunflower seed and its de-oiled cake

International Nuclear Information System (INIS)

Özsin, Gamzenur; Kilic, Murat; Pütün, Ersan; Pütün, Ayşe E.

2015-01-01

Sunflower seed wastes from oil production are a potential biomass source for bio- energy production due to extensive and excessive oil production from sunflower seeds. Considering global energy requirement, pyrolysis seems a promising route for utilisation of such industrial biomass wastes. To develop, scale-up and operate pyrolysis plants efficiently, a fundamental understanding of pyrolysis behaviour and kinetics is essential. In this study, sunflower seeds and their waste cakes after extraction were evaluated as a potential biomass feedstock in pyrolysis process. In order to enlighten pyrolytic degradation behaviours, samples were pyrolysed under dynamic conditions from room temperature to 1000 °C using multiple heating rates. The main degradation regimes of the structures were characterized by high weight loss rates. Reaction kinetics was investigated with respect to conversion degree. It is anticipated that this study will be beneficial in optimizing the thermochemical processes, which may be utilize industrial biomass wastes. (full text)

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

Science.gov (United States)

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

2017-09-01

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

Coke formation during the hydrotreatment of bio-oil using NiMo and CoMo catalysts

NARCIS (Netherlands)

Kadarwati, Sri; Hu, Xun; Gunawan, Richard; Westerhof, Roel; Gholizadeh, Mortaza; Hasan, M. D.Mahmudul; Li, Chun-Zhu

2017-01-01

This study aims to investigate the coke formation during the hydrotreatment of bio-oil at low temperature. The catalytic hydrotreatment of bio-oil produced from the pyrolysis of mallee wood was carried out using pre-sulphided NiMo and CoMo catalysts at a temperature range of 150–300 °C. Our results

Hydropyrolysis of sugar cane bagasse: effect of sample configuration on bio-oil yields and structures from two bench-scale reactors

Energy Technology Data Exchange (ETDEWEB)

Pindoria, R.V.; Chatzakis, I.N.; Lim, J.-Y.; Herod, A.A.; Dugwell, D.R.; Kandiyoti, R. [Imperial College of Science, Technology and Medicine, London (United Kingdom). Dept. of Chemical Engineering and Chemical Technology

1999-01-01

A wire-mesh reactor has been used as base-case in the study of product yields and structures from the pyrolysis and hydropyrolysis of a sample of sugar cane bagasse in a fixed bed `hot-rod` reactor. Results from the two reactors have been compared to determine how best to assess bench-scale data which might be used for eventual process development. Experiments have been carried out at 600{degree}C at pressures up to 70 bar. Structural features of the bio-oils have been examined by size exclusion chromatography and FT-infrared spectroscopy. In both reactors the effect of increasing pressure was to reduce the bio-oil and total volatile yields: hydropyrolysis bio-oil yields were marginally higher than pyrolysis yields under equivalent operating conditions. The data indicate that about one-third of the original biomass may be converted to oil by direct pyrolysis. 33 refs., 10 figs.

Renewable glycoaldehyde isolation from pyrolysis oil by reactive extraction with primary amines

NARCIS (Netherlands)

Vitasari, C.R.; Meindersma, G.W.; Haan, de A.B.

2011-01-01

The transition to a sustainable bio-based economy has rapidly increased the interest to obtain renewable platform chemicals from biomass. Glycolaldehyde is one of potential future platform chemicals, which is present in high quantity (5–13 wt%) in wood-derived pyrolysis oil. Water addition to

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.

Production, properties and utilisation of pyrolysis oil

Energy Technology Data Exchange (ETDEWEB)

Sipilae, K; Oasmaa, A; Arpiainen, V; Solantausta, Y; Leppaemaeki, E; Kuoppala, E; Levander, J; Kleemola, J; Saarimaeki, P [VTT Energy, Jyvaeskylae (Finland). Energy Production Technologies

1997-12-01

In this project VTT Energy co-ordinates the EU JOULE Project `Biofuel oil for power plants and boilers` supporting the development projects of Finnish enterprises, and participates in the Pyrolysis Project of IEA Bioenergy Agreement. Presently two pyrolysis devices with capacities of 150 g/h and 1 kg/h are used for the project. Hot gas filtering tests by using one ceramic candle equipment have been carried out with the 1 kg/h device for pyrolysis oil. The solids and alkali contents of the product oil were reduced clearly. Suitable conditions are being defined for continuous hot gas filtering. A PDU device of 20 kg/h is being commissioned. The main aim of the chemical characterisation of pyrolysis oil was to develop as simple a method as possible for differentiating pyrolysis oils and for finding correlations between the characteristics and behaviour of pyrolysis oils. Pyrolysis oils produced from various raw materials (hardwood, pine, straw) were analysed and compared with each other. VTT Energy participates in the pyrolysis network (EU/PYNE) of EU, the aim of which is to collect and disseminate research results of pyrolysis studies, i.e., through a journal with a wide circulation. VTT also participates in the pyrolysis activity of IEA (PYRA), the other partners being Great Britain, EU, Canada and the United States. I.e., quality criteria and improvement, occupational safety and pyrolysis kinetics are discussed in IEA/PYRA

Spray pyrolysis synthesis of γ-Al_2O_3 supported metal and metal phosphide catalysts and their activity in the hydrodeoxygenation of a bio-oil model compound

International Nuclear Information System (INIS)

Ly, Hoang Vu; Im, Kyungmin; Go, Youngchae; Galiwango, Emmanuel; Kim, Seung-Soo; Kim, Jinsoo; Choi, Jae Hyung; Woo, Hee Chul

2016-01-01

Highlights: • Spherical γ-Al_2O_3 supported metal and metal phosphide catalysts were synthesized by spray pyrolysis method. • Hydrodeoxygenation (HDO) of 2-furyl methyl ketone (FMK) was conducted using metal/metal phosphide catalysts. • FMK was converted into 2-allyl furan and methyl cyclohexane. • The highest FMK conversion of 83% was achieved over 10 wt% Ni/γ-Al_2O_3 catalysts at reaction temperature of 400 °C. - Abstract: In this study, spherical γ-Al_2O_3 supported metal and metal phosphide (Ni, Co, Ni_2P and CoP) catalysts were successfully prepared by combining sol-gel and spray pyrolysis methods. First boehmite sol was prepared based on the Yoldas process and then the corresponding metal salts were added to the sol at the desired concentration, followed by spray pyrolysis of the mixed solution. As the well-mixed solution was transformed to spherical γ-Al_2O_3 supported metal and metal phosphide catalysts during spray pyrolysis process, the metal species were uniformly distributed in the mesoporous γ-Al_2O_3 supports. The product catalysts were investigated under different conditions for hydrodeoxygenation of bio-oil model compound, 2-furyl methyl ketone (FMK), which is the main component of the bio-oil product from pyrolysis of Saccharina japonica. Among the investigated catalysts, the 10 wt% Ni/γ-Al_2O_3 catalyst after calcination at 800 °C showed the highest FMK conversion of 83.02% at the reaction temperature of 400 °C. The gas and liquid products were analyzed by gas chromatography (GC) with TCD/FID detectors and GC–MS, respectively, to determine the product compositions.

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.

A case study of pyrolysis of oil palm wastes in Malaysia

Science.gov (United States)

Abdullah, Nurhayati; Sulaiman, Fauziah; Aliasak, Zalila

2013-05-01

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

The effects of catalysts on the conversion of organic matter and bio-fuel production in the microwave pyrolysis of sludge at different temperatures.

Science.gov (United States)

Ma, Rui; Huang, Xiaofei; Zhou, Yang; Fang, Lin; Sun, Shichang; Zhang, Peixin; Zhang, Xianghua; Zhao, Xuxin

2017-08-01

Adding catalyst could improve the yields and qualities of bio-gas and bio-oil, and realize the oriented production. Results showed that the catalytic gas-production capacities of CaO were higher than those of Fe 2 O 3 , and the bio-gas yield at 800°C reached a maximum of 35.1%. Because the polar cracking active sites of CaO reduced the activation energy of the pyrolysis reaction and resulted in high catalytic cracking efficiencies. In addition, the quality of bio-oil produced by CaO was superior to that by Fe 2 O 3 , although the bio-oil yield of CaO was relatively weak. The light bio-fuel oriented catalytic pyrolysis could be realized when adding different catalysts. At 800°C, CaO was 45% higher than Fe 2 O 3 in aspect of H 2 production while Fe 2 O 3 was 103% higher than CaO in aspect of CH 4 production. Therefore, CaO was more suitable for H 2 production and Fe 2 O 3 was more suitable for CH 4 production. Copyright © 2017 Elsevier Ltd. All rights reserved.

