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.

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

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.

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

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.

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

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.

Competition Between Hydrotreating and Polymerization Reactions During Pyrolysis Oil Hydrodeoxygenation

NARCIS (Netherlands)

Mercader, F. De Miguel; Koehorst, P. J. J.; Heeres, H. J.; Kersten, S. R. A.; Hogendoorn, J. A.

2011-01-01

Hydrodeoxygenation (HDO) of pyrolysis oil is an upgrading step that allows further coprocessing of the oil product in (laboratory-scale) standard refinery units to produce advanced biofuels. During HDO, desired hydrotreating reactions are in competition with polymerization reactions that can lead to

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.

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.

In-situ catalytic upgrading of biomass pyrolysis vapor: Co-feeding with methanol in a multi-zone fixed bed reactor

International Nuclear Information System (INIS)

Asadieraghi, Masoud; Wan Daud, Wan Mohd Ashri

2015-01-01

Highlights: • Aromatics yield improved with increasing H/C eff ratio of the feed. • HZSM-5 catalyst was an effective catalyst for in-situ bio-oil upgrading. • Biomass/methanol co-feeding attenuated the coke formation. • Methanol co-feeding enhanced the bio-oil quality. - Abstract: The in-situ catalytic upgrading of the biomass pyrolysis vapor and its mixture with methanol were conducted in a fixed bed multi-zone reactor. The steps were comprised; thermally converting the biomass in the pyrolysis reactor, passing its vapor in contact with the HZSM-5 zeolite catalyst in the presence of methanol vapor, and transformation of the resulting upgraded pyrolysis vapor into the liquid product. The biomass pyrolysis and catalytic pyrolysis vapor upgrading were performed at 500 °C. The highly valuable chemicals production was a function of the hydrogen to carbon effective ratio (H/C eff ) of the feed. This ratio was regulated by changing the relative amount of biomass and methanol. More aromatic hydrocarbons (50.02 wt.%) and less coke deposition on the catalyst (1.3 wt.%) were yielded from the biomass, when methanol was co-fed to the catalytic pyrolysis process (H/C eff = 1.35). In this contribution, the deposited coke on the catalyst was profoundly investigated. The coke, with high contents of oxo-aromatics and aromatic compounds, was generated by polymerization of biomass lignin derived components activated by catalyst acid sites

Pyrolysis oil production, properties, and utilization; Pyrolyysioeljyn valmistus, ominaisuudet ja kaeyttoe

Energy Technology Data Exchange (ETDEWEB)

Sipilae, K.; Oasmaa, A.; Arpiainen, V.; Kuoppala, E.; Leppaemaeki, E.; Solantausta, Y.; Levander, J. VTT Energia

1995-12-31

The main tasks for 1995 were: design and assembling of experimental reactors, and physical and chemical characterisation of pyrolysis oils. A PDU-unit (20 kg/h) has been designed and it will be assembled in April 1996. A 1 kg/h pyrolyzer has been constructed with a hot-filtration system (a ceramic candle filter) and direct quenching with a hydrocarbon oil. The equipment has worked well. Pine saw dust has been used as a feed and a good-quality solids-free product oil has been obtained. In addition to this, a smaller (150 g/h) pyrolyzer has been bought from Canada (University of Waterloo). The small equipment will be used for example for catalytic upgrading of pyrolysis vapours. Chemical characterisation of pyrolysis oil has been carried out 1995. Water extraction has been developed for a fractionation method. Pyrolysis oil samples produced from mixed hardwood, eucalyptus and straw have been employed. The objective of the study has been to develop a simple characterisation method for comparison of different pyrolysis oils. For example reactive compounds have been identified. Main analytical method for analysing the water-soluble fraction has been GC-MS. The research will be continued 1996. A literature review of chemical and physical characterization of pyrolysis oils has been published 1995. Testing of fuel oil analyses has been continued within the IEA pyrolysis project. VTT Energy is responsible for fuel oil analytical methods

Pyrolysis oil production, properties, and utilization; Pyrolyysioeljyn valmistus, ominaisuudet ja kaeyttoe

Energy Technology Data Exchange (ETDEWEB)

Sipilae, K; Oasmaa, A; Arpiainen, V; Kuoppala, E; Leppaemaeki, E; Solantausta, Y; Levander, J. VTT Energia

1996-12-31

The main tasks for 1995 were: design and assembling of experimental reactors, and physical and chemical characterisation of pyrolysis oils. A PDU-unit (20 kg/h) has been designed and it will be assembled in April 1996. A 1 kg/h pyrolyzer has been constructed with a hot-filtration system (a ceramic candle filter) and direct quenching with a hydrocarbon oil. The equipment has worked well. Pine saw dust has been used as a feed and a good-quality solids-free product oil has been obtained. In addition to this, a smaller (150 g/h) pyrolyzer has been bought from Canada (University of Waterloo). The small equipment will be used for example for catalytic upgrading of pyrolysis vapours. Chemical characterisation of pyrolysis oil has been carried out 1995. Water extraction has been developed for a fractionation method. Pyrolysis oil samples produced from mixed hardwood, eucalyptus and straw have been employed. The objective of the study has been to develop a simple characterisation method for comparison of different pyrolysis oils. For example reactive compounds have been identified. Main analytical method for analysing the water-soluble fraction has been GC-MS. The research will be continued 1996. A literature review of chemical and physical characterization of pyrolysis oils has been published 1995. Testing of fuel oil analyses has been continued within the IEA pyrolysis project. VTT Energy is responsible for fuel oil analytical methods

Evolution of Functional Groups during Pyrolysis Oil Upgrading

Energy Technology Data Exchange (ETDEWEB)

Stankovikj, Filip [Department; Tran, Chi-Cong [Department; Kaliaguine, Serge [Department; Olarte, Mariefel V. [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Garcia-Perez, Manuel [Department

2017-07-14

In this paper, we examine the evolution of functional groups (carbonyl, carboxyl, phenol, and hydroxyl) during stabilization at 100–200 °C of two typical wood derived pyrolysis oils from BTG and Amaron in a batch reactor over Ru/C catalyst for 4h. An aqueous and an oily phase were obtained. The content of functional groups in both phases were analyzed by GC/MS, 31P-NMR, 1H-NMR, elemental analysis, KF titration, carbonyl groups by Faix, Folin – Ciocalteu method and UV-Fluorescence. The consumption of hydrogen was between 0.007 and 0.016 g/g oil, and 0.001-0.020 g of CH4/g of oil, 0.005-0.016 g of CO2/g oil and 0.03-0.10 g H2O/g oil were formed. The content of carbonyl, hydroxyl, and carboxyl groups in the volatile GC-MS detectable fraction decreased (80, 65, and ~70% respectively), while their behavior in the total oil and hence in the non-volatile fraction was more complex. The carbonyl groups initially decreased having minimum at ~125-150°C and then increased, while the hydroxyl groups had reversed trend. This might be explained by initial hydrogenation of the carbonyl groups to form hydroxyls, followed by continued dehydration reactions at higher temperatures that may increase their content. The 31P-NMR was on the limit of its sensitivity for the carboxylic groups to precisely detect changes in the non-volatile fraction, however the more precise titration method showed that the concentration of carboxylic groups in the non-volatile fraction remains constant with increased stabilization temperature. The UV-Fluorescence results show that repolymerization increases with temperature. ATR-FTIR method coupled with deconvolution of the region between 1490 and 1850 cm-1 showed to be a good tool for following the changes in carbonyl groups and phenols of the stabilized pyrolysis oils. The deconvolution of the IR bands around 1050 and 1260 cm-1 correlated very well with the changes in the 31P-NMR silent O groups (likely ethers). Most of the H2O formation could be

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.

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.

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

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.

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

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.

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.

Integrating sustainable biofuel and silver nanomaterial production for in situ upgrading of cellulosic biomass pyrolysis

International Nuclear Information System (INIS)

Xue, Junjie; Dou, Guolan; Ziade, Elbara; Goldfarb, Jillian L.

2017-01-01

Graphical abstract: Integrated production of biotemplated nanomaterials and upgraded biofuels (solid lines indicate current processes, dashed lines indicated proposed pathway). - Highlights: • Novel integrated process to co-produce nanomaterials and biofuels via pyrolysis. • Impregnation of biomass with silver nitrate upgrades bio-oil during pyrolysis. • Co-synthesis enhances syngas produced with more hydrogen. • Biomass template impacts bio-fuels and morphology of resulting nanomaterials. - Abstract: Replacing fossil fuels with biomass-based alternatives is a potential carbon neutral, renewable and sustainable option for meeting the world’s growing energy demand. However, pyrolytic conversions of biomass-to-biofuels suffer marginal total energy gain, and technical limitations such as bio-oils’ high viscosity and oxygen contents that result in unstable, corrosive and low-value fuels. This work demonstrates a new integrated biorefinery process for the co-production of biofuels and silver nanomaterials. By impregnating pure cellulose and corn stalk with silver nitrate, followed by pyrolysis, the gas yield (especially hydrogen) increases substantially. The condensable bio-oil components of the impregnated samples are considerably higher in furfurals (including 5-hydroxymethylfurfural). Though the overall activation energy barrier, as determined via the Distributed Activation Energy Model, does not change significantly with the silver nitrate pre-treatment, the increase in gases devolatilized, and improved 5-hydroxymethylfurfural yield, suggest a catalytic effect, potentially increasing decarboxylation reactions. After using this metal impregnation to improve pyrolysis fuel yield, following pyrolysis, the silver-char composite materials are calcined to remove the biomass template to yield silver nanomaterials. While others have demonstrated the ability to biotemplate such nanosilver on cellulosic biomass, they consider only impregnation and oxidation of the

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.

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

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.)

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.

Pyrolysis of waste tyres: a review.

Science.gov (United States)

Williams, Paul T

2013-08-01

Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H(2), C(1)-C(4) hydrocarbons, CO(2), CO and H(2)S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale. Copyright © 2013 Elsevier Ltd. All rights reserved.

Evaluation of the production potential of bio-oil from Vietnamese biomass resources by fast pyrolysis

International Nuclear Information System (INIS)

Phan, Binh M.Q.; Duong, Long T.; Nguyen, Viet D.; Tran, Trong B.; Nguyen, My H.H.; Nguyen, Luong H.; Nguyen, Duc A.; Luu, Loc C.

2014-01-01

Agricultural activities in Vietnam generate about 62 million tonnes of biomass (rice straw, rice husk, bagasse, corn cob, corn stover, etc.) annually. In this work, four different types of biomass from Vietnam, namely rice straw, rice husk, factory bagasse, and corn cob, have been studied as potential raw materials to produce bio-oil by fast pyrolysis technology. Test runs were conducted in a fluidized-bed reactor at a temperature of 500 °C and residence time less than 2 s. Size and moisture content of the feed were less than 2 mm and 2%, respectively. It was found that yields of bio-oil as a liquid product obtained from pyrolysis of these feedstocks were more than 50% and that obtained from the bagasse was the highest. Bio-oil quality from Vietnamese biomass resources satisfies ASTM D7544-12 standard for pyrolysis liquid biofuels. These results showed the potential of using biomass in Vietnam to produce bio-oil which could be directly used as a combustion fuel or upgraded into transportation fuels and chemicals. - Highlights: • Four types of Vietnamese biomass were firstly analyzed in detail. • Optimal conditions for fast pyrolysis reaction for Vietnamese biomass types. • Bio-oil product adapted to the standard specification for pyrolysis liquid biofuel

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)

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

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. .

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.

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.

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

In-situ catalytic upgrading of biomass pyrolysis vapor: Using a cascade system of various catalysts in a multi-zone fixed bed reactor

International Nuclear Information System (INIS)

Asadieraghi, Masoud; Wan Daud, Wan Mohd Ashri

2015-01-01

Highlights: • A cascade system of different catalysts exhibited the best performance to produce high quality bio-oil. • Meso-HZSM-5, Ga (1 wt.%)/meso-HZSM-5 and Cu (5 wt.%)/SiO 2 were employed in a cascade system. • The incorporation of the appropriate gallium amount to meso-HZSM-5 enhanced the aromatics selectivity. • Meso-HZSM-5 indicated a very good activity in bio-oil upgrading. - Abstract: The in-situ catalytic upgrading of palm kernel shell (PKS) fast pyrolysis vapors was performed over each individual meso-H-ZSM-5, Ga/meso-HZSM-5 and Cu/SiO 2 catalyst or a cascade system of them in a multi-zone fixed bed reactor. The effects of mesoporosity creation into the parent H-ZSM-5 catalyst and also gallium incorporation into mesoporous H-ZSM-5 on the produced bio-oil chemical composition and distribution were studied. Key upgrading reactions for different oxygenated compounds in pyrolysis oil (small oxygenates, lignin derived and sugar derived components), including aldol condensation, alkylation, hydrogenation, aromatization, and deoxygenation were discussed. The catalysts were characterized using SEM, XRF, XRD, N 2 adsorption and NH 3 -TPD methods. Furthermore, the produced bio-oils (catalytic and non-catalytic) were analyzed using GC–MS, FTIR, CHNS/O elemental analyzer and Karl Fischer titration. Production of the upgraded bio-oil with lower content of oxygenated compound was the main objective of this investigation. Among different catalysts, meso-H-ZSM-5 zeolite demonstrated a very good activity in aromatization and deoxygenation during the upgrading of pyrolytic vapors, although it decreased the bio-oil yield (32.6 wt.%). The gallium incorporation into the meso-HZSM-5 zeolite increased the bio-oil yield from 32.6 wt.% (meso-HZSM-5) to 35.8 wt.% (using 1.0 wt.% Ga). Furthermore, the aromatics selectivity was enhanced when the appropriate amount of gallium (1.0 wt.%) was introduced. A cascade system of various catalysts comprising meso-HZSM-5, Ga (1

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.