Bio-Oil Deployment in the Home Heating Market

Energy Technology Data Exchange (ETDEWEB)

Butcher, T. A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Trojanowski, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Mante, O. [Brookhaven National Lab. (BNL), Upton, NY (United States); Wei, G. [Brookhaven National Lab. (BNL), Upton, NY (United States); Celebi, Y. [Brookhaven National Lab. (BNL), Upton, NY (United States); Huber, J. [Brookhaven National Lab. (BNL), Upton, NY (United States)

2016-07-01

Distillate fuel oil is used in many stationary heating applications, predominantly in the Northeastern part of the United States. Total estimated non-transportation distillate use in 2014 was estimated to be 10.9 billion gallons. This study has focused on potentially displacing part of this petroleum use with biofuel derived from woody biomass. The fuel production route considered is pyrolysis which creates a liquid fuel high in oxygen, organic acids, and water. While this fuel can be used in stationary applications without significant further processing, to do so would require significant upgrades in current heating equipment. Alternatively this raw pyrolysis oil can be upgraded through catalytic hydrogenation to produce a bio-oil with near-negligible oxygen, water, and acidity. The focus of this work has been exploration of such upgraded fuels. The quality of upgraded fuels is affected by process conditions and there is a cost /quality tradeoff.

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.

Olive bagasse (Olea europa L.) pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Sensoz, S.; Demiral, I. [Osmangazi Univ., Eskisehir (Turkey). Dept. of Chemical Engineering; Gercel, H.F. [Anadolu Univ., Eskisehir (Turkey). Dept. of Chemical Engineering

2006-02-15

Olive bagasse (Olea europea L.) was pyrolysed in a fixed-bed reactor. The effects of pyrolysis temperature, heating rate, particle size and sweep gas flow rates on the yields of the products were investigated. Pyrolysis runs were performed using pyrolysis temperatures between 350 and 550 {sup o}C with heating rates of 10 and 50 {sup o}C min{sup -} {sup 1}. The particle size and sweep gas flow rate varied in the ranges 0.224-1.8 mm and 50-200 cm{sup 3} min {sup -1}, respectively. The bio-oil obtained at 500 {sup o}C was analysed and at this temperature the liquid product yield was the maximum. The various characteristics of bio-oil obtained under these conditions were identified on the basis of standard test methods. The empirical formula of the bio-oil with heating value of 31.8 MJ kg{sup -1} was established as CH{sub 1.65}O{sub 0.25}N{sub 0.03}. The chemical characterization showed that the bio-oil obtained from olive bagasse may be potentially valuable as a fuel and chemical feedstock. (author)

Influence of biomass pretreatment on upgrading of bio-oil: Comparison of dry and hydrothermal torrefaction.

Science.gov (United States)

Xu, Xiwei; Tu, Ren; Sun, Yan; Li, Zhiyu; Jiang, Enchen

2018-08-01

The dry and hydrothermal torrefacation of on Camellia Shell (CS) was carried on three different devices- batch autoclave, quartz tube, and auger reactor. The torrefied bio-char products were investigated via TGA, elemental analysis and industrial analysis. Moreover, the pyrolysis and catalytic pyrolysis properties of torrefied bio-char were investigated. The results showed torrefaction significantly influenced the content of hemicellulose in CS. And hydrothermal torrefaction via batch autoclave and dry torrefaction via auger reactors promoted the hemicellulose to strip from the CS. Quartz tube and auger reactor were beneficial for devolatilization and improving heat value of torrefied bio-char. The result showed that the main products were phenols and acids. And hydrothermal torrefaction pretreatment effectively reduced the acids content from 34.5% to 13.2% and enriched the content of phenols (from 27.23% to 60.05%) in bio-oil due to the decreasing of hemicellulos in torrefied bio-char. And the catalyst had slight influence on the bio-oil distribution. Copyright © 2018 Elsevier Ltd. All rights reserved.

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.

Catalysis Meets Nonthermal Separation for the Production of (Alkyl)phenols and Hydrocarbons from Pyrolysis Oil.

Science.gov (United States)

Cao, Zhengwen; Engelhardt, Jan; Dierks, Michael; Clough, Matthew T; Wang, Guang-Hui; Heracleous, Eleni; Lappas, Angelos; Rinaldi, Roberto; Schüth, Ferdi

2017-02-20

A simple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass. The overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoC x /C is a promising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired Ar-OH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography, serving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass, no further synthetic steps, and no input of additional (e.g., petrochemical) platform molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast pyrolysis of creosote treated wood ties in a fluidized bed reactor and analytical characterization of product fractions

International Nuclear Information System (INIS)

Jung, Su-Hwa; Koo, Won-Mo; Kim, Joo-Sik

2013-01-01

A fraction of creosote treated wood ties was pyrolyzed in a pyrolysis plant equipped with a fluidized bed reactor and char-separation system at different temperatures. Analyses of each pyrolysis product, especially the oil, were carried out using a variety of analytical tools. The maximum oil yield was obtained at 458 °C with a value of 69.3 wt%. Oils obtained were easily separated into two phases, a creosote-derived fraction (CDF) and a wood-derived fraction (WDF). Major compounds of the WDF were acetic acid, furfural and levoglucosan, while the CDF was mainly composed of polycyclic aromatic hydrocarbons (PAHs), such as 1-methylnaphthalene, biphenyl, acenaphthene, dibenzofuran, fluorene, phenanthrene, anthracene, fluoranthene and pyrene. HPLC analysis showed that the concentration of PAHs of the CDF obtained at 458 °C constituted about 22.5 wt% of the oil. - Highlights: • Creosote treated wood ties was stably pyrolyzed in a fluidized bed reactor. • Pyrolysis oil contained extremely low metal content due to the char removal system. • Bio-oil components was quantitatively analyzed by relative response factor. • Creosote-derived pyrolysis oil fraction was composed of PHAs and has a high caloric value (39 MJ/kg)

Upgrading of the liquid fuel from fast pyrolysis of biomass over MoNi/γ-Al2O3 catalysts

International Nuclear Information System (INIS)

Xu, Ying; Wang, Tiejun; Ma, Longlong; Zhang, Qi; Liang, Wei

2010-01-01

The hydrotreatment of bio-oil, which obtained from fast pyrolysis of pine sawdust, was investigated over MoNi/γ-Al 2 O 3 catalyst under mild conditions (373 K, 3 MPa hydrogen pressure). Acetic acid was taken as a model compound to investigate the effects of Mo promoter contents and reducing temperatures of catalysts on the catalysts activity under the condition of 473 K and 3 MPa hydrogen pressure. X-ray diffraction and temperature programmed reduction showed that the addition of Mo promoter benefited the uniformity of nickel species and inhibited the formation of NiAl 2 O 4 spinel in the catalysts. The GC spectrum of liquid products showed the mechanism of the model reaction. The maximum conversion of acetic acid (33.20%) was attained over 0.06MoNi/γ-Al 2 O 3 catalysts being reduced at 873 K. This catalyst was chosen for the upgrading of raw bio-oil. After the upgrading process, the pH value of the bio-oil increased from 2.33 to 2.77. The water content increased from 35.52 wt.% to 41.55 wt.% and the gross calorific value increased from 13.96 MJ/kg to 14.17 MJ/kg. The hydrogen content in the bio-oil increased from 6.25 wt.% to 6.95 wt.%. The product properties of the upgraded bio-oil, particularly the hydrogen content and the acidity were considerably improved. The results of gas chromatography-mass spectrometry analysis showed that both hydrotreatment and esterification had happened over 0.06MoNi/γ-Al 2 O 3 (873) catalyst during the upgrading process.

H2CAP - Hydrogen assisted catalytic biomass pyrolysis for green fuels

DEFF Research Database (Denmark)

Arndal, Trine Marie Hartmann; Høj, Martin; Jensen, Peter Arendt

2014-01-01

Pyrolysis of biomass produces a high yield of condensable oil at moderate temperature and low pressure.This bio-oil has adverse properties such as high oxygen and water contents, high acidity and immiscibility with fossil hydrocarbons. Catalytic hydrodeoxygenation (HDO) is a promising technology...... that can be used to upgrade the crude bio-oil to fuel-grade oil. The development of the HDO process is challenged by rapid catalyst deactivation, instability of the pyrolysis oil, poorly investigated reaction conditions and a high complexity and variability of the input oil composition. However, continuous...... catalytic hydropyrolysis coupled with downstream HDO of the pyrolysis vapors before condensation shows promise (Figure 1). A bench scale experimental setup will be constructed for the continuous conversion of solid biomass (100g /h) to low oxygen, fuel-grade bio-oil. The aim is to provide a proof...