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.

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

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...

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.

Oxidative desulfurization of tire pyrolysis oil

Directory of Open Access Journals (Sweden)

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 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

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

Energy Technology Data Exchange (ETDEWEB)

Xu, Ying; Wang, Lu [Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou Guangdong 510640 (China); Key Laboratory of Renewable Energy and Gas Hydrate, CAS, Guangzhou Guangdong 510640 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100039 (China); Wang, Tiejun; Ma, Longlong; Zhang, Qi [Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou Guangdong 510640 (China); Key Laboratory of Renewable Energy and Gas Hydrate, CAS, Guangzhou Guangdong 510640 (China)

2009-08-15

High amounts of acid compounds in bio-oil not only lead to the deleterious properties such as corrosiveness and high acidity, but also set up many obstacles to its wide applications. By hydrotreating the bio-oil under mild conditions, some carboxylic acid compounds could be converted to alcohols which would esterify with the unconverted acids in the bio-oil to produce esters. The properties of the bio-oil could be improved by this method. In the paper, the raw bio-oil was produced by vacuum pyrolysis of pine sawdust. The optimal production conditions were investigated. A series of nickel-based catalysts were prepared. Their catalytic activities were evaluated by upgrading of model compound (glacial acetic acid). Results showed that the reduced Mo-10Ni/{gamma}-Al{sub 2}O{sub 3} catalyst had the highest activity with the acetic acid conversion of 33.2%. Upgrading of the raw bio-oil was investigated over reduced Mo-10Ni/{gamma}-Al{sub 2}O{sub 3} catalyst. After the upgrading process, the pH value of the bio-oil increased from 2.16 to 2.84. The water content increased from 46.2 wt.% to 58.99 wt.%. The H element content in the bio-oil increased from 6.61 wt.% to 6.93 wt.%. The dynamic viscosity decreased a little. The results of GC-MS spectrometry analysis showed that the ester compounds in the upgraded bio-oil increased by 3 times. It is possible to improve the properties of bio-oil by hydrotreating and esterifying carboxyl group compounds in the bio-oil. (author)

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

Catalytic Hydrodeoxygenation of Biomass Pyrolysis Vapor Model Compounds over Molybdenum Sulfide Catalysts: Influence of Support, H₂S and Water

DEFF Research Database (Denmark)

Arndal, Trine Marie Hartmann; Høj, Martin; Pintos, Delfina Garcia

value, acidity and stability [1,2]. Upgrading ofcondensed pyrolysis oil is challenged by severe polymerization and coking upon heating. Instead, it is proposed toperform pyrolysis in the presence of hydrogen and an HDO catalyst for immediate stabilization and upgrading ofreactive pyrolysis products...

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

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

Science.gov (United States)

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

2014-12-01

Aqueous phase hydrodeoxygenation of lignin pyrolysis oil and related model compounds were investigated using four noble metals supported on activated carbon. The hydrodeoxygenation of guaiacol has three major reaction pathways and the demethylation reaction, mainly catalyzed by Pd, Pt and Rh, produces catechol as the products. The presence of catechol and guaiacol in the reaction is responsible for the coke formation and the catalysts deactivation. As expected, there was a significant decrease in the specific surface area of Pd, Pt and Rh catalysts during the catalytic reaction because of the coke deposition. In contrast, no catechol was produced from guaiacol when Ru was used so a completely hydrogenation was accomplished. The lignin pyrolysis oil upgrading with Pt and Ru catalysts further validated the reaction mechanism deduced from model compounds. Fully hydrogenated bio-oil was produced with Ru catalyst. Copyright © 2014 Elsevier Ltd. All rights reserved.

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...

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.

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

International Nuclear Information System (INIS)

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

2014-01-01

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

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

Energy Technology Data Exchange (ETDEWEB)

Wang, Wen-liang [MOE Key Laboratory of Wooden Material Science and Application, College of Material Science and Technology, Wood Science and Technology, Beijing Forestry University, 100083 Beijing (China); Chang, Jian-min, E-mail: cjianmin@bjfu.edu.cn [MOE Key Laboratory of Wooden Material Science and Application, College of Material Science and Technology, Wood Science and Technology, Beijing Forestry University, 100083 Beijing (China); Cai, Li-ping [Mechanical and Energy Engineering Department, University of North Texas, 3940 N. Elm, Denton 72076, TX (United States); Shi, Sheldon Q., E-mail: Sheldon.Shi@unt.edu [Mechanical and Energy Engineering Department, University of North Texas, 3940 N. Elm, Denton 72076, TX (United States)

2014-12-15

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

Combustion Properties of Biomass Flash Pyrolysis Oils: Final Project Report

Energy Technology Data Exchange (ETDEWEB)

C. R. Shaddix; D. R. Hardesty

1999-04-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-11-17

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

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

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...

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...

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.

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

Science.gov (United States)

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

2015-02-01

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

Coprocessing of biooils from biomass pyrolysis and bitumen from oil sands

Energy Technology Data Exchange (ETDEWEB)

Feng, M.; Daruwalla, S.; Daruwalla, D.D. [Southwest Research Inst., San Antonia, TX (United States). Dept. of Chemical Engineering

2009-07-01

Liquid biooils can be produced from the thermochemical treatment of biomass by pyrolysis. However, because of their poor volatility, high viscosity, coking, corrosiveness, and cold flow problems, biooils cannot be used directly as transportation fuel. Biooils can be upgraded into a liquid transportation fuel by hydrodeoxygenation with typical hydrotreating procedure with sulfided cobalt and molybdenum (CoMo) or nickel molybdenum (NiMo) as catalysts in the current oil refinery facilities. Coprocessing of biooils and bitumen from oil sand provides an opportunity to process the two feeds at the same time which can be achieved by injection of pyrolytic biooils and vacuum gas oil (VGO) from bitumen into a fluid catalytic cracking (FCC) unit if the acid number of the biooils is below 35. Typically the biooils are diluted to about 1.5 to 5 per cent in the VGO feed to be processed. For the blends of VGO and biooils, the biooils appear to facilitate the cracking of the VGO and shift yields toward light ends, lower light cycle oil. They also clarify slurry oil, which makes the process more cost effective. This paper briefly reviewed the typical methods for bitumen pretreatment and preliminary upgrading. The paper also discussed the current status of coprocessing of biooils and hydrocarbons, and suggested two possible processes for coprocessing bitumen with biooils and biopitches. The impact on the hydrodesulphurization process conversion of dibenzothiophenic compounds was also studied, showing no differences of the inhibiting effect between these molecules. 8 refs., 4 tabs., 6 figs.

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)

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...

Method for Hot Real-Time Analysis of Pyrolysis Vapors at Pilot Scale

Energy Technology Data Exchange (ETDEWEB)

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

2017-09-29

Pyrolysis oils contain more than 400 compounds, up to 60% of which do not re-volatilize for subsequent chemical analysis. Vapor chemical composition is also complicated as additional condensation reactions occur during quenching 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 at the pilot scale, many challenges must be overcome.

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.

Catalytic upgrading of sugar fractions from pyrolysis oils in supercritical mono-alcohols over Cu doped porous metal oxide

NARCIS (Netherlands)

Yin, Wang; Venderbosch, Hendrikus; Bottari, Giovanni; Krawzcyk, Krzysztof K.; Barta, Katalin; Heeres, Hero Jan

In this work, we report on the catalytic valorization of sugar fractions, obtained by aqueous phase extraction of fast pyrolysis oils, in supercritical methanol (scMeOH) and ethanol (scEtOH) over a copper doped porous metal oxide (Cu-PMO). The product mixtures obtained are, in principle, suitable

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.

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

Science.gov (United States)

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

2014-12-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Elliott, Douglas [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Olarte, M. V. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Hart, T. R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2016-07-21

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-04-06

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

Microwave-assisted co-pyrolysis of brown coal and corn stover for oil production.

Science.gov (United States)

Zhang, Yaning; Fan, Liangliang; Liu, Shiyu; Zhou, Nan; Ding, Kuan; Peng, Peng; Anderson, Erik; Addy, Min; Cheng, Yanling; Liu, Yuhuan; Li, Bingxi; Snyder, John; Chen, Paul; Ruan, Roger

2018-07-01

The controversial synergistic effect between brown coal and biomass during co-pyrolysis deserves further investigation. This study detailed the oil production from microwave-assisted co-pyrolysis of brown coal (BC) and corn stover (CS) at different CS/BC ratios (0, 0.33, 0.50, 0.67, and 1) and pyrolysis temperatures (500, 550, and 600 °C). The results showed that a higher CS/BC ratio resulted in higher oil yield, and a higher pyrolysis temperature increased oil yield for brown coal and coal/corn mixtures. Corn stover and brown coal showed different pyrolysis characteristics, and positive synergistic effect on oil yield was observed only at CS/BC ratio of 0.33 and pyrolysis temperature of 600 °C. Oils from brown coal mainly included hydrocarbons and phenols whereas oils from corn stover and coal/corn mixtures were dominated by ketones, phenols, and aldehydes. Positive synergistic effects were observed for ketones, aldehydes, acids, and esters whereas negative synergistic effects for hydrocarbons, phenols and alcohols. Copyright © 2018 Elsevier Ltd. All rights reserved.

Spectroscopic and chromatographic analysis of oil from an oil shale flash pyrolysis unit

Energy Technology Data Exchange (ETDEWEB)

Khraisha, V.H.; Irqsousi, N.A. [University of Jordan, Amman (Jordan). Dept. of Chemical Engineering; Shabib, I.M. [Applied Science Univ., Amman (Jordan). Dept. of Chemistry

2003-01-01

In this investigation, spectroscopic (FT-IR, UV-Vis, {sup 1}H NMR) and chromatographic (GC) techniques were used to analyze two Jordanian shale oils, Sultani and El-Lajjun. The oils were extracted at different pyrolysis temperatures (400-500{sup o}C) using a fluidized bed reactor. The spectroscopic and chromatographic analyses show that the variation of pyrolysis temperature has no significant effect on the composition of the produced oil. The {sup 1}H NMR results indicate that the protons of methyl and methelyene represent the bulk of the hydrogen ({approx}90%) in most shale oil samples. GC analysis reveals that the oil samples contain n-alkanes with a predominant proportion of n-C{sub 25}. (Author)

Influence of Promotor, H₂O and H₂S on the Hydrodeoxygenation of Biomass Pyrolysis Vapor over MoS₂ Catalysts

DEFF Research Database (Denmark)

Arndal, Trine M. H.; Høj, Martin; Gaur, Abhijeet

Catalytic hydropyrolysis combines fast pyrolysis with catalytic upgrading by hydrodeoxygenation (HDO) in a single step for the production of fuel oil from biomass in which reactive pyrolysis vapors are upgraded before condensation. Catalyst activity and lifetime is challenged by carbon deposition...

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

Science.gov (United States)

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

2013-08-27

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

Review of fuel oil quality and combustion of fast pyrolysis bio-oils from lignocellulosic biomass

International Nuclear Information System (INIS)

Lehto, Jani; Oasmaa, Anja; Solantausta, Yrjö; Kytö, Matti; Chiaramonti, David

2014-01-01

Highlights: • Review of state-of-the-art fast pyrolysis oil combustion in burner applications. • Fast pyrolysis oil has been found to be suitable for industrial scale utilization. • Curves for NO x -emissions for air-assisted atomization burners are presented. • Quality control, combined with standards and specifications is recommended. - Abstract: Fast pyrolysis bio-oils are completely different from petroleum fuels and other bio-fuels available in the market, as regards both to their physical properties and chemical composition. When the unusual properties of these bio-oils are carefully taken into account in system and burner design, their combustion without a pilot flame or support fuel is possible on an industrial scale. The aim of the paper is to review the work done on combustion of fast pyrolysis bio-oils and highlight the latest and most important findings of its combustion from laboratory fundamentals to industrial scale. The main focus of the paper is on the bio-oil burner applications. In recent industrial scale bio-oil combustion tests, bio-oil has been found to be technically suitable for replacing heavy fuel oil in district heating. In addition, it has also been found out that limited possibilities for further lowering particulate emissions exist, since the majority of the particulates are typically incombustible matter. Curves for NO x -emissions of fast pyrolysis bio-oil combustion for air-assisted atomization burners are presented in the paper. Current burner designs are quite sensitive to the changes in the quality of the bio-oil, which may cause problems in ignition, flame detection and flame stabilization. Therefore, in order to be able to create reliable bio-oil combustion systems that operate at high efficiency, bio-oil grades should be standardized for combustion applications. Careful quality control, combined with standards and specifications, all the way from feedstock harvesting through production to end-use is recommended in

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

Alberta oil sands crudes : upgrading and marketing

International Nuclear Information System (INIS)

Ashar, M.

2008-01-01

Open pit mining and in situ techniques, such as steam stimulation, are used to recover Alberta's bitumen and heavy oil resources, which have higher viscosities than conventional hydrocarbons. The bitumen is typically upgraded to synthetic crude oil (SCO). In the simplest processing scheme, the bitumen is blended with diluent for ease in pipeline transport and then processed at refineries with upgrading facilities. The bitumen is also upgraded to light SCO at world-scale upgraders in Alberta. The SCO is then processed at refineries in downstream markets. The 2 categories of upgrading, notably primary and secondary upgrading, were described in this article along with technology options for both categories. Slurry hydrocracking is regarded as the most interesting emerging residual fuel upgrading technology. It combines special catalyst mixes with the latest slurry reactor designs as well as innovative catalyst capture and recycle schemes to produce very high conversions and potentially superior upgrading economics. The increase in volume and rate of SCO from Alberta provides refiners in the oil sands marketing sector an unprecedented choice of opportunities to improve profitability. Key trends indicate that production will increase substantially from 2008 to 2030. 5 figs

Alberta oil sands crudes : upgrading and marketing

Energy Technology Data Exchange (ETDEWEB)

Ashar, M. [Suncor Energy, Fort McMurray, AB (Canada)

2008-05-15

Open pit mining and in situ techniques, such as steam stimulation, are used to recover Alberta's bitumen and heavy oil resources, which have higher viscosities than conventional hydrocarbons. The bitumen is typically upgraded to synthetic crude oil (SCO). In the simplest processing scheme, the bitumen is blended with diluent for ease in pipeline transport and then processed at refineries with upgrading facilities. The bitumen is also upgraded to light SCO at world-scale upgraders in Alberta. The SCO is then processed at refineries in downstream markets. The 2 categories of upgrading, notably primary and secondary upgrading, were described in this article along with technology options for both categories. Slurry hydrocracking is regarded as the most interesting emerging residual fuel upgrading technology. It combines special catalyst mixes with the latest slurry reactor designs as well as innovative catalyst capture and recycle schemes to produce very high conversions and potentially superior upgrading economics. The increase in volume and rate of SCO from Alberta provides refiners in the oil sands marketing sector an unprecedented choice of opportunities to improve profitability. Key trends indicate that production will increase substantially from 2008 to 2030. 5 figs.

Scrap tire pyrolysis using a new type two-stage pyrolyzer: Effects of dolomite and olivine on producing a low-sulfur pyrolysis oil

International Nuclear Information System (INIS)

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

2016-01-01

Scrap tire pyrolysis was performed using a two-stage pyrolyzer consisting of an auger reactor and a fluidized bed reactor to produce a low-sulfur pyrolysis oil. In the experiments, the effect of the residence time of the feed material in the auger reactor was investigated at ∼300 (auger reactor) and 500 °C (fluidized bed reactor). In addition, natural dolomite and olivine and calcined dolomite and olivine were used as the fluidized bed materials to examine their effects on reducing the sulfur content of pyrolysis oil. In the experiments, the yields of the oil from the auger reactor were 1.4–3.7 wt%, and it was enriched with DL-limonene whose content in the oil was 40–50 wt%. The yields of the oil from the fluidized bed reactor were 42–46 wt%. The optimum residence time of the feed material in the auger reactor turned out to be 3.5 min. Calcined dolomite and olivine significantly decreased the sulfur content of pyrolysis oil. Metal oxides of the additives appeared to react with H_2S to form metal sulfides. The sulfur content of pyrolysis oil obtained with calcined olivine was 0.45 wt%. - Highlights: • Scrap tires were successfully pyrolyzed in a new type two-stage pyrolyzer. • The two-stage pyrolyzer is composed of an auger and fluidized bed reactors. • Calcination of olivine and dolomite led to a strong decrease in sulfur. • The lowest sulfur content of pyrolysis oil was 0.45 wt%. • Pyrolysis oil yields from the fluidized bed reactor were 43–46 wt%.

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.

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

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.

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

Co-Pyrolysis Behaviors of the Cotton Straw/PP Mixtures and Catalysis Hydrodeoxygenation of Co-Pyrolysis Products over Ni-Mo/Al2O3 Catalyst

Directory of Open Access Journals (Sweden)

Derun Hua

2015-12-01

Full Text Available The doping of PP (polypropylene with cotton straw improved the bio-oil yield, which showed there was a synergy in the co-pyrolysis of the cotton straw and PP at the range of 380–480 °C. In a fixed-bed reactor, model compounds and co-pyrolysis products were used for reactants of hydrodeoxygenation (HDO over Ni-Mo/Al2O3. The deoxygenation rate of model compounds decreased over Ni-Mo/Al2O3 in the following order: alcohol > aldehyde > acetic acid > ethyl acetate. The upgraded oil mainly consisted of C11 alkane.

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.

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

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

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-02-04

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

Feasibility study for thermal treatment of solid tire wastes in Bangladesh by using pyrolysis technology

International Nuclear Information System (INIS)

Islam, M.R.; Joardder, M.U.H.; Hasan, S.M.; Takai, K.; Haniu, H.

2011-01-01

In this study on the basis of lab data and available resources in Bangladesh, feasibility study has been carried out for pyrolysis process converting solid tire wastes into pyrolysis oils, solid char and gases. The process considered for detailed analysis was fixed-bed fire-tube heating pyrolysis reactor system. The comparative techno-economic assessment was carried out in US$ for three different sizes plants: medium commercial scale (144 tons/day), small commercial scale (36 tons/day), pilot scale (3.6 tons/day). The assessment showed that medium commercial scale plant was economically feasible, with the lowest unit production cost than small commercial and pilot scale plants for the production of crude pyrolysis oil that could be used as boiler fuel oil and for the production of upgraded liquid-products.

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.

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.

Kinetic Study of the Catalytic Pyrolysis of Oil-Containing Waste

Directory of Open Access Journals (Sweden)

Kirill Chalov

2016-10-01

Full Text Available Basing on the experimental data the optimal parameters of the pyrolysis of heavy and residual hydrocarbons of oil were defined as follows: temperature of 500 °С; catalyst  of CoCl2 with the catalyst loading 5% (wt. of the substrate weight. Under the optimal conditions the kinetic investigation of the pyrolysis process was carried out using the thermogravimetric method. According to the investigation, it was found that the activation energy of the catalytic pyrolysis of oil-containing waste decreased by 20-30 kJ/mol in comparison to non-catalytic process. Copyright © 2016 BCREC GROUP. All rights reserved Received: 13th July 2015; Revised: 25th March 2016; Accepted: 1st April 2016 How to Cite: Chalov, K., Lugovoy, Y., Kosivtsov, Y., Sulman, M., Sulman, E., Matveeva, V., Stepacheva, A. (2016. Kinetic Study of the Catalytic Pyrolysis of Oil-Containing Waste. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (3: 330-338 (doi:10.9767/bcrec.11.3.572.330-338 Permalink/DOI: http://doi.org/10.9767/bcrec.11.3.572.330-338

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)

Pore Scale Analysis of Oil Shale/Sands Pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Lin, Chen-Luh [Univ. of Utah, Salt Lake City, UT (United States); Miller, Jan [Univ. of Utah, Salt Lake City, UT (United States)

2011-03-01

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

Life-Cycle Assessment of Pyrolysis Bio-Oil Production*

Energy Technology Data Exchange (ETDEWEB)

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

2012-07-01

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

Kinetic Study on Pyrolysis of Oil Palm Frond

International Nuclear Information System (INIS)

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

2016-01-01

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

Upgrading of raw tall oil soap into fuel oils and lubricants; Raakasuovan jalostus poltto- ja voiteluoeljyksi

Energy Technology Data Exchange (ETDEWEB)

Oasmaa, A; Arpiainen, V; McKeough, P; Tapola, E; Haekkinen, R; Kuoppala, E; Koskela, K [VTT Energy, Jyvaeskylae (Finland). Energy Production Technologies

1997-12-01

Thermochemical processing of tall oil soap originating from various mixtures of birch and pine has been experimentally investigated. The organic matter of tall oil soap, which is a by- product of Kraft pulping, originates mainly from wood extractives. Conventional processing of tall oil soap involves acidulation with sulphuric acid to yield crude tall oil and subsequent distillation of the oil at centralised refineries. Because tall oil originating from birch wood is far less valuable than that from pine, there is an economic incentive in the Nordic countries to develop alternative conversion processes for the tall oil soap produced at pulp mills where birch is widely used as feedstock. Furthermore, thermochemical processing of tall oil soap does not introduce sulphur into the chemical recovery cycle. This would be a significant advantage in future mills employing closure of water circuits and/or sulphur-free pulping. In small-scale experiments tall oil soaps from wood mixtures with high birch content have been processed using both liquid-phase thermal treatment and pyrolysis. The liquid-phase thermal treatment at 450 deg C under a nitrogen atmosphere yielded a good-quality oil product at high yield (about 50 % of the energy content of the tall oil soap). In the atmospheric pyrolysis of birch tall oil soap a separation of inorganic and organic constituents was obtained. The energy value of the product gases was high. Both processes are promising, but the pyrolysis alternative has the greater economic potential, providing that the promising preliminary experimental results have given a true picture of the performance of the full-scale pyrolysis process. (orig.)

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...

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.

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

Science.gov (United States)

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

2010-01-01

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

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.)

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

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

Science.gov (United States)

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

2015-10-01

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

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

Science.gov (United States)

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

Down-hole catalytic upgrading of heavy crude oil

Energy Technology Data Exchange (ETDEWEB)

Weissman, J.G.; Kessler, R.V.; Sawicki, R.A.; Belgrave, J.D.M.; Laureshen, C.J.; Mehta, S.A.; Moore, R.G.; Ursenbach, M.G. [University of Calgary, Calgary, AB (Canada). Dept. of Chemical and Petroleum Engineering

1996-07-01

Several processing options have been developed to accomplish near-well bore in-situ upgrading of heavy crude oils. These processes are designed to pass oil over a fixed bed of catalyst prior to entering the production well, the catalyst being placed by conventional gravel pack methods. The presence of brine and the need to provide heat and reactant gases in a down-hole environment provide challenges not present in conventional processing. These issues were addressed and the processes demonstrated by use of a modified combustion tube apparatus. Middle-Eastern heavy crude oil and the corresponding brine were used at the appropriate reservoir conditions. In-situ combustion was used to generate reactive gases and to drive fluids over a heated sand or catalysts bed, simulating the catalyst contacting portion of the proposed processes. The heavy crude oil was found to be amenable to in-situ combustion at anticipated reservoir conditions, with a relatively low air requirement. Forcing the oil to flow over a heated zone prior to production results in some upgrading of the oil, as compared to the original oil, due to thermal effects. Passing the oil over a hydroprocessing catalyst located in the heated zone results in a product that is significantly upgraded as compared to either the original oil or thermally processed oil. Catalytic upgrading is due to hydrogenation and the results in about a 50% sulfur removal and an 8{degree} API gravity increase. Additionally, the heated catalyst was found to be efficient at converting CO to additional H{sub 2}. While all of the technologies needed for a successful field trial of in-situ catalytic upgrading exist, a demonstration has yet to be undertaken. 27 refs., 5 figs., 5 tabs.

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.

Molten salt pyrolysis of milled beech wood using an electrostatic precipitator for oil collection

Directory of Open Access Journals (Sweden)

Heidi S. Nygård

2015-07-01

Full Text Available A tubular electrostatic precipitator (ESP was designed and tested for collection of pyrolysis oil in molten salt pyrolysis of milled beech wood (0.5-2 mm. The voltage-current (V-I characteristics were studied, showing most stable performance of the ESP when N2 was utilized as inert gas. The pyrolysis experiments were carried out in FLiNaK and (LiNaK2CO3 over the temperature range of 450-600 ℃. The highest yields of pyrolysis oil were achieved in FLiNaK, with a maximum of 34.2 wt% at 500 ℃, followed by a decrease with increasing reactor temperature. The temperature had nearly no effect on the oil yield for pyrolysis in (LiNaK2CO3 (19.0-22.5 wt%. Possible hydration reactions and formation of HF gas during FLiNaK pyrolysis were investigated by simulations (HSC Chemistry software and measurements of the outlet gas (FTIR, but no significant amounts of HF were detected.

Catalytic upgrading of bio-oil produced from hydrothermal liquefaction of Nannochloropsis sp.