Upgrading pyrolysis bio-oil through hydrodeoxygenation (HDO) using non-sulfided Fe-Co/SiO2 catalyst

International Nuclear Information System (INIS)

Cheng, Shouyun; Wei, Lin; Julson, James; Rabnawaz, Muhammad

2017-01-01

Highlights: • Fe-Co/SiO 2 catalyst with medium acidity was more effective for bio-oil upgrading. • Co-loading of Fe and Co on SiO 2 support improved catalyst performance. • Catalyst showing the best catalytic activity had a Fe/Co mole ratio of 1. • Biofuel produced by Fe-Co(1)/SiO 2 had the higher hydrocarbons content at 22.44%. • The mechanism of bio-oil HDO on Fe-Co/SiO 2 catalysts is proposed. - Abstract: Hydrodeoxygenation (HDO) is an effective route to upgrade bio-oil to hydrocarbon bio-oil, but the development of efficient catalysts for bio-oil HDO still remains a challenge. In this study, non-sulfided Fe-Co/SiO 2 catalysts were used to upgrade bio-oil using HDO. A series of Fe-Co/SiO 2 catalysts with different Fe/Co mole ratios were prepared, characterized and evaluated. The Fe and/or Co loading did not change SiO 2 crystalline structure. The Fe and/or Co metals increased the amount and strength of Fe-Co/SiO 2 catalyst acidity. Physicochemical properties of upgraded bio-oils produced using Fe-Co/SiO 2 catalysts such as water content, total acid number, viscosity and higher heating values improved in comparison to raw bio-oil. Bimetallic Fe-Co/SiO 2 catalysts resulted in better HDO performance than monometallic Fe/SiO 2 or Co/SiO 2 catalysts. This was due to the synergistic effect of Fe and Co occurring on the SiO 2 support. Fe-Co/SiO 2 catalyst having medium amount of acidity was more effective for bio-oil upgrading. The highest hydrocarbons content produced using Fe-Co(1)/SiO 2 catalyst was 22.44%. The mechanism of bio-oil HDO on Fe-Co/SiO 2 catalysts is proposed.

Bio-Chemicals Derived from Waste: Building on the Concept of a Bio-Refinery

International Nuclear Information System (INIS)

Habib, M.; Habib, U.; Khan, A.U.; Rehman, Z.U.; Zeb, A.; Moeed, A.; Pasha, M.K.; Memon, A.R.

2013-01-01

The work presented here has looked into the thermal-conversion of wheat and barley spent grains (SG). Wheat fermentation was carried in the laboratory to get a mashed product while barley grain residues were sourced from a local brewing company. Pyrolysis carried at 460, 520 and 540 Degree C at ambient conditions of pressure in a bench scale fluidized bed reactor resulted in producing bio-oil, charcoal and non-condensable gases. These products were characterized by using the Gas Chromatography Mass Spectrometry (GC-MS), Differential Thermo-glavemetric Analysis (DTG), Elemental Analyzer (E.A) and a Bomb Calorimeter. The final pyrolysis product analysis revealed that the bio-oil production yields and Higher Heating Value (HHV) largely depended on the pyrolysis temperature and the sample type. In comparison with original raw grain samples, the analysis of thermally treated (pyrolysis) spent grains revealed the presence of high carbon and low oxygen contents. Results gathered in this work have shown that high bio-crude-oil production yields can be obtained at 520 Degree C (53 and 37wt percentage bio-oil from wheat and barley SG). Pyrolysis of wheat and barley SG resulted in giving a Higher Heating Value (HHV) of 21.80 and 21.86 MJ/kg at 540 and 460 Degree C, which is considerably more in comparison to their virgin counterparts. This suggested route thus has a potential for further up-gradation of waste bio-mass for use as an intermediate fuel or as a raw material source for producing other bio-chemicals. (author)

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. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Source and Biological Response of Biochar Organic Compounds Released into Water; Relationships with Bio-Oil Composition and Carbonization Degree.

Science.gov (United States)

Ghidotti, Michele; Fabbri, Daniele; Mašek, Ondřej; Mackay, Colin Logan; Montalti, Marco; Hornung, Andreas

2017-06-06

Water-soluble organic compounds (WSOCs) were extracted from corn stalk biochar produced at increasing pyrolysis temperatures (350-650 °C) and from the corresponding vapors, collected as bio-oil. WSOCs were characterized by gas chromatography (semivolatile fraction), negative electron spray ionization high resolution mass spectrometry (hydrophilic fraction) and fluorescence spectroscopy. The pattern of semivolatile WSOCs in bio-oil was dominated by aromatic products from lignocellulose, while in biochar was featured by saturated carboxylic acids from hemi/cellulose and lipids with concentrations decreasing with decreasing H/C ratios. Hydrophilic species in poorly carbonized biochar resembled those in bio-oil, but the increasing charring intensity caused a marked reduction in the molecular complexity and degree of aromaticity. Differences in the fluorescence spectra were attributed to the predominance of fulvic acid-like structures in biochar and lignin-like moieties in bio-oil. The divergence between pyrolysis vapors and biochar in the distribution of WSOCs with increasing carbonization was explained by the hydrophobic carbonaceous matrix acting like a filter favoring the release into water of carboxylic and fulvic acid-like components. The formation of these structures was confirmed in biochar produced by pilot plant pyrolysis units. Biochar affected differently shoot and root length of cress seedlings in germination tests highlighting its complex role on plant growth.

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.

Hydrotreatment of bio-oil over Ni-based catalyst.

Science.gov (United States)

Zhang, Xinghua; Wang, Tiejun; Ma, Longlong; Zhang, Qi; Jiang, Ting

2013-01-01

Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrotreatments using phenol as model compound. HZSM-5, a zeolite with different ratio of Si/Al and γ-Al(2)O(3) were impregnated with Ni(NO(3))(2) · 6H(2)O and calcined at 450 °C. Conversion rates and product distribution for treatment of phenol at 160-240 °C in the presence of catalysts with nickel loads of 6, 10, 14 and 17 wt.% were determined. Phenol conversion was highest (91.8%) at 240 °C in the presence of HZSM-5(Si/Al = 38) loaded with 10% Ni. When hydrotreatment was carried out with bio-oil obtained from pyrolysis of pine sawdust under the optimal conditions determined for phenol, the pH of bio-oil increased from 2.27 to 4.07, and the hydrogen content increased from 6.28 to 7.01 wt.%. The decrease in acidity is desirable for the use of upgraded bio-oil. Copyright © 2012. Published by Elsevier Ltd.

Production of bio-oils from wood by flash pyrolysis; Herstellung von Bio-Oelen aus Holz in einer Flash-Pyrolyseanlage

Energy Technology Data Exchange (ETDEWEB)

Meier, D; Ollesch, T [Bundesforschungsanstalt fuer Forst- und Holzwirtschaft, Hamburg (Germany). Inst. fuer Holzchemie und Chemische Technologie des Holzes; Gerdes, C; Kaminsky, W [Hamburg Univ. (Germany). Inst. fuer Technische und Makromolekulare Chemie (ITMCh)

1998-09-01

Flash pyrolysis is a medium-temperature process (around 475 C) in which biomass is heated up rapidly in the absence of oxygen. The pyrolysis products are cooled down rapidly, condensing into a reddish-brown liquid with around half the calorific value of a conventional heating oil. In contrast to conventional charcoal production, flash pyrolysis is a modern process whose process parameters enure high liquid yields. Modern fluidized-bed reactors for flash pyrolysis of biomass tend to have high heating rates and short times of residue. In the `Hamburg process`, fluidized-bed reactors are used successfully for pyrolysis of plastics. A flash pyrolysis plant for biomass treatment was constructed in cooperation with Hamburg University with funds provided by the `Bundesstiftung Umwelt`. This contribution describes the first series of experiments, mass balances and oil analyses using beech wood as material to be pyrolyzed. (orig./SR) [Deutsch] Flash-Pyrolyse ist ein Mitteltemperatur-Prozess (ca. 475 C), in dem Biomasse unter Sauerstoffausschluss sehr schnell erhitzt wird. Die entstehenden Pyrolyseprodukte werden schnell abgekuehlt und kondensieren zu einer roetlich-braunen Fluessigkeit, die etwa die Haelfte des Heizwertes eines konventionellen Heizoeles besitzt. Flash-Pyrolyse ist, im Gegensatz zur konventionellen Holzverkohlung, ein modernes Verfahren, dessen spezielle Verfahrensparameter hohe Fluessigausbeuten ermoeglichen. Hohe Aufheizraten, verbunden mit kurzen Verweilzeiten, werden mit stationaeren Wirbelbettreaktoren erzielt die gegenwaertig vorwiegend fuer die Flash-Pyrolyse von Biomasse eingesetzt werden. Im `Hamburger Verfahren` haben sich Wirbelbettreaktoren im Bereich der Kunststoffpyrolyse bewaehrt. Daher wurde in Zusammenarbeit mit der Universitaet Hamburg und finanzieller Foerderung der Bundesstiftung Umwelt eine Flash-Pyrolyseanlage fuer Biomasse gebaut: In dieser Arbeit werden erste Versuchsreihen, Massenbilanzen und Oelanalysen aus der Pyrolyse von

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.

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...

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.

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.

Water extraction of pyrolysis oil: the first step for the recovery of renewable chemicals

NARCIS (Netherlands)

Vitasari, C.R.; Meindersma, G.W.; Haan, de A.B.