Science.gov (United States)

Shakya, Rajdeep; Adhikari, Sushil; Mahadevan, Ravishankar; Hassan, El Barbary; Dempster, Thomas A

2018-03-01

Upgrading of bio-oil obtained from hydrothermal liquefaction (HTL) of algae is necessary for it to be used as a fuel. In this study, bio-oil obtained from HTL of Nannochloropsis sp. was upgraded using five different catalysts (Ni/C, ZSM-5, Ni/ZSM-5, Ru/C and Pt/C) at 300 °C and 350 °C. The upgraded bio-oil yields were higher at 300 °C; however, higher quality upgraded bio-oils were obtained at 350 °C. Ni/C gave the maximum upgraded bio-oil yield (61 wt%) at 350 °C. However, noble metal catalysts (Ru/C and Pt/C) gave the better upgraded bio-oils in terms of acidity, heating values, and nitrogen values. The higher heating value of the upgraded bio-oils ranged from 40 to 44 MJ/kg, and the nitrogen content decreased from 5.37 to 1.29 wt%. Most of the upgraded bio-oils (35-40 wt%) were in the diesel range. The major components present in the gaseous products were CH 4 , CO, CO 2 and lower alkanes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons

Science.gov (United States)

Gordon, John Howard

2014-09-09

A method of upgrading an oil feedstock by removing heteroatoms and/or one or more heavy metals from the oil feedstock composition. This method reacts the oil feedstock with an alkali metal and an upgradant hydrocarbon. The alkali metal reacts with a portion of the heteroatoms and/or one or more heavy metals to form an inorganic phase separable from the organic oil feedstock material. The upgradant hydrocarbon bonds to the oil feedstock material and increases the number of carbon atoms in the product. This increase in the number of carbon atoms of the product increases the energy value of the resulting oil feedstock.

Effect of hydrothermal pretreatment on product distribution and characteristics of oil produced by the pyrolysis of Huadian oil shale

International Nuclear Information System (INIS)

Jiang, Haifeng; Deng, Sunhua; Chen, Jie; Zhang, Mingyue; Li, Shu; Shao, Yifei; Yang, Jiaqi; Li, Junfeng

2017-01-01

Highlights: • The maximum yield of pyrolysis oil is obtained at the pretreatment time of 2.0 h. • The higher H/C ratio of oil is obtained after hydrothermal pretreatment. • Hydrothermal treatment promotes the formation of aliphatic hydrocarbons in the oil. • Long pretreatment time causes the increase of heavier oil fraction in the oil. - Abstract: In this work, Huadian oil shale from China was treated by hydrothermal pretreatment at 200 °C with 1.0–2.5 h in order to investigate the effect of hydrothermal pretreatment on pyrolysis product distribution and characteristics of oil. The differences in the elemental composition and thermal behavior between the untreated and treated oil shale were analyzed and compared. The hydrothermal treatment process could decompose oxygen functional groups and remove some water soluble inorganics in oil shale, which decreased the formation of gas and water during the pyrolysis. However, hydrothermal pretreatment was conducive to increasing shale oil yield. The maximum of oil yield was obtained at the pretreatment time of 2.0 h. The enhancement of the free-radical reactions during the pyrolysis and the reduction of the secondary cracking reactions of the generated oil vapors were considered as the main reasons. The oil obtained by the treated oil shale had a higher H/C ratio, indicating it had high energy content. The analysis results of chemical compositions in oils showed that the relative content of aliphatic hydrocarbons significantly increased after hydrothermal pretreatment. The further analysis demonstrated that the increase in the pretreatment time caused the generated long chain hydrocarbons tended to be directly released from oil shale particles, and were condensed into the oil.

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.

Integrated oil production and upgrading using molten alkali metal

Science.gov (United States)

Gordon, John Howard

2016-10-04

A method that combines the oil retorting process (or other process needed to obtain/extract heavy oil or bitumen) with the process for upgrading these materials using sodium or other alkali metals. Specifically, the shale gas or other gases that are obtained from the retorting/extraction process may be introduced into the upgrading reactor and used to upgrade the oil feedstock. Also, the solid materials obtained from the reactor may be used as a fuel source, thereby providing the heat necessary for the retorting/extraction process. Other forms of integration are also disclosed.

Characterization of pyrolytic oil obtained from pyrolysis of TDF (Tire Derived Fuel)

International Nuclear Information System (INIS)

Banar, Müfide; Akyıldız, Vildan; Özkan, Aysun; Çokaygil, Zerrin; Onay, Özlem

2012-01-01

Highlights: ► We pyrolyzed Tire Derived Fuel (TDF) at different heating rates and temperatures. ► We determine convenient pyrolysis temperature for pyrolytic oil. ► The product can be used as fuel for combustion system in industry. ► TDF pyrolysis is advisable recycling system because of low hazardous constituents. - Abstract: In recent years, waste utilization before disposing to the land is the most important point about waste management. Due to the increasing emphasis on recycling, related to the two European Commission Directives (EC End of Life Vehicle Directive, EC Waste Landfill Directive) affecting the management of waste tires, there is interest in the development of alternative technologies for recycling waste tires. One of them is pyrolysis. For this purpose, a fixed bed reactor was used to pyrolysis of Tire Derived Fuel (TDF) at the temperatures of 350, 400, 450, 500, 550 and 600 °C with the heating rates of 5 and 35 °C/min. The maximum pyrolytic oil yield (38.8 wt.%) was obtained at 400 °C with 5 °C/min heating rate. The yield of pyrolytic oil decreased with increasing pyrolysis temperatures whereas the yield of gases increased. The fuel properties of the pyrolytic oil including higher heating value (HHV), elemental composition, flash point, viscosity, distillation and density were determined. Pyrolytic oil was characterized by fourier transform infrared spectroscopy (FT-IR), hydrogen nuclear magnetic resonance spectroscopy ( 1 H NMR) and gas chromatography–mass spectroscopy (GC–MS) techniques and also, the amount of polychlorinated dibenzodioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) and congener distribution characteristics were studied for determination of environmental effects. It was seen that the pyrolytic oils have similar fuel properties with the diesel. It was also found that pyrolytic oil contained 0.00118 I-TEQs/g at very low level. Finally, the pyrolytic oil can be evaluated for energy recovery according to Regulation

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

Energy Technology Data Exchange (ETDEWEB)

Fletcher, Thomas; Pugmire, Ronald

2015-01-01

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

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 and dehalogenation of plastics from waste electrical and electronic equipment (WEEE): a review.

Science.gov (United States)

Yang, Xiaoning; Sun, Lushi; Xiang, Jun; Hu, Song; Su, Sheng

2013-02-01

Plastics from waste electrical and electronic equipment (WEEE) have been an important environmental problem because these plastics commonly contain toxic halogenated flame retardants which may cause serious environmental pollution, especially the formation of carcinogenic substances polybrominated dibenzo dioxins/furans (PBDD/Fs), during treat process of these plastics. Pyrolysis has been proposed as a viable processing route for recycling the organic compounds in WEEE plastics into fuels and chemical feedstock. However, dehalogenation procedures are also necessary during treat process, because the oils collected in single pyrolysis process may contain numerous halogenated organic compounds, which would detrimentally impact the reuse of these pyrolysis oils. Currently, dehalogenation has become a significant topic in recycling of WEEE plastics by pyrolysis. In order to fulfill the better resource utilization of the WEEE plastics, the compositions, characteristics and dehalogenation methods during the pyrolysis recycling process of WEEE plastics were reviewed in this paper. Dehalogenation and the decomposition or pyrolysis of WEEE plastics can be carried out simultaneously or successively. It could be 'dehalogenating prior to pyrolysing plastics', 'performing dehalogenation and pyrolysis at the same time' or 'pyrolysing plastics first then upgrading pyrolysis oils'. The first strategy essentially is the two-stage pyrolysis with the release of halogen hydrides at low pyrolysis temperature region which is separate from the decomposition of polymer matrixes, thus obtaining halogenated free oil products. The second strategy is the most common method. Zeolite or other type of catalyst can be used in the pyrolysis process for removing organohalogens. The third strategy separate pyrolysis and dehalogenation of WEEE plastics, which can, to some degree, avoid the problem of oil value decline due to the use of catalyst, but obviously, this strategy may increase the cost of

Methods and apparatuses for deoxygenating pyrolysis oil

Science.gov (United States)

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

2017-09-12

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

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 %)

The use of tyre pyrolysis oil in diesel engines.

Science.gov (United States)

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

2008-12-01

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

Effect of temperature on energy potential of pyrolysis products from oil palm shells

OpenAIRE

Lina María Romero Millán; María Alejandra Cruz Domínguez; Fabio Emiro Sierra Vargas

2016-01-01

Context: Taking into account that near 220 000 tons of oil palm shells are produced every year in Colombia, as a waste of the Elaeis Guineensis palm oil transformation process, the aim of this work is to determine the energy potential of oil palm shells, when transformed through slow pyrolysis process. Methods: Using a fixed bed lab scale reactor, different oil palm shells pyrolysis tests were performed between 300°C and 500°C. The effect of the temperature in the process product yield an...

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.

Catalytic partial oxidation of pyrolysis oils

Science.gov (United States)

Rennard, David Carl

2009-12-01

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

Pyrolysis of rice husk over Zeolite based catalysts

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 utilization of biomass and other alternative fuel sources, rather than existing fossil fuels, would offer more environmentally acceptable processes for energy production and will aid in conserving the limited supplies of fossil fuels. Pyrolysis of biomass is one of the most promising tools to provide alternative energy sources. However, pyrolytic oils are not always completely volatile and contain high levels of oxygen, this being the major factor responsible for the high viscosity and corrosiveness. The upgrading of pyrolytic oils is a necessary process and involves the removal of oxygen by catalyst. In this study, various type of zeolites such as HZSM-5, HY, USY, Al-MCM-41; Al-SBA-15 etc. were applied. The upgraded oil was analyzed by GC-MS, GC, and elemental analysis etc. The results indicated that more stable oil was produced by transforming oxygen over various zeolite into H 2 O, CO and CO 2 . (author)

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

Science.gov (United States)

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

2014-03-01

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

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.

Production of brown algae pyrolysis oils for liquid biofuels depending on the chemical pretreatment methods

International Nuclear Information System (INIS)

Choi, Joonhyuk; Choi, Jae-Wook; Suh, Dong Jin; Ha, Jeong-Myeong; Hwang, Ji Won; Jung, Hyun Wook; Lee, Kwan-Young; Woo, Hee-Chul

2014-01-01

Highlights: • Pyrolysis of Saccharina japonica, brown algae to produce hydrocarbons. • Sulfuric acid pretreatment of macroalgae to remove inorganic elements. • CaCl 2 treatment of macroalgae to remove valuable fucoidan. • Sulfuric acid pretreatment suppressed the formation of large biochar chunks. • The pretreatment methods allowed the continuous operation of pyrolysis. - Abstract: Based on observations of rapidly growing biochar in fluidization beds, kelp (Saccharina japonica), a species of brown algae, was pretreated for the efficient operation of pyrolysis processes to produce pyrolysis oils. The removal of catalytically active inorganic minerals and the softening of polymeric seaweed structures were performed by means of chemical treatments, including a CaCl 2 treatment to isolate valuable and sticky fucoidan and a sulfuric acid treatment to remove catalytically active minerals. The sulfuric acid pretreatment significantly reduced the inorganic elements but did not significantly affect the properties of the pyrolysis oil compared to the non-treated kelp pyrolysis oil. Whereas the non-treated kelp produced significantly large chunks of biochar, which hindered the continuous operation of pyrolysis, the kelp treated with sulfuric acid did not produce aggregated large particles of biochar, thereby offering a means of developing reliable continuous pyrolysis processes

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.

Converting of oil shale and biomass into liquid hydrocarbons via pyrolysis

International Nuclear Information System (INIS)

Kılıç, Murat; Pütün, Ayşe Eren; Uzun, Başak Burcu; Pütün, Ersan

2014-01-01

Highlights: • Co-processing of oil shale with an arid land biomass for hydrocarbon production. • Co-pyrolysis in TGA and fixed-bed reactor. • Characterization of oil and char. - Abstract: In this study, co-pyrolytic behaviors of oil shale and Euphorbia rigida were investigated at different temperatures in a fixed bed reactor at 450, 500, and 550 °C with a heating rate of 10 °C/min in the presence of nitrogen atmosphere. The obtained solid product (char) and liquid product (tar) were analyzed by using different types of characterization techniques. Experimental results showed co-pyrolysis of oil shale and biomass could be an environmental friendly way for the transformation of these precursors into valuable products such as chemicals or fuels

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.

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

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

Science.gov (United States)

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

2016-02-01

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

Maximizing heavy oil value while minimizing environmental impact with HTL upgrading of heavy to light oil

Energy Technology Data Exchange (ETDEWEB)

Koshka, E. [Ivanhoe Energy Inc., Calgary, AB (Canada)

2009-07-01

This presentation described Ivanhoe Energy Inc.'s proprietary HTL upgrading technology which was designed to process heavy oil in the field to cost effectively produce an upgraded synthetic oil that meets pipeline requirements. Steam and electricity are generated from the energy produced during the process. HTL improves the economics of heavy oil production by reducing the need for natural gas and diluent, and by capturing most of the heavy to light oil price differential. Integrated HTL heavy oil production also provides many environmental benefits regarding greenhouse gas (GHG) emissions. The HTL upgrading process is ready for full scale application. tabs., figs.

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 temperature on energy potential of pyrolysis products from oil palm shells

Directory of Open Access Journals (Sweden)

Lina María Romero Millán

2016-06-01

Full Text Available Context: Taking into account that near 220 000 tons of oil palm shells are produced every year in Colombia, as a waste of the Elaeis Guineensis palm oil transformation process, the aim of this work is to determine the energy potential of oil palm shells, when transformed through slow pyrolysis process. Methods: Using a fixed bed lab scale reactor, different oil palm shells pyrolysis tests were performed between 300°C and 500°C. The effect of the temperature in the process product yield and in the energy content of produced solids and gases were analyzed. Results: With a maximum mass yield of 50%, the char is considered the main product of oil palm shells pyrolysis, containing up to 73% of the raw biomass energy. The heating value of char raised with the temperature, from 29,6 MJ/kg at 300°C to 31,34 MJ/kg at 500°C. Moreover, the gas produced in the established temperature range had up to 13% of the energy content of the raw biomass, with a heating value near 12,5 MJ/m3. Conclusions: According to the results, slow pyrolysis can be considered an interesting process for the valorization of residual biomass as oil palm shells, through the production of solids and gases that can be used as fuels, or as precursor of other value-added products.

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 distillation on performance, emission, and combustion of a DI diesel engine, using tyre pyrolysis oil diesel blends

Directory of Open Access Journals (Sweden)

Murugan Sivalingam

2008-01-01

Full Text Available Conversion of waste to energy is one of the recent trends in minimizing not only the waste disposal but also could be used as an alternate fuel for internal combustion engines. Fuels like wood pyrolysis oil, rubber pyrolysis oil are also derived through waste to energy conversion method. Early investigations report that tyre pyrolysis oil derived from vacuum pyrolysis method seemed to possess properties similar to diesel fuel. In the present work, the crude tyre pyrolisis oil was desulphurised and distilled to improve the properties and studied the use of it. Experimental studies were conducted on a single cylinder four-stroke air cooled engine fuelled with two different blends, 30% tyre pyrolysis oil and 70% diesel fuel (TPO 30 and 30% distilled tyre pyrolysis oil and 70% diesel fuel (DTPO 30. The results of the performance, emission and combustion characteristics of the engine indicated that NOx is reduced by about 8% compared to tire pyrolysis oil and by about 10% compared to diesel fuel. Hydrocarbon emission is reduced by about 2% compared to TPO 30 operation. Smoke increased for DTPO 30 compared to TPO 30 and diesel fuel.

Catalytic and noncatalytic gasification of pyrolysis oil

NARCIS (Netherlands)

van Rossum, G.; Kersten, Sascha R.A.; van Swaaij, Willibrordus Petrus Maria

2007-01-01

Gasification of pyrolysis oil was studied in a fluidized bed over a wide temperature range (523−914 °C) with and without the use of nickel-based catalysts. Noncatalytically, a typical fuel gas was produced. Both a special designed fluid bed catalyst and a crushed commercial fixed bed catalyst showed

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

Science.gov (United States)

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

2018-04-01

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

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.

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

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

Science.gov (United States)

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

2017-05-01

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

Synthesis of carbon nanotubes and porous carbons from printed circuit board waste pyrolysis oil

International Nuclear Information System (INIS)

Quan Cui; Li Aimin; Gao Ningbo

2010-01-01

The possibility and feasibility of using pyrolysis oil from printed circuit board (PCB) waste as a precursor for advanced carbonaceous materials is presented. The PCB waste was first pyrolyzed in a laboratory scale fixed bed reactor at 600 deg. C to prepare pyrolysis oil. The analysis of pyrolysis oil by gas chromatography-mass spectroscopy indicated that it contained a very high proportion of phenol and phenol derivatives. It was then polymerized in formaldehyde solution to synthesize pyrolysis oil-based resin which was used as a precursor to prepare carbon nanotubes (CNTs) and porous carbons. Scanning electron microscopy and transmission microscopy investigation showed that the resulting CNTs had hollow cores with outer diameter of ∼338 nm and wall thickness of ∼86 nm and most of them were filled with metal nanoparticles or nanorods. X-ray diffraction reveals that CNTs have an amorphous structure. Nitrogen adsorption isotherm analysis indicated the prepared porous carbons had a Brunauer-Emmett-Teller surface area of 1214 m 2 /g. The mechanism of the formation of the CNTs and porous carbons was discussed.

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)

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

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.

Upgrading Unconventional Oil Resources with the EST Process

Energy Technology Data Exchange (ETDEWEB)

Delbianco, Alberto; Meli, Salvatori; Panariti, Nicolleta; Rispoli, Giacomo

2007-07-01

We strongly believe that unconventional oils will play a much larger role in the growth of supply than is currently recognized. As a matter of fact, whereas the earth's conventional proven world oil reserves are 1.3 trillion barrels, extra-heavy plus bitumen resources amount to about 4 trillion barrels. The unconventional oils are characterized by low API gravity (<10), high viscosity and high concentration of poisons such as sulphur, nitrogen, metals, and asphaltenes. For this reason, a key role for the full exploitation of these hydrocarbon resources is played by the downstream processes that are required to upgrade and convert them into valuable products. In this scenario, Eni has developed a novel hydrocracking process (EST: Eni Slurry Technology) which is particularly well-suited for the conversion and upgrading of heavy feedstocks (conventional vacuum residues, extra-heavy oils and bitumen). EST employs nano-sized hydrogenation catalysts and an original process scheme that allow complete feedstock conversion to an upgraded synthetic crude oil (SCO) with an API gravity gain greater than 20 and avoid the production of residual by-products, such as pet-coke or heavy fuel oil. A Commercial Demonstration Unit (CDP) of 1200 bbl/d capacity is successfully operating in the Eni's Taranto refinery since November 2005. (auth)

Upgrading of raw tall oil soap into fuel oils and lubricants. Final report; Raakasuovan jalostus poltto- ja voiteluoeljyksi. Loppuraportti

Energy Technology Data Exchange (ETDEWEB)

Oasmaa, A.; Arpiainen, V.; McKeough, P.

1997-12-31

Thermochemical processing of tall oil soap originating from various mixtures of birch and pine has been experimentally investigated. The organic matter of tall oil soap, which is a by- product of Kraft pulping, originated mainly from wood extractives. Conventional processing of tall oil soap involves acidification with sulfuric acid to yield crude tall oil and subsequent distillation of the oil at centralized refineries. Because tall oil originating from birch wood is far less valuable than that from pine, there is an economic incentive in the Nordic Countries to develop alternative conversion processes for the tall oil soap produced at pulp mills where birch is widely used as feedstock. Furthermore, thermochemical processing of tall oil soap does not introduce sulfur into the chemical recovery cycle. This would be a significant advantage in future mills employing closure of water circuits and/or sulfur-free pulping. In small-scale experiments tall oil soaps from wood mixtures with high birch content have been processed using both liquid-phase thermal treatment and pyrolysis. The liquid-phase thermal treatment at 450 deg C under a nitrogen atmosphere yielded a good-quality oil product at high yield (about 50 % of the energy content of the tall oil soap). Also in the atmospheric pyrolysis of birch tall oil soap a separation of inorganic and organic constituents was obtained. The energy value of the product gases was high. Both processes are promising, but the pyrolysis alternative has the greater economic potential, providing that the promising preliminary experimental results have given a true picture of the performance of the full-scale pyrolysis process Bioenergy Research Programme; 3 refs., 3 figs.

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.

Review of Heterogeneous Catalysts for Catalytically Upgrading Vegetable Oils into Hydrocarbon Biofuels

Directory of Open Access Journals (Sweden)

Xianhui Zhao

2017-03-01

Full Text Available To address the issues of greenhouse gas emissions associated with fossil fuels, vegetable oilseeds, especially non-food oilseeds, are used as an alternative fuel resource. Vegetable oil derived from these oilseeds can be upgraded into hydrocarbon biofuel. Catalytic cracking and hydroprocessing are two of the most promising pathways for converting vegetable oil to hydrocarbon biofuel. Heterogeneous catalysts play a critical role in those processes. The present review summarizes current progresses and remaining challenges of vegetable oil upgrading to biofuel. The catalyst properties, applications, deactivation, and regeneration are reviewed. A comparison of catalysts used in vegetable oil and bio-oil upgrading is also carried out. Some suggestions for heterogeneous catalysts applied in vegetable oil upgrading to improve the yield and quality of hydrocarbon biofuel are provided for further research in the future.

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-10-19

with model AFBO excluding guaiacol were also conducted. NF membranes showed retention factors of glucose greater than 80% and of acetic acid less than 15% when operated at transmembrane pressures near 60 bar. Task 3.0 Acid Removal by Catalytic Processing It was found that the TAN reduction in bio-oil was very difficult using low temperature hydrogenation in flow and batch reactors. Acetic acid is very resilient to hydrogenation and we could only achieve about 16% conversion for acetic acid. Although it was observed that acetic acid was not responsible for instability of aqueous fraction of bio-oil during ageing studies (described in task 5). The bimetallic catalyst PtRe/ceria-zirconia was found to be best catalyst because its ability to convert the acid functionality with low conversion to gas phase carbon. Hydrogenation of the whole bio-oil was carried out at 125°C, 1450 psi over Ru/C catalyst in a flow reactor. Again, negligible acetic acid conversion was obtained in low temperature hydrogenation. Hydrogenation experiments with whole bio-oil were difficult to perform because of difficulty to pumping the high viscosity oil and reactor clogging. Task 4.0 Acid Removal using Ion Exchange Resins DOWEX M43 resin was used to carry out the neutralization of bio-oil using a packed bed column. The pH of the bio-oil increased from 2.43 to 3.7. The GC analysis of the samples showed that acetic acid was removed from the bio-oil during the neutralization and recovered in the methanol washing. But it was concluded that process would not be economical at large scale as it is extremely difficult to regenerate the resin once the bio-oil is passed over it. Task 5.0 Characterization of Upgraded Bio-oils We investigated the viscosity, microstructure, and chemical composition of bio-oils prepared by a fast pyrolysis approach, upon aging these fuels at 90ºC for periods of several days. Our results suggest that the viscosity increase is not correlated with the acids or char present in the

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.

Identification and classification of components in flash pyrolysis oil and hydrodeoxygenated oils by two-dimensional gas chromatography and time-of-flight mass spectrometry

NARCIS (Netherlands)

Marsman, J. H.; Wildschut, J.; Evers, P.; Heeres, H. J.; Koning de, S.

2008-01-01

Hydrodeoxygenated pyrolysis oils (HDO) are considered promising renewable liquid energy carriers. To gain insights in the various reaction pathways taking place during the hydrodeoxygenation reaction of pyrolysis oil, two-dimensional gas chromatography with time-of-flight mass spectrometric analyses

Improvement of Waste Tire Pyrolysis Oil and Performance Test with Diesel in CI Engine

Directory of Open Access Journals (Sweden)

M. N. Islam

2016-01-01

Full Text Available The standard of living, quality of life, and development of a nation depend on its per capita energy consumption. Global energy supply that mainly depends on fossil fuel is decreasing day by day. It is estimated that the energy demand will be increased five times by the year 2021 from present scenario. Due to the fossil fuel crisis, the development of alternative fuel technologies has drawn more attraction to deliver the replacement of fossil fuel. Pyrolysis is one of the promising alternative fuel technologies which produces valuable oil, char, and gas product from organic waste. Early investigations report that tire pyrolysis oil extracted from vacuum pyrolysis method seemed to have properties similar to diesel fuel. The main concern of this paper is to produce and improve the properties of crude tire pyrolysis oil by desulfurizing, distilling, and utilizing it with diesel in CI engine to analyze the efficiency for various compositions.

Heavy crude oils - From Geology to Upgrading - An Overview

International Nuclear Information System (INIS)

Huc, A.Y.

2010-01-01

Heavy oils, extra-heavy oils and tar sands are major players for the future of energy. They represent a massive world resource, at least the size of conventional oils. They are found all over the world but Canada and Venezuela together account, by themselves, for more than half of world deposits. They share the same origin as the lighter conventional oils, but their geological fate drove them into thick, viscous tar-like crude oils. Most of them result from alteration processes mediated by microbial degradation. They are characterized by a low content of lighter cuts and a high content of impurities such as sulfur and nitrogen compounds and metals; so, their production is difficult and deployment of specific processes is required in order to enhance their transportability and to upgrade them into valuable products meeting market needs, and honouring environmental requirements. Although these resources are increasingly becoming commercially producible, less than 1% of total heavy crude oil deposits worldwide are under active development. The voluntarily wide scope of this volume encompasses geology, production, transportation, upgrading, economics and environmental issues of heavy oils. It does not pretend to be exhaustive, but to provide an authoritative view of this very important energy resource. Besides presenting the current status of knowledge and technology involved in exploiting heavy oils, the purpose is to provide an insight into technical, economic and environmental challenges that should be taken up in order to increase the efficiency of production and processing, and finally to give a prospective view of the emerging technologies which will contribute to releasing the immense potential reserves of heavy oil and tar deposits. Contents: Part 1. Heavy Crude Oils.1. Heavy Crude Oils in the Perspective of World Oil Demand. 2. Definitions and Specificities. 3. Geological Origin of Heavy Crude Oils. 4. Properties and composition. Part 2. Reservoir Engineering

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.

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)

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.