2011-01-01

The interest in biomass as a source of renewable energy and chemicals has been increasing in keeping up with the transition to a sustainable bio-based economy. An important initial step of chemicals recovery from biomass-derived pyrolysis oil is water extraction where most of polar compounds are

Suspension Combustion of Wood: Influence of Pyrolysis Conditions on Char Yield, Morphology, and Reactivity

DEFF Research Database (Denmark)

Dall'Ora, Michelangelo; Jensen, Peter Arendt; Jensen, Anker Degn

2008-01-01

Chars from pine and beech wood were produced by fast pyrolysis in an entrained flow reactor and by slow pyrolysis in a thermogravimetric analyzer. The influence of pyrolysis temperature, heating rate and particle size on char yield and morphology was investigated. The applied pyrolysis temperature...... varied in the range 673−1673 K for slow pyrolysis and between 873 and 1573 K for fast pyrolysis. The chars were oxidized in a thermogravimetric analyzer and the mass loss data were used to determine char oxidation reactivity. Char yield from fast pyrolysis (104−105 K/s) was as low as 1 to 6% on a dry ash......, char oxidation reactivity decreased as pyrolysis temperature increased. The amount and composition of the ash forming matter of the wood fuels seems to play an important role in determining the differences in char yield, morphology and reactivity....

Fast pyrolysis product distribution of biopretreated corn stalk by methanogen.

Science.gov (United States)

Wang, Tipeng; Ye, Xiaoning; Yin, Jun; Jin, Zaixing; Lu, Qiang; Zheng, Zongming; Dong, Changqing

2014-10-01

After pretreated by methanogen for 5, 15 and 25 days, corn stalk (CS) were pyrolyzed at 250, 300, 350, 400, 450 and 500 °C by Py-GC/MS and product distribution in bio-oil was analyzed. Results indicated that methanogen pretreatment changed considerably the product distribution: the contents of sugar and phenols increased; the contents of linear carbonyls and furans decreased; the contents of linear ketones and linear acids changed slightly. Methanogen pretreatment improved significantly the pyrolysis selectivity of CS to phenols especially 4-VP. At 250 °C, the phenols content increased from 42.25% for untreated CS to 79.32% for biopretreated CS for 5 days; the 4-VP content increased from 28.6% to 60.9%. Increasing temperature was contributed to convert more lignin into 4-VP, but decreased its content in bio-oil due to more other chemicals formed. The effects of biopretreatment time on the chemicals contents were insignificant. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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

Method for Hot Real-Time Sampling of Pyrolysis Vapors

Energy Technology Data Exchange (ETDEWEB)

Pomeroy, Marc D [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2017-09-29

Biomass Pyrolysis has been an increasing topic of research, in particular as a replacement for crude oil. This process utilizes moderate temperatures to thermally deconstruct the biomass which is then condensed into a mixture of liquid oxygenates to be used as fuel precursors. Pyrolysis oils contain more than 400 compounds, up to 60 percent of which do not re-volatilize for subsequent chemical analysis. Vapor chemical composition is also complicated as additional condensation reactions occur during the condensation and collection of the product. Due to the complexity of the pyrolysis oil, and a desire to catalytically upgrade the vapor composition before condensation, online real-time analytical techniques such as Molecular Beam Mass Spectrometry (MBMS) are of great use. However, in order to properly sample hot pyrolysis vapors, many challenges must be overcome. Sampling must occur within a narrow range of temperatures to reduce product composition changes from overheating or partial condensation or plugging of lines from condensed products. Residence times must be kept at a minimum to reduce further reaction chemistries. Pyrolysis vapors also form aerosols that are carried far downstream and can pass through filters resulting in build-up in downstream locations. The co-produced bio-char and ash from the pyrolysis process can lead to plugging of the sample lines, and must be filtered out at temperature, even with the use of cyclonic separators. A practical approach for considerations and sampling system design, as well as lessons learned are integrated into the hot analytical sampling system of the National Renewable Energy Laboratory's (NREL) Thermochemical Process Development Unit (TCPDU) to provide industrially relevant demonstrations of thermochemical transformations of biomass feedstocks at the pilot scale.

Effluent Gas Flux Characterization During Pyrolysis of Chicken Manure

Science.gov (United States)

Clark, S. C.; Ryals, R.; Miller, D. J.; Mullen, C. A.; Pan, D.; Zondlo, M. A.; Boateng, A. A.; Hastings, M. G.

2017-12-01

Pyrolysis is a viable option for the production of agricultural resources from diverted organic waste streams and renewable bioenergy. This high temperature thermochemical process yields material with beneficial reuses, including bio-oil and biochar. Gaseous forms of carbon (C) and nitrogen (N) are also emitted during pyrolysis. The effluent mass emission rates from pyrolysis are not well characterized, thus limiting proper evaluation of the environmental benefits or costs of pyrolysis products. We present the first comprehensive suite of C and N mass emission rate measurements of a biomass pyrolysis process using chicken manure as feedstock to produce biochar and bio-oil. Two chicken manure fast pyrolysis experiments were conducted at controlled temperature ranges of 450 - 485 °C and 550 - 585 °C. Mass emission rates of N2O, NO, CO, CO2, CH4 and NH3 were measured using trace gas analyzers. Based on the system mass balance, 23-25% of the total mass of the manure feedstock was emitted as gas, while 52-55% and 23% were converted to bio-oil and biochar, respectively. CO2 and NH3 were the dominant gaseous species by mass, accounting for 58 - 65% of total C mass emitted and 99% of total reactive N mass emitted, respectively. Our gas flux measurements suggest that 1.4 to 2.7 g NH3 -N would be produced from the pyrolysis of one kg of manure. Conservatively scaling up these NH3 pyrolysis emissions in the Chesapeake Bay Watershed, where an estimated 8.64 billion kg of poultry manure is applied to agricultural soils every year, as much as 1.2 x 107 kg of NH3 could be emitted into the atmosphere annually, increasing the potential impact of atmospheric N deposition without a mechanism to capture the gas exhaust during pyrolysis. However, this is considerably less than the potential emissions from NH3 volatilization of raw chicken manure applications, which can be 20-60% of total N applied, and amount to 3.4 x 107 - 1.0 x 108 kg NH3-N yr-1. Pyrolysis has the potential to

Upgrading of the liquid fuel from fast pyrolysis of biomass over MoNi/{gamma}-Al{sub 2}O{sub 3} catalysts

Energy Technology Data Exchange (ETDEWEB)

Xu, Ying; Liang, Wei [Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, Guangdong (China); Graduate School of the Chinese Academy of Sciences, Beijing (China); Wang, Tiejun; Ma, Longlong; Zhang, Qi [Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, Guangdong (China); Key Laboratory of Renewable Energy and Gas Hydrate, Chinese Academy of Sciences, Guangzhou, Guangdong (China)

2010-09-15

The hydrotreatment of bio-oil, which obtained from fast pyrolysis of pine sawdust, was investigated over MoNi/{gamma}-Al{sub 2}O{sub 3} catalyst under mild conditions (373 K, 3 MPa hydrogen pressure). Acetic acid was taken as a model compound to investigate the effects of Mo promoter contents and reducing temperatures of catalysts on the catalysts activity under the condition of 473 K and 3 MPa hydrogen pressure. X-ray diffraction and temperature programmed reduction showed that the addition of Mo promoter benefited the uniformity of nickel species and inhibited the formation of NiAl{sub 2}O{sub 4} spinel in the catalysts. The GC spectrum of liquid products showed the mechanism of the model reaction. The maximum conversion of acetic acid (33.20%) was attained over 0.06MoNi/{gamma}-Al{sub 2}O{sub 3} catalysts being reduced at 873 K. This catalyst was chosen for the upgrading of raw bio-oil. After the upgrading process, the pH value of the bio-oil increased from 2.33 to 2.77. The water content increased from 35.52 wt.% to 41.55 wt.% and the gross calorific value increased from 13.96 MJ/kg to 14.17 MJ/kg. The hydrogen content in the bio-oil increased from 6.25 wt.% to 6.95 wt.%. The product properties of the upgraded bio-oil, particularly the hydrogen content and the acidity were considerably improved. The results of gas chromatography-mass spectrometry analysis showed that both hydrotreatment and esterification had happened over 0.06MoNi/{gamma}-Al{sub 2}O{sub 3} (873) catalyst during the upgrading process. (author)

Production of gaseous and liquid bio-fuels from the upgrading of lignocellulosic bio-oil in sub- and supercritical water: Effect of operating conditions on the process

International Nuclear Information System (INIS)

Remón, J.; Arcelus-Arrillaga, P.; García, L.; Arauzo, J.