Development of advanced technologies for biomass pyrolysis

Science.gov (United States)

Xu, Ran

the entering vapors and gases to spin, providing good heat transfer and driving the condensed droplets to the wall through cyclonic action. This condenser design has been successfully demonstrated for the application on the pilot fluidized bed pyrolysis unit. After condensation, a stable aerosol is also typically formed which is difficult to be efficiently captured with conventional technologies. A pilot scale helicoidal rotary demister, a novel technology for removing persistent fine bio-oil droplets from gases using dynamic centrifugal forces, has been developed. The demister uses a helicoidal element, which consists of a metal sheet wound as a spiral, designed to rotate at high speeds within a cyclone body. Larger droplets are separated as they enter the cyclone housing, while the smaller droplets are carried by the gas into the helicoidal path of the rotating element, where they are centrifuged towards the outer collecting walls and, as a result of a specially designed baffle, may flow counter-currently to the gas and are drained out from the bottom of the rotating element. The mist-free gas leaves through a channel located at the center of the spiral. This unique demister design has demonstrated a high separation efficiency when tested offline with artificial submicron mist and tested online for demisting bio-oil aerosol on the pyrolysis unit. Bio-oil Upgrading: Very often, phase separation of bio-oil occurs naturally upon condensation of the bio-oil vapors, typically through the use of cyclonic condensers. The bio-oil is separated into an organic phase and an aqueous phase. Research has been conducted on the possibility to enhance the fuel properties and energy performance of the organic phase by reducing its water content, enhancing its heating value and improving its stability. Through the use of drying agents, a remarkable reduction of water content and an increase of heating value can be achieved. Moreover, the volumetric energy density can be greatly

Preliminary evaluation of fuel oil produced from pyrolysis of waste ...

African Journals Online (AJOL)

It could be refined further to produce domestic kerosene and gasoline. The physical and structural properties of the fuel oil produced compared favorably with that of Aviation fuel JP-4 (a wide-cut US Air force fuel). Presently African countries are importing aviation fuels. The fuel oil produced from the pyrolysis of waste water ...

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.

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

DEFF Research Database (Denmark)

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

2013-01-01

Fast pyrolysis may be used for sewage sludge treatment with the advantages of a significant reduction of solid waste volume and production of a bio-oil that can be used as fuel. A study of the influence of the reaction temperature on sewage sludge pyrolysis has been carried out using a pyrolysis...... of 392 g/mol, and metal concentrations lower than 0.14 wt % on a dry basis (db). Less optimal oil properties with respect to industrial applications were observed for oil samples obtained at 475 and 625 °C. Char properties of the 575 °C sample were an ash content of 81 wt % and a HHV of 6.1 MJ/kg db...

Volatile characteristic of trace elements during microwave pyrolysis of oil shale

Energy Technology Data Exchange (ETDEWEB)

Bai, Jing-ru; Wang, Qing; Kong, Ling-wen; Bai, Zhang [Northeast Dianli Univ., Jilin (China). Engineering Research Centre

2013-07-01

Oil shale is abundant in the world. Today, the industry of oil shale retorting for producing shale oil is developing owing to high price of oil in the world. In order to study migratory behavior of trace elements in oil shale at microwave pyrolysis, tests were performed in laboratory with oil shale of the Huadian deposit of China at different powers from 400 to 700 W. The trace elements As, Cd, Hg, Mo, Pb, Se, Cr, Cu, Ni, V, Zn, Ba, Co, Mn present in oil shale and shale char were determined by the inductively coupled plasma-mass spectrometry (ICP-MS). By comparing the content of trace elements in oil shale and shale char, distribution characteristics of trace elements at retorting were studied. The overall trends of volatile ratio of trace elements are ascending with higher microwave power and higher than the conventional pyrolysis. The differences in the volatile ratio indicate that the trace elements investigated are bound with the oil shale kerogen and its mineral matter in different manner. So Float-sink experiments (FSE) were performed on oil shale. Huadian oil shale has more included mineral. The volatilization of organic matter is not the main reason for the volatilization of trace elements in oil shale. The trace elements combined with the mineral elements may be also certain volatility.

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

In situ upgrading of heavy oil under steam injection with tetralin and catalyst

Energy Technology Data Exchange (ETDEWEB)

Mohammad, A.A. [Texas A and M Univ., College Station, TX (United States); Mamora, D.D. [Society of Petroleum Engineers, Richardson, TX (United States)]|[Texas A and M Univ., College Station, TX (United States)

2008-10-15

Steam injection has become the most successful thermal recovery method for heavy oil production. Heavy oil refineries use upgrading processes to improve oil quality. They generally involve the use of catalysts that are used to remove heavy metals, sulfur and nitrogen, or used in hydro-treating and hydro-cracking. In-situ upgrading is thought to have advantages over conventional surface upgrading technology. Experiments were performed to verify the feasibility of in-situ upgrading of heavy crude oil. A hydrogen donor called tetralin was used along with an organometallic catalyst, at steam injection temperatures and pressures normally encountered in the field. Crude oil from the Jobo Oil Field, located in Venezuela was used. The paper described the experimental methodology with reference to the injection cell; fluid injection system; fluid production system; data measurement and recording system; and experimental procedure. It also discussed the extent of upgrading by comparing the properties of the original and produced oil. Oil properties that were measured and compared included hydrogen-to-carbon ratio; heavy metal content; viscosity; and API gravity. The paper also presented a comparison of oil recovery and fluid production between all cases. It was concluded that in the field, the reaction time was significantly longer than encountered in the experiments and may lead to further upgrading, assuming the catalyst could be dispersed in the formation. 10 refs., 1 tab., 9 figs.

A Review of Laboratory-Scale Research on Upgrading Heavy Oil in Supercritical Water

Directory of Open Access Journals (Sweden)

Ning Li

2015-08-01

Full Text Available With the growing demand for energy and the depletion of conventional crude oil, heavy oil in huge reserve has attracted extensive attention. However, heavy oil cannot be directly refined by existing processes unless they are upgraded due to its complex composition and high concentration of heteroatoms (N, S, Ni, V, etc.. Of the variety of techniques for heavy oil upgrading, supercritical water (SCW is gaining popularity because of its excellent ability to convert heavy oil into valued, clean light oil by the suppression of coke formation and the removal of heteroatoms. Based on the current status of this research around the world, heavy oil upgrading in SCW is summarized from three aspects: Transformation of hydrocarbons, suppression of coke, and removal of heteroatoms. In this work, the challenge and future development of the orientation of upgrading heavy oil in SCW are pointed out.

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

Effect of pyrolysis temperature on the composition of the oils obtained from sewage sludge

International Nuclear Information System (INIS)

Sanchez, M.E.; Menendez, J.A.; Dominguez, A.; Pis, J.J.; Martinez, O.; Calvo, L.F.; Bernad, P.L.

2009-01-01

Sewage sludge was pyrolysed in a quartz reactor at 350, 450, 550 and 950 o C. The pyrolysis oils from the sewage sludge were characterized in detail by means of gas chromatography-mass spectrometry (GC-MS). Changes in the composition of the oils related to the process conditions were assessed by normalizing the areas of the peaks. It was demonstrated that, as the temperature of pyrolysis increased from 350 to 950 o C, the concentration of mono-aromatic hydrocarbons in the oils also increased. Conversely, phenol and its alkyl derivatives showed a strong decrease in their concentration as temperature rose. Polycyclic aromatic hydrocarbons (PAHs) with two to three rings passed through a maximum at a pyrolysis temperature of 450 o C. PAHs with 4-5 rings also presented a major increase as temperature increased up to 450 o C, the concentration at 950 o C being slightly higher than that at 450 o C. Quantification of the main compounds showed that sewage sludge pyrolysis oils contain significant quantities of potentially high-value hydrocarbons such as mono-aromatic hydrocarbons and phenolic compounds. The oils also contain substantial concentrations of PAHs, even at the lowest temperature of 350 o C. The pathway to PAH formation is believed to be via the Diels-Alder reaction and also via secondary reactions of oxygenated compounds such as phenols.

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.

Upgrader alley : oil sands fever strikes Edmonton

International Nuclear Information System (INIS)

Griffiths, M.; Dyer, S.

2008-01-01

Large-scale industrial complexes called upgraders are similar to oil refineries. Several upgraders are planned for the area just northeast of Edmonton, known as Upgrader Alley. Concerns have been expressed over the potential congestion and environmental impacts of these upgraders. Upgraders will also attract other industry, and the cumulative effects of development will have major impacts on the region, its people and the natural environment. The report provided an overview of Upgrader Alley, with reference to what is driving development; upgrading issues; what Upgrader Alley will look like; and how much water Upgrader Alley needs. The report also discussed impacts on the land, air quality, and greenhouse gases. Water demand issues were discussed with reference to impacts on the North Saskatchewan River, water levels, water quality, a water management framework, and groundwater resources. Cumulative impacts were also presented. It was concluded that if all the projects for which applications had been submitted were approved, the rapid pace of growth in Upgrader Alley would mimic that of Fort McMurray. If the rate of development were somewhat slower, there would be more time to develop and implement plans to reduce the impacts. 189 refs., 6 tabs., 14 figs

A fundamental research for upgrading heavy oil using syngas as hydrogen source

Energy Technology Data Exchange (ETDEWEB)

Yan, D.; Yuan, M.; Sun, X.; Zhao, S. [China Univ. of Petroleum, Beijing (China). State Key Laboratory of Heavy Oil Processing

2006-07-01

The stock of heavy oil and residue from petroleum fractions has become more important as a component in supplying demands for fuel and petrochemical feeds. Finding economical means of upgrading heavy oils is extremely important in order to ensure future fuel supply. A number of new technologies for upgrading heavy oils have been evaluated, including residual fluid catalytic cracking (RFCC), hydrogenation, thermal conversion, and solvent deasphalting. However, the commercial application of such technologies is mainly constrained by the metal and residual carbon concentrations that are present in all heavy oils. Conventional technologies used to upgrade vacuum residue (VR) result in heavy coke formation, with a consequential reduction in the life of expensive, high-performance catalysts. The hydro upgrading process can significantly remove the concentration of heteroatom such as sulfur, nitrogen, and metals in the liquid products. This paper investigated upgrading of heavy oil using syngas as an alternative hydrogen source with a dispersed catalyst. The paper discussed the experiment with reference to the feedstock and catalyst precursors; finely dispersed catalysts preparation; experimental apparatus; experimental design and procedure; and analysis. The results were presented in terms of effects of catalyst dispersion; effect of hydro-upgrading heavy oil using syngas as alternative source; and effects of different catalysts on residue hydrocracking. Last, the paper discussed the properties of the hydrocracked oil treated with syngas. The study confirmed the effectiveness of the slurry bed hydrocracking catalyst using syngas as a hydrogen source. 23 refs., 8 tabs., 16 figs.

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

Directory of Open Access Journals (Sweden)

Renato O. Arazo

2017-01-01

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

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

Staged catalytic gasification/steam reforming of pyrolysis oil

NARCIS (Netherlands)

van Rossum, G.; Kersten, Sascha R.A.; van Swaaij, Willibrordus Petrus Maria

2009-01-01

Gasification/steam reforming of pyrolysis oil was studied in a staged reactor concept, which consisted of an inert fluidized bed and a catalytic fixed bed. Methane and C2−C3 free syngas is produced at a single temperature around 800 °C at atmospheric pressure. By lowering the temperature of the

Multi-scale Multi-dimensional Imaging and Characterization of Oil Shale Pyrolysis

Science.gov (United States)

Gao, Y.; Saif, T.; Lin, Q.; Al-Khulaifi, Y.; Blunt, M. J.; Bijeljic, B.

2017-12-01

The microstructural evaluation of fine grained rocks is challenging which demands the use of several complementary methods. Oil shale, a fine-grained organic-rich sedimentary rock, represents a large and mostly untapped unconventional hydrocarbon resource with global reserves estimated at 4.8 trillion barrels. The largest known deposit is the Eocene Green River Formation in Western Colorado, Eastern Utah, and Southern Wyoming. An improved insight into the mineralogy, organic matter distribution and pore network structure before, during and after oil shale pyrolysis is critical to understanding hydrocarbon flow behaviour and improving recovery. In this study, we image Mahogany zone oil shale samples in two dimensions (2-D) using scanning electron microscopy (SEM), and in three dimensions (3-D) using focused ion beam scanning electron microscopy (FIB-SEM), laboratory-based X-ray micro-tomography (µCT) and synchrotron X-ray µCT to reveal a complex and variable fine grained microstructure dominated by organic-rich parallel laminations which are tightly bound in a highly calcareous and heterogeneous mineral matrix. We report the results of a detailed µCT study of the Mahogany oil shale with increasing pyrolysis temperature. The physical transformation of the internal microstructure and evolution of pore space during the thermal conversion of kerogen in oil shale to produce hydrocarbon products was characterized. The 3-D volumes of pyrolyzed oil shale were reconstructed and image processed to visualize and quantify the volume and connectivity of the pore space. The results show a significant increase in anisotropic porosity associated with pyrolysis between 300-500°C with the formation of micron-scale connected pore channels developing principally along the kerogen-rich lamellar structures.

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....

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

Proceedings of the 5. NCUT upgrading and refining conference 2009 : bitumen, synthetic crude oil and heavy oil

International Nuclear Information System (INIS)

2009-01-01

This conference examined various upgrading technologies related to bitumen production. It provided a forum to review new developments to exploit oil sands bitumen and extra heavy crudes in terms of production, upgrading and environmental issues facing the industry. This 2009 conference focused on the many existing and emerging technical solutions that will help consolidate the position of the vast reserves in Western Canada as a sustainable source of crudes for North America and other selected markets. Some of the technical challenges that have an effect on upgrading include poor quality bitumen and heavy oils; bitumen and diluent blending; pipeline issues; desalting; fouling and corrosion; high costs; dependence on natural gas for energy; poor middle distillates; and greenhouse gas emissions. The sessions of the conference were entitled: heavy oil and bitumen upgrading technologies; secondary upgrading and refining technologies; bitumen transportation; and bitumen and heavy oil processability. The conference featured a total of 50 presentations and posters, of which 43 have been catalogued separately for inclusion in this database. tabs., figs

Experimental optimization of catalytic process in-situ for heavy oil and bitumen upgrading

Energy Technology Data Exchange (ETDEWEB)

Shah, A.; Fishwick, R.P.; Leeke, G.A.; Wood, J. [Birmingham Univ., Birmingham (United Kingdom); Rigby, S.P.; Greaves, M. [Bath Univ., Bath (United Kingdom)

2010-07-01

Peak crude oil production is expected to occur in the second decade of this century, followed by a phase of permanent decline in conventional crude oil production. However, very large resources of heavy oil and bitumen exist throughout the world, most notably in Canada and Venezuela. The high viscosity and density of these non-conventional crude oils require more energy intensive operations for production and upgrading, and also for transportation. As such, they are more costly to extract. This paper described some of the technological innovations that are being considered to extract heavier oil supplies with reduced environmental impact. The toe-to-heel air injection (THAI) process and its catalytic added-on (CAPRI) process combine in-situ combustion with catalytic upgrading using an annular catalyst packed around a horizontal producer well. Results of an experimental study concerning optimization of catalyst type and operating conditions showed that CAPRI can effect further upgrading of partially upgraded THAI oil, with upgrading levels of viscosity and API gravity dependent upon temperature and flow rate. 20 refs., 8 tabs., 10 figs.

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

Science.gov (United States)

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

2017-11-01

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

Oxidation and low temperature properties of biofuels obtained from pyrolysis and alcoholysis of soybean oil and their blends with petroleum diesel

Energy Technology Data Exchange (ETDEWEB)

Sharma, Brajendra K. [Food and Industrial Oil Research Unit, National Center for Agricultural Utilization Research, United States Department of Agriculture, Agricultural Research Service, 1815N. University St., Peoria, IL 61604 (United States); Department of Chemical Engineering, The Pennsylvania State University, University Park, PA 16802 (United States); Suarez, Paulo A.Z. [Food and Industrial Oil Research Unit, National Center for Agricultural Utilization Research, United States Department of Agriculture, Agricultural Research Service, 1815N. University St., Peoria, IL 61604 (United States); LMC-IQ, Universidade de Brasilia, CP 4478, CEP 70919-970, Brasilia-DF (Brazil); Perez, Joseph M. [Department of Chemical Engineering, The Pennsylvania State University, University Park, PA 16802 (United States); Erhan, Sevim Z. [Food and Industrial Oil Research Unit, National Center for Agricultural Utilization Research, United States Department of Agriculture, Agricultural Research Service, 1815N. University St., Peoria, IL 61604 (United States)

2009-10-15

Diesel-like fuels were synthesized by a pyrolysis method using soybean oil (pyrodiesel, PD) and soybean soapstock (SPD), respectively, as starting material. These pyrodiesel samples were compared with soy biodiesel (BD) samples. All these three biofuels (PD, SPD and BD) and their blends with high sulfur (HSD) and low sulfur (LSD) diesel fuels were evaluated by measuring a number of fuel properties, such as oxidative stability, low-temperature performance, acid value and corrosion properties. Compared to BD blends, PD and SPD and their blends were found to have better oxidative stability, though inferior acid values. SPD and its blends have better flow performance at low-temperature compared to BD and PD blends. All the biofuels and their blends met the copper corrosion requirement prescribed by US and European standard. Based on the results reported here, pyrodiesels from these two-different feedstocks have potential and will require some upgrading or change in pyrolysis conditions, if they are to be used as fuel blending component. (author)

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

Science.gov (United States)

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

2013-07-17

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

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

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.

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.

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

Techno-economic analysis of biotrade chains. Upgraded biofuels from Russia and from Canada to the Netherlands

International Nuclear Information System (INIS)

McKeough, P.; Solantausta, Y.; Kylloenen, H.; Faaij, A.; Hamelinck, C.; Wagener, M.; Beckman, D.; Kjellstroem, B.

2005-11-01

This study consisted of in-depth techno-economic analyses of biofuel upgrading processes and of whole biotrade chains. The chains encompassed the production of pyrolysis oil or pellets from biomass residues in the source regions, the transportation of the upgraded fuels internationally over long distances and the final utilisation of the fuels. Four international biotrade chains were analysed in detail. The chains cover two source regions, North-Western Russia and Eastern Canada, and two traded commodities, pyrolysis oil and pellets. The chains terminate in the Netherlands where the imported biofuels are co-fired with coal in condensing power stations. The costs of the delivered biofuels were estimated to be in the range 18.30 EUR/MWh, with the costs of pellets about 25% lower than those of pyrolysis oil. The estimated electricity-generation costs displayed little dependence on the type of biofuel. Local-utilisation alternatives were also evaluated. It was concluded that, particularly when the local reference energy system is carbon intensive, local utilisation can be a more cost-efficient and a more resource-efficient option than international trade and use of biomass resources elsewhere. In practice, there are many factors which may limit local utilisation or make utilisation of biomass resources elsewhere more attractive. Overall, it was concluded that biotrade will have a definite and important role to play in reducing humankind's dependency on fossil fuels. (orig.)

Recovery of useful chemicals from palm oil mill wastewater

Science.gov (United States)

Ratanaporn, Yuangsawad; Duangkamol, Na-Ranong; Teruoki, Tago; Takao, Masuda

2017-11-01

A two-step process consisting of pyrolysis of dried sludge and catalytic upgrading of pyrolysed liquid was proposed. Wastewater from a palm oil mill was separated to solid cake and liquid by filtration. The solid cake was dried and pyrolysed at 773 K. Liquid product obtained from the pyrolysis had two immiscible aqueous and oil phases (PL-A and PL-O). Identification of chemicals in PL-A and PL-O indicated that both phases contained various chemicals with unsaturated bonds, such as carboxylic acids and alcohols, however, most of the chemicals could not be identified. Catalytic upgrading of PL-A and PL-O over ZrO2·FeOx were separately performed using a fixed bed reactor at various conditions, T = 513-723 K and mass of catalyst to feed rate = 0.25-10 h. The main components in the liquid products of PL-A upgrading were methanol and acetone whereas they were acetone and phenol in the case of PL-O upgrading. More than 15% of carbon in raw material was deposited on the catalyst. To reduce the carbon deposition, the used catalyst was treated with air at 823 K. This simple treatment could reasonably regenerate the catalyst only for the case of PL-A catalytic upgrading.

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

Science.gov (United States)

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

2017-02-01

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

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

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

Upgrading of bio-oil to boiler fuel by catalytic hydrotreatment and esterification in an efficient process

International Nuclear Information System (INIS)

Zhang, Xinghua; Chen, Lungang; Kong, Wei; Wang, Tiejun; Zhang, Qi; Long, Jinxing; Xu, Ying; Ma, Longlong

2015-01-01

Bio-oil can't be directly used as fuel due to its deteriorate properties. Here, an efficient catalytic upgrading process for the bio-oil, including esterification, hydrogenation, hydrodeoxygenation and depolymerization, is proposed with multifunctional catalyst Ni/SiO 2 –ZrO 2 and biomass-derived solvent ethanol. Results showed that esters, alcohols, phenolics, and cyclo-ketones were the main components in the upgraded bio-oil while aldehydes were removed completely via catalytic hydrogenation and acids were removed by catalytic esterification with supercritical ethanol. The pH value of upgraded bio-oil rose drastically from 2.38 to 5.24, and the high heating value increased to 24.4 MJ kg −1 . Comparison characterization on the upgraded and crude bio-oil using FT-IR, GPC (Gel permeation chromatography) and 13 C NMR (Nuclear Magnetic Resonance) demonstrated that lignin-derived oligomers contained in crude bio-oil were further depolymerized over Ni/SiO 2 –ZrO 2 catalyst. The improved properties suggest that the upgraded bio-oil is more suitable to be used as boiler fuel. Furthermore, the loss of carbon is negligible because formation of coke is suppressed during the upgrading process. - Highlights: • Acid can be converted via catalytic esterification in supercritical ethanol. • Aldehydes can be removed completely during the upgrading process. • Lignin-derived oligomers were further depolymerized during the upgrading process. • Formation of coke is effectively inhibited during the upgrading process

Directions in refining and upgrading of heavy oil and bitumen

International Nuclear Information System (INIS)

Dawson, B.; Parker, R. J.; Flint, L.

1997-01-01

The expansion of heavy oil transportation, marketing and refining facilities over the past two decades have been reviewed to show the strides that several Canadian refiners have taken to build up the facilities required to process synthetic crude oil (SCO). Key points made at a conference, convened by the National Centre for Upgrading Technology (NCUT), held in Edmonton during September 1997 to discuss current and future directions in the refining and marketing of heavy oil, bitumen and SCO, were summarized. Among the key points mentioned were: (1) the high entry barriers faced by centralized upgraders, (2) the advantages of integrating SCO or heavy oil production with downstream refining, (3) the stiff competition from Venezuela and Mexico that both SCO and heavy oil will face in the U.S. PADD II market, (4) the differences between Canadian refiners who have profited from hydrocracking and are better able to handle coker-based SCO, and American refiners who rely chiefly on catalytic cracking and are less able to process the highly aromatic SCO, and (5) the disproportionate cost in the upgrading process represented by the conversion of asphaltenes. Challenges and opportunities for key stakeholders, i.e. producers, refiners, marketers and technology licensors also received much attention at the Edmonton conference

Catalytic Pyrolysis of Chilean Oak: Influence of Brønsted Acid Sites of Chilean Natural Zeolite

Directory of Open Access Journals (Sweden)

Serguei Alejandro Martín

2017-11-01

Full Text Available This paper proposes the Chilean natural zeolite as catalyst on bio-oil upgrade processes. The aim of this study was to analyze chemical composition of bio-oil samples obtained from catalytic pyrolysis of Chilean native oak in order to increase bio-oil stability during storage. In order to identify chemical compounds before and after storage, biomass pyrolysis was carried out in a fixed bed reactor at 623 K and bio-oil samples were characterized by gas chromatography/mass spectrophotometry (GC/MS. A bio-oil fractionation method was successfully applied here. Results indicate that bio-oil viscosity decreases due to active sites on the zeolite framework. Active acids sites were associated with an increment of alcohols, aldehydes, and hydrocarbon content during storage. Higher composition on aldehydes and alcohols after storage could be attributed to the occurrence of carbonyl reduction reactions that promotes them. These reactions are influenced by zeolite surface characteristics and could be achieved via the direct contribution of Brønsted acid sites to Chilean natural zeolite.

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...

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

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

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

Directory of Open Access Journals (Sweden)

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.

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

Science.gov (United States)

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

2018-05-01

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

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.

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).

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.

In Situ Catalytic Pyrolysis of Low-Rank Coal for the Conversion of Heavy Oils into Light Oils

Directory of Open Access Journals (Sweden)

Muhammad Nadeem Amin

2017-01-01

Full Text Available Lighter tars are largely useful in chemical industries but their quantity is quite little. Catalytic cracking is applied to improve the yield of light tars during pyrolysis. Consequently, in situ upgrading technique through a MoS2 catalyst has been explored in this research work. MoS2 catalyst is useful for the conversion of high energy cost into low energy cost. The variations in coal pyrolysis tar without and with catalyst were determined. Meanwhile, the obtained tar was analyzed using simulated distillation gas chromatograph and Elemental Analyzer. Consequently, the catalyst reduced the pitch contents and increased the fraction of light tar from 50 to 60 wt.% in coal pyrolysis tar. MoS2 catalyst increased the liquid yield from 18 to 33 (wt.%, db and decreased gas yield from 27 to 12 (wt.%, db compared to coal without catalyst. Moreover, it increased H content and hydrogen-to-carbon ratio by 7.9 and 3.3%, respectively, and reduced the contents of nitrogen, sulphur, and oxygen elements by 8.1%, 15.2%, and 23.9%, respectively, in their produced tars compared to coal without catalyst.

Post Retort, Pre Hydro-treat Upgrading of Shale Oil

Energy Technology Data Exchange (ETDEWEB)

Gordon, John

2012-09-30

Various oil feedstocks, including oil from oil shale, bitumen from tar sands, heavy oil, and refin- ery streams were reacted with the alkali metals lithium or sodium in the presence of hydrogen or methane at elevated temperature and pressure in a reactor. The products were liquids with sub- stantially reduced metals, sulfur and nitrogen content. The API gravity typically increased. Sodi- um was found to be more effective than lithium in effectiveness. The solids formed when sodium was utilized contained sodium sulfide which could be regenerated electrochemically back to so- dium and a sulfur product using a "Nasicon", sodium ion conducting membrane. In addition, the process was found to be effective reducing total acid number (TAN) to zero, dramatically reduc- ing the asphaltene content and vacuum residual fraction in the product liquid. The process has promise as a means of eliminating sulfur oxide and carbon monoxide emissions. The process al- so opens the possibility of eliminating the coking process from upgrading schemes and upgrad- ing without using hydrogen.