2016-01-01

Highlights: • Bio-oil valorisation in sub-/supercritical water: a promising route for bio-fuels. • Effect of P, T, t, catalyst and water regime on bio-oil upgrading studied in depth. • Tailor-made route for H_2, CH_4 and liquid bio-fuel production in a single process. • Upgraded liquid with high proportions of C and H, higher HHV and less O content. - Abstract: This work analyses the influence of the temperature (310–450 °C), pressure (200–260 bar), catalyst/bio-oil mass ratio (0–0.25 g catalyst/g bio-oil), and reaction time (0–60 min) on the reforming in sub- and supercritical water of bio-oil obtained from the fast pyrolysis of pinewood. The upgrading experiments were carried out in a batch micro-bomb reactor employing a co-precipitated Ni–Co/Al–Mg catalyst. This reforming process turned out to be highly customisable for the valorisation of bio-oil for the production of either gaseous or liquid bio-fuels. Depending on the operating conditions and water regime (sub/supercritical), the yields to upgraded bio-oil (liquid), gas and solid varied as follows: 5–90%, 7–91% and 3–31%, respectively. The gas phase, having a LHV ranging from 2 to 17 MJ/m"3 STP, was made up of a mixture of H_2 (9–31 vol.%), CO_2 (41–84 vol.%), CO (1–22 vol.%) and CH_4 (1–45 vol.%). The greatest H_2 production from bio-oil (76% gas yield with a relative amount of H_2 of 30 vol.%) was achieved under supercritical conditions at a temperature of 339 °C, 200 bar of pressure and using a catalyst/bio-oil ratio of 0.2 g/g for 60 min. The amount of C, H and O (wt.%) in the upgraded bio-oil varied from 48 to 74, 4 to 9 and 13 to 48, respectively. This represents an increase of up to 37% and 171% in the proportions of C and H, respectively, as well as a decrease of up to 69% in the proportion of O. The HHV of the treated bio-oil shifted from 20 to 35 MJ/kg, which corresponds to an increase of up to 89% with respect to the HHV of the original bio-oil. With a

Upgrading of syngas hydrotreated fractionated oxidized bio-oil to transportation grade hydrocarbons

International Nuclear Information System (INIS)

Luo, Yan; Hassan, El Barbary; Guda, Vamshi; Wijayapala, Rangana; Steele, Philip H.

2016-01-01

Highlights: • Hydrotreating of fractionated oxidized bio-oil with syngas was feasible. • Hydrocarbon properties were similar with all syngas H_2/CO molar ratios except viscosity. • Syngas with H_2/CO molar ratio of (4:6) produced the highest hydrocarbon yield. • The produced hydrocarbons were in the range of gasoline, jet fuel and diesel boiling points. - Abstract: Fast pyrolysis bio-oils have the potential to replace a part of transportation fuels obtained from fossil. Bio-oil can be successfully upgraded into stable hydrocarbons (gasoline, jet fuel and diesel) through a two-stage hydrodeoxygenation process. Consumption large amount of expensive hydrogen during this process is the major hurdle for commercialization of this technology. Applying syngas in the hydrotreating step can significantly reduce the cost of the whole process and make it competitive. In this study, four different models of syngas with different H_2 concentrations (H_2/CO molar ratios = 2:8, 4:6, 6:4 and 8:2) were used for the 1st-stage hydrotreating step of oxidized fractionated bio-oil (OFB). The 2nd-stage hydrocracking step was performed on the produced organic liquid products (OLPs) by using pure H_2 gas. The effect of syngas H_2 concentrations on the yields and properties of OLPs and the 2nd-stage hydrocarbons (HCs) was investigated. Physical and chemical properties of the 2nd-stage hydrocarbons were similar regardless syngas H_2 content, with the exception of the viscosity. Syngas with H_2/CO molar ratio of 4:6 gave significantly highest HCs yield (24.8 wt.%) based on the OFB. Simulated distillation analysis proved that all 2nd-stage hydrocarbons were mixture from a wide range boiling point fuels. These results also indicated that the successful 1st-stage syngas hydrotreating step was having the potential to produce different hydrocarbons.

Main routes for the thermo-conversion of biomass into fuels and chemicals. Part 1: Pyrolysis systems

International Nuclear Information System (INIS)

Balat, Mustafa; Balat, Mehmet; Kirtay, Elif; Balat, Havva

2009-01-01

Since the energy crises of the 1970s, many countries have become interest in biomass as a fuel source to expand the development of domestic and renewable energy sources and reduce the environmental impacts of energy production. Biomass is used to meet a variety of energy needs, including generating electricity, heating homes, fueling vehicles and providing process heat for industrial facilities. The methods available for energy production from biomass can be divided into two main categories: thermo-chemical and biological conversion routes. There are several thermo-chemical routes for biomass-based energy production, such as direct combustion, liquefaction, pyrolysis, supercritical water extraction, gasification, air-steam gasification and so on. The pyrolysis is thermal degradation of biomass by heat in the absence of oxygen, which results in the production of charcoal (solid), bio-oil (liquid), and fuel gas products. Pyrolysis liquid is referred to in the literature by terms such as pyrolysis oil, bio-oil, bio-crude oil, bio-fuel oil, wood liquid, wood oil, liquid smoke, wood distillates, pyroligneous tar, and pyroligneous acid. Bio-oil can be used as a fuel in boilers, diesel engines or gas turbines for heat and electricity generation.

Photocatalytic Desulfurization of Waste Tire Pyrolysis Oil

Directory of Open Access Journals (Sweden)

Napida Hinchiranan

2011-11-01

Full Text Available Waste tire pyrolysis oil has high potential to replace conventional fossil liquid fuels due to its high calorific heating value. However, the large amounts of sulfurous compounds in this oil hinders its application. Thus, the aim of this research was to investigate the possibility to apply the photo-assisted oxidation catalyzed by titanium dioxide (TiO2, Degussa P-25 to partially remove sulfurous compounds in the waste tire pyrolysis oil under milder reaction conditions without hydrogen consumption. A waste tire pyrolysis oil with 0.84% (w/w of sulfurous content containing suspended TiO2 was irradiated by using a high-pressure mercury lamp for 7 h. The oxidized sulfur compounds were then migrated into the solvent-extraction phase. A maximum % sulfur removal of 43.6% was achieved when 7 g/L of TiO2 was loaded into a 1/4 (v/v mixture of pyrolysis waste tire oil/acetonitrile at 50 °C in the presence of air. Chromatographic analysis confirmed that the photo-oxidized sulfurous compounds presented in the waste tire pyrolysis oil had higher polarity, which were readily dissolved and separated in distilled water. The properties of the photoxidized product were also reported and compared to those of crude oil.

Pyrolysis Strategies for Effective Utilization of Lignocellulosic and Algal Biomass

Science.gov (United States)

Maddi, Balakrishna

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

Oxidative desulfurization of tire pyrolysis oil

OpenAIRE

Ahmad Shahzad; Ahmad Muhammad Imran; Naeem Khawar; Humayun Muhammad; Sebt-E-Zaeem; Faheem Farrukh

2016-01-01

This paper presents a low cost method for the purification of oils obtained from the pyrolysis of used tires. Oxidative desulfurization is a promising route for purification of tire pyrolysis oils as hydro-desulfurization may not be affordable for small scale industries. Different additives and acids have been employed for the enhancement of properties of pyrolytic oils. The experimental conditions were kept identical throughout, i.e. atmospheric pressure a...

Bio-Oil Hydrotreatment for Enhancing Solubility in Biodiesel and the Oxydation Stability of Resulting Blends.

Science.gov (United States)

Botella, Lucía; Stankovikj, Filip; Sánchez, José L; Gonzalo, Alberto; Arauzo, Jesús; Garcia-Pérez, Manuel

2018-01-01

The major challenge for the pyrolytic conversion of lignocellulosic materials into crude bio-oil is the poor quality of the final product. Several strategies (addition of solvents, production of emulsions, and extraction with biodiesel) have been studied to improve its fuel properties. The extraction with biodiesel is an interesting solution because it allows direct utilization of some bio-oil fractions as fuels. However, fraction extracted with biodiesel is typically between 10 and 18 wt. %. In this paper we studied mild hydrotreatment of pyrolysis oil to enhance its solubility in biodiesel. The study was conducted with BTG and Amaron oils hydrotreated at temperatures between 200 and 325°C in the presence of Ru/C catalyst. Hydrotreated oils generated three phases: top oil (light hydrocarbons), middle aqueous phase and bottom heavy oil phase. Each of the phases was characterized and the content of acetic acid, phenols, aromatic compounds, and linear alkane hydrocarbons quantified. The upgraded bio-oils were more soluble in biodiesel than the crude bio-oils, obtaining blends with up to 48 and 38 wt. % for the BTG and Amaron bio-oil, respectively. Some of the fuel properties of the resulting blends are also reported here.

Bio-oil Hydrotreatment for Enhancing Solubility in Biodiesel and the Oxydation Stability of Resulting Blends

Science.gov (United States)

Botella, Lucía; Stankovikj, Filip; Sánchez, José L.; Gonzalo, Alberto; Arauzo, Jesús; Garcia-Pérez, Manuel

2018-04-01

The major challenge for the pyrolytic conversion of lignocellulosic materials into crude bio-oil is the poor quality of the final product. Several strategies (addition of solvents, production of emulsions, and extraction with biodiesel) have been studied to improve its fuel properties. The extraction with biodiesel is an interesting solution because it allows direct utilization of some bio-oil fractions as fuels. However, fraction extracted with biodiesel is typically between 10 and 18 wt. %. In this paper we studied mild hydrotreatment of pyrolysis oil to enhance its solubility in biodiesel. The study was conducted with BTG and Amaron oils hydrotreated at temperatures between 200 and 325 °C in the presence of Ru/C catalyst. Hydrotreated oils generated three phases: top oil (light hydrocarbons), middle aqueous phase and bottom heavy oil phase. Each of the phases was characterized and the content of acetic acid, phenols, aromatic compounds and linear alkane hydrocarbons quantified. The upgraded bio-oils were more soluble in biodiesel than the crude bio-oils, obtaining blends with up to 48 and 38 wt. % for the BTG and Amaron bio-oil, respectively. Some of the fuel properties of the resulting blends are also reported here.

Bio-Oil Hydrotreatment for Enhancing Solubility in Biodiesel and the Oxydation Stability of Resulting Blends

Directory of Open Access Journals (Sweden)

Lucía Botella

2018-04-01

Full Text Available The major challenge for the pyrolytic conversion of lignocellulosic materials into crude bio-oil is the poor quality of the final product. Several strategies (addition of solvents, production of emulsions, and extraction with biodiesel have been studied to improve its fuel properties. The extraction with biodiesel is an interesting solution because it allows direct utilization of some bio-oil fractions as fuels. However, fraction extracted with biodiesel is typically between 10 and 18 wt. %. In this paper we studied mild hydrotreatment of pyrolysis oil to enhance its solubility in biodiesel. The study was conducted with BTG and Amaron oils hydrotreated at temperatures between 200 and 325°C in the presence of Ru/C catalyst. Hydrotreated oils generated three phases: top oil (light hydrocarbons, middle aqueous phase and bottom heavy oil phase. Each of the phases was characterized and the content of acetic acid, phenols, aromatic compounds, and linear alkane hydrocarbons quantified. The upgraded bio-oils were more soluble in biodiesel than the crude bio-oils, obtaining blends with up to 48 and 38 wt. % for the BTG and Amaron bio-oil, respectively. Some of the fuel properties of the resulting blends are also reported here.

Bio-Oil Hydrotreatment for Enhancing Solubility in Biodiesel and the Oxydation Stability of Resulting Blends

Science.gov (United States)

Botella, Lucía; Stankovikj, Filip; Sánchez, José L.; Gonzalo, Alberto; Arauzo, Jesús; Garcia-Pérez, Manuel

2018-01-01

The major challenge for the pyrolytic conversion of lignocellulosic materials into crude bio-oil is the poor quality of the final product. Several strategies (addition of solvents, production of emulsions, and extraction with biodiesel) have been studied to improve its fuel properties. The extraction with biodiesel is an interesting solution because it allows direct utilization of some bio-oil fractions as fuels. However, fraction extracted with biodiesel is typically between 10 and 18 wt. %. In this paper we studied mild hydrotreatment of pyrolysis oil to enhance its solubility in biodiesel. The study was conducted with BTG and Amaron oils hydrotreated at temperatures between 200 and 325°C in the presence of Ru/C catalyst. Hydrotreated oils generated three phases: top oil (light hydrocarbons), middle aqueous phase and bottom heavy oil phase. Each of the phases was characterized and the content of acetic acid, phenols, aromatic compounds, and linear alkane hydrocarbons quantified. The upgraded bio-oils were more soluble in biodiesel than the crude bio-oils, obtaining blends with up to 48 and 38 wt. % for the BTG and Amaron bio-oil, respectively. Some of the fuel properties of the resulting blends are also reported here. PMID:29675406

BioBoost. Biomass based energy intermediates boosting bio-fuel production

Energy Technology Data Exchange (ETDEWEB)

Niebel, Andreas [Karlsruher Institut fuer Technologie (KIT), Karlsruhe (Germany). Institut fuer Katalyseforschung und -technologie (IKFT)

2013-10-01

To increase the share of biomass for renewable energy in Europe conversion pathways which are economic, flexible in feedstock and energy efficient are needed. The BioBoost project concentrates on dry and wet residual biomass and wastes as feedstock for de-central conversion by fast pyrolysis, catalytic pyrolysis and hydrothermal carbonization to the intermediate energy carriers oil, coal or slurry. Based on straw the energy density increases from 2 to 20-30 GJ/m{sup 3}, enabling central GW scale gasification plants for bio-fuel production. A logistic model for feedstock supply and connection of de-central with central conversion is set up and validated allowing the determination of costs, the number and location of de-central and central sites. Techno/economic and environmental assessment of the value chain supports the optimization of products and processes. The utilization of energy carriers is investigated in existing and coming applications of heat and power production and synthetic fuels and chemicals. (orig.)

Physical characterization of biomass-based pyrolysis liquids. Application of standard fuel oil analyses

Energy Technology Data Exchange (ETDEWEB)

Oasmaa, A; Leppaemaeki, E; Koponen, P; Levander, J; Tapola, E [VTT Energy, Espoo (Finland). Energy Production Technologies

1998-12-31

The main purpose of the study was to test the applicability of standard fuel oil methods developed for petroleum-based fuels to pyrolysis liquids. In addition, research on sampling, homogeneity, stability, miscibility and corrosivity was carried out. The standard methods have been tested for several different pyrolysis liquids. Recommendations on sampling, sample size and small modifications of standard methods are presented. In general, most of the methods can be used as such but the accuracy of the analysis can be improved by minor modifications. Fuel oil analyses not suitable for pyrolysis liquids have been identified. Homogeneity of the liquids is the most critical factor in accurate analysis. The presence of air bubbles may disturb in several analyses. Sample preheating and prefiltration should be avoided when possible. The former may cause changes in the composition and structure of the pyrolysis liquid. The latter may remove part of organic material with particles. The size of the sample should be determined on the basis of the homogeneity and the water content of the liquid. The basic analyses of the Technical Research Centre of Finland (VTT) include water, pH, solids, ash, Conradson carbon residue, heating value, CHN, density, viscosity, pourpoint, flash point, and stability. Additional analyses are carried out when needed. (orig.) 53 refs.

Improved lignin pyrolysis for phenolics production in a bubbling bed reactor--Effect of bed materials.

Science.gov (United States)

Li, Dongbing; Briens, Cedric; Berruti, Franco

2015-01-01

Lignin pyrolysis was studied in a bubbling fluidized bed reactor equipped with a fractional condensation train, using nitrogen as the fluidization gas. The effect of different bed materials (silica sand, lignin char, activated lignin char, birch bark char, and foamed glass beads) on bio-oil yield and quality was investigated for a pyrolysis temperature of 550 °C. Results how that a bed of activated lignin char is preferable to the commonly used silica sand: pyrolysis of Kraft lignin with a bed of activated lignin char not only provides a pure char product, but also a higher dry bio-oil yield (with a relative increase of 43%), lower pyrolytic water production, and better bio-oil quality. The bio-oil obtained from Kraft lignin pyrolysis with a bed of activated lignin char has a lower average molecular weight, less tar, more phenolics, and less acidity than when sand is used as bed material. Copyright © 2015 Elsevier Ltd. All rights reserved.

The potential of pyrolysis technology in climate change mitigation – influence of process design and –parameters, simulated in SuperPro Designer Software

DEFF Research Database (Denmark)

Thomsen, Tobias; Hauggaard-Nielsen, Henrik; Bruun, Esben

This report investigates whether or not it would be possible to produce carbon-negative energy from pyrolysis of wheat straw in a series of Danish agricultural scenarios. A combination of process simulation in SuperPro Designer software, correlations derived from literature studies and experimental...... on scenario settings. The final results of the study have been compared to another study with convincing results. Results concluded that the primary force of the pyrolysis technology is the recalcitrant char product and not the pyrolysis oil. Based on this, the study suggests that despite the trend...... in commercial pyrolysis technology that focuses on fast pyrolysis processes with maximized bio-oil production, the twin challenge of climate mitigation and sustainable energy production is most efficiently addressed with a combination of slow pyrolysis and complete biomass conversion through combustion...

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

Energy Technology Data Exchange (ETDEWEB)

Chum, Helena L. [National Renewable Energy Lab. (NREL), Golden, CO (United States)

2018-01-01

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

Preparation and characterization of nanostructured metal oxides for application to biomass upgrading Polar (111) metal oxide surfaces for pyrolysis oil upgrading and lignin depolymerization

Science.gov (United States)

Finch, Kenneth

2013-01-01

Pyrolysis oil, or bio-oil, is one of the most promising methods to upgrade a variety of biomass to transportation fuels. Moving toward a more "green" catalytic process requires heterogeneous catalysis over homogeneous catalysis to avoid extraction solvent waste. Nanoscale catalysts are showing great promise due to their high surface area and unusual surfaces. Base catalyzed condensation reactions occur much quicker than acid catalyzed condensation reactions. However, MgO is slightly soluble in water and is susceptible to degradation by acidic environments, similar to those found in fast-pyrolysis oil. Magnesium oxide (111) has a highly active Lewis base surface, which can catalyze Claisen-Schmidt condensation reactions in the organic phase. It has been shown previously that carbon coating a catalyst, such as a metal oxide, provides integrity while leaving the catalytic activity intact. Here, carbon-coated MgO(111) will be discussed with regards to synthesis, characterization and application to bio-oil upgrading through model compounds. Raman spectroscopy and HR-TEM are used to characterize the thickness and carbon-bonding environment of the carbon coating. Propanal self-condensation reactions have been conducted in the aqueous phase with varying amounts of acetic acid present. Quantitative analysis by gas chromatography was completed to determine the catalytic activity of CC-MgO(111). ICP-OES analysis has been conducted to measure the magnesium concentration in the product solution and give insight into the leaching of the catalyst into the reaction solution.

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

Science.gov (United States)

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

2017-11-01

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

Pyrolysis of flax straw: Characterization of char, liquid, and gas as fuel

Science.gov (United States)

Tushar, Mohammad Shahed Hasan Khan

pyrolysis of flax straw, the experiments were carried out at different pressures, ranging from 10 to 40 psig. The three types of products thus obtained (gas, liquid, char) were thoroughly quantified and analyzed. The yields of the products were found to be dependent on the experimental conditions. It was observed that 10 psig of pressure gave the maximum yield of bio-oil, while 20 psig pressure lead to maximum char yield. The gaseous products were analyzed using an online GC, while the bio-oils were characterized using an offline GC/MS. SEM studies were performed to study the char morphology and porosity. The main gaseous products observed were CO, H2, CO2, CH 4, and C3. The bio-oils were mainly composed of phenolic compounds, carboxylic acids, and furfural. The pH and density of the bio-oils was found to increase as pyrolysis pressure increased. SEM investigation gave insights into the porosity of chars; as pressure increased, an increase in the porosity of char was noted. XRD studies showed that amorphous hydrocarbon and graphitic carbons are the major constituents of char, which was supported by TPO experiments. A TGA study showed two reaction zones for char oxidation. The kinetic parameters of oxidation were estimated using a power law model, which was also used for isothermal pyrolysis and isothermal char oxidation kinetics. Based on the data generated, the pressure of 10 psig was found to be optimum for bio-oil production, while a pressure of 20 psig was optimum for char production. With the increase in pressure, the production of individual gas components increased within the pressure range studied. Finally, with the increase in reaction pressure, temperature and time, the produced chars became less reactive.

Oxidative desulfurization of tire pyrolysis oil

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Ahmad Shahzad

2016-01-01

Full Text Available This paper presents a low cost method for the purification of oils obtained from the pyrolysis of used tires. Oxidative desulfurization is a promising route for purification of tire pyrolysis oils as hydro-desulfurization may not be affordable for small scale industries. Different additives and acids have been employed for the enhancement of properties of pyrolytic oils. The experimental conditions were kept identical throughout, i.e. atmospheric pressure and 50°C temperature for comparison of performance of various additives. The use of hydrogen peroxide-acetic acid mixture (10 wt.% was found more economical and effective in desulfurization and improvement of fuel properties of sample oils. The contribution of sulfuric acid in desulfurization and decreasing viscosity was also satisfactory but due to high price of concentrated sulfuric acid its use may not be economical. Calcium oxide and Fuller’s earth was not found to be effective in desulfurization. Results indicate that oxidative desulfurization could render tire pyrolysis oils suitable for blending as heating fuel.

Validation Results for Core-Scale Oil Shale Pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Staten, Josh; Tiwari, Pankaj

2015-03-01

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

Flash pyrolysis of forestry residues from the Portuguese Central Inland Region within the framework of the BioREFINA-Ter project.

Science.gov (United States)

Amutio, Maider; Lopez, Gartzen; Alvarez, Jon; Moreira, Rui; Duarte, Gustavo; Nunes, Joao; Olazar, Martin; Bilbao, Javier

2013-02-01

The feasibility of the valorization by flash pyrolysis of forest shrub wastes, namely bushes (Cytisus multiflorus, Spartium junceum, Acacia dealbata and Pterospartum tridentatum) has been studied in a conical spouted bed reactor operating at 500 °C, with a continuous biomass feed and char removal. High bio-oil yields in the 75-80 wt.% range have been obtained for all of the materials, with char yields between 16 and 23 wt.% and low gas yields (4-5 wt.%). Bio-oils are composed mainly of water (accounting for a concentration in the 34-40 wt.% range in the bio-oil), phenols, ketones, acids and furans, with lower contents of saccharides, aldehydes and alcohols. Although their composition depends on the raw material, the compounds are similar to those obtained with more conventional feedstocks. Copyright © 2012 Elsevier Ltd. All rights reserved.

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)

Effect of acid catalysts and accelerated aging on the reaction of methanol with hydroxy-acetaldehyde in bio-oil

Directory of Open Access Journals (Sweden)

Bhattacharya, P.

2010-05-01

Full Text Available Bio-oil is a promising alternative source of energy produced from fast pyrolysis of biomass. Increasing the viscosity of bio-oil during storage is a major problem that can be controlled by the addition of methanol or other alcohols. This paper reports the results of our investigation of the reactions of short chain alcohols with aldehydes and acids in bio-oil. The reaction of methanol with hydroxyacetaldehyde (HA to form the acetal was catalyzed by the addition of 7 x 10-4 M strong acids such as sulfuric, hydrochloric, p-toluene sulfonic acid, and methanesulfonic acid. HA formed 2,2-dimethoxyethanol (DME, and at 60 oC the equilibrium was reached in less than one hour. Smaller amounts of DME were formed in the absence of strong acid. HA, acetaldehyde, and propanal formed their corresponding acetals when reacted with methanol, ethanol, 1-propanol or 1-butanol. Esters of acetic acid and hydroxyacetic acid were observed from reactions with these same four alcohols. Other acetals and esters were observed by GC/MS analysis of the reaction products. The results from accelerated aging experiments at 90 oC suggest that the presence of methanol slows polymerization by formation of acetals and esters from low molecular weight aldehydes and organic acids.

Wood pyrolysis oil for diesel engines

Energy Technology Data Exchange (ETDEWEB)

Paro, D.; Gros, S.; Hellen, G.; Jay, D.; Maekelae, T.; Rantanen, O.; Tanska, T. [Wartsila Diesel International Ltd Oy, Vaasa (Finland)

1996-12-01

Wood Pyrolysis oil (WPO) has been identified by the Technical Research Centre of Finland (VTT) as the most competitive biofuel product which can be produced from biomass. The fuel is produced by a fast pyrolysis technique, using wood chipping`s or sawdust. The process can be applied to other recycling products such as straw etc. The use of WPO as a Diesel power plant fuel has been studied, and a fuel specification has been developed. The fuel characteristics have been analysed. There are several fuel properties addressed in the paper which have had to be overcome. New materials have been used in the fuel injection system. The fuel injection system development has progressed from a pump-line-pipe system to a common rail system. The fuel requires a pilot fuel oil injection to initiate combustion. The targets for the fuel injection system have been 1500 bar and 30 deg C injection period with a fuel of 15 MJ/kg lower heating value and 1220 Kg/m{sup 3} density. The combustion characteristics from both a small 80 mm bore engine initially, and then later with a single cylinder test of a 320 mm bore Waertsilae engine, have been evaluated. (author)

Formation of nitrogen-containing compounds during microwave pyrolysis of microalgae: Product distribution and reaction pathways.

Science.gov (United States)

Huang, Feng; Tahmasebi, Arash; Maliutina, Kristina; Yu, Jianglong

2017-12-01

The formation of nitrogen-containing compounds in bio-oil during microwave pyrolysis of Chlorella and Spirulina microalgae has been investigated in this study. Activated carbon (AC) and magnetite (Fe 3 O 4 ) were used as microwave receptors during microwave pyrolysis experiments. It has been found that the use of Fe 3 O 4 increased the total yield of bio-oil. The use of different microwave receptors did not seem to have affected the total yield of nitrogen-containing compounds in the bio-oil. However, Fe 3 O 4 promoted the formation of nitrogen-containing aliphatics, thereby reducing the formation of nitrogen-containing aromatics. The use of AC promoted the dehydration reactions during amino acid decomposition, thereby enhancing the formation of nitrogen-containing aromatics during pyrolysis. From the gas chromatography-mass spectrometry (GC-MS) analysis results, the major high-value nitrogen-containing compounds in the pyrolysis bio-oil of Chlorella and Spirulina were identified as indole and dodecamide. The formation mechanisms of nitrogen-containing compounds were proposed and discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

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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.

Survival of Salmonella, Escherichia coli 0157:H7, non-0157 shiga toxin producing E.coli, and potential surrogate bacteria in crop soil as affected by the addition of fast pyrolysis-generated switchgrass biochar

Science.gov (United States)

Fast pyrolysis of switchgrass (and resultant biochar) can be used for bio-fuel production, soil amendments for fertilizing crops, binding heavy metals, and sequestering environmental biocarbon. To determine the influence of fast pyrolysis-generated switchgrass biochar on survival of foodborne path...

Hydrogenation of fast pyrolyis oil and model compounds in a two-phase aqueous organic system using homogeneous ruthenium catalysts

NARCIS (Netherlands)

Mahfud, F. H.; Ghijsen, F.; Heeres, H. J.

2007-01-01

The use of homogeneous ruthenium catalysts to hydrogenate the water-soluble fraction of pyrolysis oil is reported. Pyrolysis oil, which is obtained by fast pyrolysis of lignocellulosic biomass at 450-600 degrees C, contains significant amounts of aldehydes and ketones (e.g. 1-hydroxy-2-propanone (1)

Effects of pressure on morphology and structure of bio-char from pressurized entrained-flow pyrolysis of microalgae

Directory of Open Access Journals (Sweden)

Kristina Maliutina

2018-06-01

Full Text Available The present dataset describes the entrained-flow pyrolysis of Microalgae Chlorella vulgaris and the results obtained during bio-char characterization. The dataset includes a brief explanation of the experimental procedure, experimental conditions and the influence of pyrolysis conditions on bio-chars morphology and carbon structure. The data show an increase in sphericity and surface smoothness of bio-chars at higher pressures and temperatures. Data confirmed that the swelling ratio of bio-chars increased with pressure up to 2.0 MPa. Consequently, changes in carbon structure of bio-chars were investigated using Raman spectroscopy. The data showed the increase in carbon order of chars at elevated pressures. Changes in the chemical structure of bio-char as a function of pyrolysis conditions were investigated using FTIR analysis. Keywords: Microalgae, Bio-char, Particle swelling, Pressurized pyrolysis

Perspectives for pyrolysis oil production and market in Scandinavia

International Nuclear Information System (INIS)

Sipilae, K.; Oasmaa, A.; Solantausta, Y.; Arpiainen, V.; Nyroenen, T.

1999-01-01

Commercial power production from biomass is mainly based on various combustion technologies, new gasification technologies being on pilot and demonstration scale in Europe. From the market viewpoint, there will be an attractive and large market volume for small and medium-scale combined heat and power production (CHP) and for liquid bioenergy products in order to meet the Kyoto challenges in Europe by the year 2010. Biomass pyrolysis technology offers a novel method of converting solid biomass to a liquid product which can easily be transported, stored and utilised for electricity production by diesel engines and gas turbines. The overall efficiency in pyrolysis oil production can be increased from 65 to 90 % (LHV) by integrating the big-oil production to a conventional boiler plant, the-system identified by VTT. A modern diesel power plant has an efficiency of 40 - 44 % with a high power-to-heat ratio. Parallel to diesel power plants, the big-oil can be used in existing heating oil boilers with minor burner modifications. The paper comprises an overview of market assessments in Scandinavia and a summary of pyrolysis oil production, stability and properties tests. The challenge of today is to understand and improve the properties of pyrolysis oils in order to reach a 12-month storage time without any changes in the homogeneity of pyrolysis oils. Reliable operation of oil-fired boilers and diesel power plants has to be demonstrated. As soon as these problems have been solved, biomass pyrolysis technologies will offer new attractive bioenergy market opportunities where a huge potential can be reached by conversing existing petroleum-fired boilers, 0.1 - 10 MW to big-oils and followed by combined heat and power production with high-efficiency diesel power plants in 0.1 - 10 MW scale. Pyrolysis technology is clearly the most attractive method for producing liquid biofuels, compared to bioalcohols and biodiesel. With the present price structure, pyrolysis oil can be

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.

Rapid and slow pyrolysis of pistachio shell: effect of pyrolysis conditions on the product yields and characterization of the liquid product

Energy Technology Data Exchange (ETDEWEB)

Putun, Ayse E [Department of Chemical Engineering, Anadolu University, Eskisehir 26470, (Turkey); Ozbay, Nurgul [Bozuyuk Vocational School, Anadolu University, Bozuyuk/Bilecik, (Turkey); Varol, Esin Apaydin; Uzun, Basak B; Ates, Fuda [Department of Chemical Engineering, Anadolu University, Eskisehir 26470, (Turkey)

2006-10-30

This study reports the experimental results for the pyrolysis of pistachio shell under different conditions in a tubular reactor under a nitrogen flow. For the different conditions of pyrolysis temperature, nitrogen flow rate and heating rate, pyrolysis temperature of 773 K gave the highest bio-oil yield with a value of 27.7% when the heating rate and carrier gas flow rate were chosen as 300 K min{sup -1} and 100 cm{sup 3} min{sup -1}, respectively. Column chromatography was applied to this bio-oil and its subfractions were characterized by elemental analysis, FT-IR and 1H-NMR. Aliphatic subfraction was conducted to gas chromatography-mass spectroscopy for further characterization. The results for the characterization show that using pistachio shell as a renewable source to produce valuable liquid products is applicable via pyrolysis. (Author)

Historical Developments of Pyrolysis Reactors : A Review

NARCIS (Netherlands)

Garcia-Nunez, J. A.; Pelaez-Samaniego, M.R.; Garcia-Perez, M. E.; Fonts, I.; Abrego, J.; Westerhof, R. J.M.; Garcia Perez, M.

2017-01-01

This paper provides a review of pyrolysis technologies, focusing on reactor designs and companies commercializing these technologies. The renewed interest in pyrolysis is driven by the potential to convert lignocellulosic materials into bio-oil and biochar and the use of these intermediates for the

Short term endurance results on a single cylinder diesel engine fueled with upgraded bio oil biodiesel emulsion

Science.gov (United States)

Prakash, R.; Murugan, S.

2017-11-01

This paper deliberates the endurance test outcomes obtained from a single cylinder, diesel engine fueled with an upgraded bio oil biodiesel emulsion. In this investigation a bio oil obtained by pyrolysis of woody biomass was upgraded with acid treatment. The resulted bio oil was emulsified with addition of biodiesel and suitable surfactant which is termed as ATJOE15. The main objective of the endurance test was to evaluate the wear characteristics of the engine components and lubrication oil properties, when the engine is fueled with the ATJOE15 emulsion. The photographic views taken before and after the end of 100 hrs endurance test, and visual inspection of the engine components, wear and carbon deposit results, are discussed in this paper.

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

Science.gov (United States)

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

2015-01-01

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

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

Science.gov (United States)

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

2016-09-01

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

Jatropha waste meal as an alternative energy source via pressurized pyrolysis: A study on temperature effects

International Nuclear Information System (INIS)

Kongkasawan, Jinjuta; Nam, Hyungseok; Capareda, Sergio C.

2016-01-01

As an alternative energy source, Jatropha is a promising biomass resource due to its high content of oil contained in the seed. However, after the oil extraction process, more than 50% of initial weight remained as residue. This Jatropha de-oiled cake was considered a valuable feedstock for thermochemical conversion process due to its high volatile matter (73%) and energy content (20.5 MJ/kg). Pyrolysis turned biomass into solid product of biochar, liquid product (bio-oil and aqueous phase), and pyrolysis gas. The effects of pyrolysis temperature under the pressure of 0.69 MPa on the product yields and characteristics were investigated using a bench-scale batch reactor. The gross calorific value of pyrolytic oil was measured to be 35 MJ/kg with high carbon content (71%) and low oxygen content (10%). Phenols and hydrocarbons were the main compounds present in the pyrolytic oil. The heating value of the biochar was also high (28 MJ/kg), which was comparable to the fuel coke. More combustible gases were released at high pyrolysis temperature with methane as a main constituent. Pyrolysis temperature of 500 °C, was determined to be an optimum condition for the mass and energy conversions with 89% of the mass and 77% of the energy recovered. - Highlights: • Pressurized pyrolysis of Jatropha wastes at different temperatures was studied. • Full analysis of biochar, bio-oil and pyro gas at different temperatures were done. • Highest aromatics (32%) and HHV (35 MJ/kg) found in bio-oil at 500 °C. • Large amount of paraffins (C 13 –C 16 range) was found in bio-oil.

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.

Coal pyrolysis under synthesis gas, hydrogen and nitrogen

Energy Technology Data Exchange (ETDEWEB)

Ariunaa, A.; Li Bao-Qing; Li Wen; Purevsuren, B. (and others) [Chinese Academy of Sciences, Taiyuan (China)

2007-02-15

Chinese Xundian, Mongolian Shiveeovoo lignites and Khoot oil shale are pyrolyzed under synthesis gas (SG) at temperature range from 400 to 800{sup o}C for lignite and from 300 to 600{sup o}C for oil shale with heating rate of 10{sup o}C/min in a fixed bed reactor. The results were compared with those obtained by pyrolysis under hydrogen and nitrogen. The results showed that unlike pyrolysis at high pressure, there are only slight different in the yields of char and tar among pyrolyses under various gases at room pressure for lignite, while higher liquid yield with lower yields of char and gas was obtained in pyrolysis of oil shale under SG and H{sub 2} than under N{sub 2}. It is found that the pyrite S can be easily removed to partially convert to organic S under various gaseous atmosphere and the total sulfur removal for oil shale is much less than lignite, which might be related to its high ash content. The higher total sulfur removal and less organic S content in the presence of SG in comparison with those under N{sub 2} and even under H{sub 2} in pyrolysis of Xundian lignite might result from the action of CO in SG. However, CO does not show its function in pyrolysis of Khoot oil shale, which might also be related to the high ash content. The results reported show the possibility of using synthesis gas instead of pure hydrogen as the reactive gas for coal hydropyrolysis. 11 refs., 4 figs., 6 tabs.

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