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.

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.

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.

Catalytic Conversion of Biomass Pyrolysis Vapours over Sodium-Based Catalyst; A Study on teh State of Sodium on the Catalyst

NARCIS (Netherlands)

Nguyen, T.S.; Lefferts, Leonardus; Gupta, K.B. Sai Sankar; Seshan, Kulathuiyer

2015-01-01

In situ upgrading of biomass pyrolysis vapours over Na2CO3/γ-Al2O3 catalysts was studied in a laboratory-scale fixed-bed reactor at 500 °C. Catalytic oil exhibits a significant improvement over its non-catalytic counterpart, such as lower oxygen content (12.3 wt % compared to 42.1 wt %), higher

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

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

Influence of the Zeolite ZSM-5 on Catalytic Pyrolysis of Biomass via TG-FTIR

Directory of Open Access Journals (Sweden)

Ze Wang

2015-06-01

Full Text Available Bio-oil from the pyrolysis of biomass is an important renewable source for liquid fuel. However, the application of bio-oil has been severely restricted due to its high viscosity, acidity, and low heating value. Thus, it has been necessary to upgrade bio-oil for automobile fuel via catalytic deoxygenation reactions. Herein, the effects of the zeolite ZSM-5 on the pyrolysis of four biomass materials (corn cob, corn straw, pine powder, and cellulose were investigated via TG-FTIR (thermogravimetric analyzer coupled with a Fourier transform infrared spectrometer to better understand the working mechanism of ZSM-5. The contents of the products of H2O, CO, CO2, and the C-O, C=O, and OH groups evolved with increasing pyrolytic temperature were monitored by FTIR. It was found that the relative contents of the C-O and C=O groups were decreased under the catalysis of ZSM-5, while the formations of CO, H2O, and the OH containing compounds were promoted. To explain the regulations, reaction routes were speculated and the catalytic conversion mechanisms were deduced.

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.

Study of hydrodeoxygenation of bio-oil from the fast pyrolysis of biomass

Energy Technology Data Exchange (ETDEWEB)

Su-ping, Z. [ECUST, Shanghai (China). Dept. of Chemical Engineering for Energy Resources

2003-01-01

The bio-oil obtained from the fast pyrolysis of biomass has a high oxygen content. Ketones and aldehydes, carboxylic acids and esters, aliphatic and aromatic alcohols, and ethers have been detected in significant quantities. Because of the reactivity of oxygenated groups, the main problems of the oil are instability. Therefore study of the deoxygenation of bio-oil is needed. In the present work the mechanism of hydrodeoxygenation (HDO) of bio-oil in the presence of a cobalt molybdate catalyst was studied. Particularly, the effects of reaction time, temperature, and hydrogen pressure on the HDO activity were examined. On the experimental results, a kinetic model for HDO of bio-oil was proposed. (author)

SOVENT BASED ENHANCED OIL RECOVERY FOR IN-SITU UPGRADING OF HEAVY OIL SANDS

Energy Technology Data Exchange (ETDEWEB)

Munroe, Norman

2009-01-30

With the depletion of conventional crude oil reserves in the world, heavy oil and bitumen resources have great potential to meet the future demand for petroleum products. However, oil recovery from heavy oil and bitumen reservoirs is much more difficult than that from conventional oil reservoirs. This is mainly because heavy oil or bitumen is partially or completely immobile under reservoir conditions due to its extremely high viscosity, which creates special production challenges. In order to overcome these challenges significant efforts were devoted by Applied Research Center (ARC) at Florida International University and The Center for Energy Economics (CEE) at the University of Texas. A simplified model was developed to assess the density of the upgraded crude depending on the ratio of solvent mass to crude oil mass, temperature, pressure and the properties of the crude oil. The simplified model incorporated the interaction dynamics into a homogeneous, porous heavy oil reservoir to simulate the dispersion and concentration of injected CO2. The model also incorporated the characteristic of a highly varying CO2 density near the critical point. Since the major challenge in heavy oil recovery is its high viscosity, most researchers have focused their investigations on this parameter in the laboratory as well as in the field resulting in disparaging results. This was attributed to oil being a complex poly-disperse blend of light and heavy paraffins, aromatics, resins and asphaltenes, which have diverse behaviors at reservoir temperature and pressures. The situation is exacerbated by a dearth of experimental data on gas diffusion coefficients in heavy oils due to the tedious nature of diffusivity measurements. Ultimately, the viscosity and thus oil recovery is regulated by pressure and its effect on the diffusion coefficient and oil swelling factors. The generation of a new phase within the crude and the differences in mobility between the new crude matrix and the

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.

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

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.

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%

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 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

Co-pyrolysis of rice straw and polypropylene using fixed-bed pyrolyzer

Science.gov (United States)

Izzatie, N. I.; Basha, M. H.; Uemura, Y.; Mazlan, M. A.; Hashim, M. S. M.; Amin, N. A. M.; Hamid, M. F.

2016-11-01

The present work encompasses the impact of temperature (450, 500, 550, 600 °C) on the properties of pyrolysis oil and on other product yield for the co-pyrolysis of Polypropylene (PP) plastics and rice straw. Co-pyrolysis of PP plastic and rice straw were conducted in a fixed-bed drop type pyrolyzer under an inert condition to attain maximum oil yield. Physically, the pyrolysis oil is dark-brown in colour with free flowing and has a strong acrid smell. Copyrolysis between these typically obtained in maximum pyrolysis oil yields up to 69% by ratio 1:1 at a maximum temperature of 550 °C. From the maximum yield of pyrolysis oil, characterization of pyrolysis product and effect of biomass type of the composition were evaluated. Pyrolysis oil contains a high water content of 66.137 wt.%. Furfural, 2- methylnaphthalene, tetrahydrofuran (THF), toluene and acetaldehyde were the major organic compounds found in pyrolysis oil of rice straw mixed with PP. Bio-char collected from co-pyrolysis of rice straw mixed with PP plastic has high calorific value of 21.190 kJ/g and also carbon content with 59.02 wt.% and could contribute to high heating value. The non-condensable gases consist of hydrogen, carbon monoxide, and methane as the major gas components.

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

Directory of Open Access Journals (Sweden)

M.A Ebrahimi-Nik

2014-09-01

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

Pyrolysis Strategies for Effective Utilization of Lignocellulosic and Algal Biomass

Science.gov (United States)

Maddi, Balakrishna

-of-concept micro-pyrolyser (Pyroprobe) and lab-scale fixed-bed experiments were performed using oleaginous algae (Chlorella Sp.) to establish pyrolytic fractionation technique and also to determine the yields of triglyceride-specific bio-oils. As expected, triglyceride-specific bio-oils have hydrocarbons and free fatty acids that were nearly free of water, organic acids and carbohydrate degradation products. Another unique feature of the fractional pyrolysis method is that it allows upgrading of the triglyceride-specific bio-oil vapors via in situ gas-phase hydro-deoxygenation to drop-in fuels (hydrocarbons), without the need to condense the vapors. Similarly, these vapors can also be converted to other value-added products such as fatty acid methyl esters and amides though efficient catalytic and non-catalytic in situ gas-phase conversion methods. Energy requirements for this new pyrolytic fractionation method were also assessed, using energy estimates for the individual steps obtained via differential scanning calorimetry experiments. A comparison of these energy needs against those of alternative thermal processing methods of algae (hydro-thermal processing) proposed in the literature established the viability of this new method. Finally, a new TGA-based analytical method was developed in this thesis for rapid quantification of the triglyceride content of oleaginous feed stocks, by exploiting the non-overlapping thermal degradation range of triglycerides and the other major components.

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.)

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

Heavy gas oils as feedstock for petrochemicals

Energy Technology Data Exchange (ETDEWEB)

Clark, P.D. [Nova Chemicals Ltd., Calgary, AB (Canada); Du Plessis, D. [Alberta Energy Research Inst., Edmonton, AB (Canada)]|[Alberta Economic Development and Trade, Edmonton, AB (Canada)

2004-07-01

This presentation reviewed the possibilities for converting heavy aromatic compounds and gas oils obtained from Alberta bitumen into competitively priced feedstock for high value refined products and petrochemicals. Upgrading bitumen beyond synthetic crude oil to refined products and petrochemicals would add value to bitumen in Alberta by expanding the petrochemical industry by providing a secure market for co-products derived from the integration of bitumen upgrading and refining. This presentation also reviewed conventional feedstocks and processes; by-products from bitumen upgrading and refining; production of light olefins by the fluid catalytic cracking (FCC) and hydrocracking process; deep catalytic cracking, catalytic pyrolysis and PetroFCC processes; technical and economic evaluations; and opportunities and challenges. Conventional feeds for steam cracking were listed along with comparative yields on feedstock. The use of synthetic gas liquids from oil sands plants was also reviewed. Current FCC type processes for paraffinic feedstocks are not suitable for Alberta's bitumen, which require better technologies based on hydrotreating and new ring opening catalysts. tabs., figs.

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 Blended Feedstock on Pyrolysis Oil Composition

Energy Technology Data Exchange (ETDEWEB)

Smith, Kristin M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Gaston, Katherine R [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2017-09-28

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

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.

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.

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

DEFF Research Database (Denmark)

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

2013-01-01

these biomasses. The fast pyrolysis of macroalgae showed a promising result with a bio-oil yield of 65 wt% dry ash free basis (daf) and 76 % energy recovery in the bio-oil while the lignin fast pyrolysis provides a bio-oil yield of 47 wt% daf and energy recovery in bio-oil of 45 %. The physiochemical properties...... of the bio-oils were characterized with respect to higher heating value (HHV), molecular mass distribution, viscosity, pH, density, thermal behaviors, elemental concentrations, phase separation and aging. The lignin and macroalgae oil properties were different compared to those of the wood and straw oils......A fast pyrolysis study on lignin and macroalgae (non-conventional biomass) and wood and straw (conventional biomass) were carried out in a pyrolysis centrifugal reactor at pyrolysis temperature of 550 ºC. The product distributions and energy recoveries were measured and compared among...

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.

Vacuum pyrolysis of waste tires with basic additives

International Nuclear Information System (INIS)

Zhang Xinghua; Wang Tiejun; Ma Longlong; Chang Jie

2008-01-01

Granules of waste tires were pyrolyzed under vacuum (3.5-10 kPa) conditions, and the effects of temperature and basic additives (Na 2 CO 3 , NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 deg. C to 600 deg. C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48 wt% was achieved at 550 deg. C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50 wt% was achieved at 480 deg. C by adding 3 wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) ∼205 deg. C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39 wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na 2 CO 3 addition. Pyrolysis gas was mainly composed of H 2 , CO, CH 4 , CO 2 , C 2 H 4 and C 2 H 6 . Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5 wt%) was much higher

The effect of pyrolysis temperature of palm oil shell on quantity and quality of liquid smoke

International Nuclear Information System (INIS)

Ratnawati; Singgih Hartanto

2010-01-01

Palm oil shell can be processed into carbon and liquid smoke through pyrolysis reaction where liquid smoke was obtained by condensation of smoke produced. In this research, liquid smoke was produced by pyrolysis of 5 kg palm oil shell at temperature of 200 °C, 300 °C, and 400 °C for 4 hours and the composition of liquid smoke was analyzed with Gas Chromatography -Mass Spectrometry (GC-MS). The pyrolysis processes at 200°C, 300 °C, and 400 °C produced 460 mL, 510 mL, and 550 mL of liquid smoke and 3.98, 3.24 and 1.49 kg of carbon respectively. The result of liquid smoke with pyrolysis process at 200 °C were 30.73 %(w/w) of antioxidant and food flavor component (guaiacol, 2,3 - butanedione, furfural and 2-methyl-2-cyclopentanone), and 34.31 %(w/w) of harmful components (phenol , 2-propanone, 2-butanone and cyclopentanone). At 400 °C, 27.39 %(w/w) of components can be used in food products and 26.51 %(w/w) of components was harmful for health. Liquid smoke produced from this experiment cannot yet be used as food preservative because it still contains harmful components which are dangerous for health, therefore it needs further separation. (author)

Laser induced pyrolysis techniques

International Nuclear Information System (INIS)

Vanderborgh, N.E.

1976-01-01

The application of laser pyrolysis techniques to the problems of chemical analysis is discussed. The processes occurring during laser pyrolysis are first briefly reviewed. The problems encountered in laser pyrolysis gas chromatography are discussed using the analysis of phenanthrene and binary hydrocarbons. The application of this technique to the characterization of naturally occurring carbonaceous material such as oil shales and coal is illustrated

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

DC Thermal Plasma Design and Utilization for the Low Density Polyethylene to Diesel Oil Pyrolysis Reaction

Directory of Open Access Journals (Sweden)

Hossam A. Gabbar

2017-06-01

Full Text Available The exponential increase of plastic production produces 100 million tonnes of waste plastics annually which could be converted into hydrocarbon fuels in a thermal cracking process called pyrolysis. In this research work, a direct current (DC thermal plasma circuit is designed and used for conversion of low density polyethylene (LDPE into diesel oil in a laboratory scale pyrolysis reactor. The experimental setup uses a 270 W DC thermal plasma at operating temperatures in the range of 625 °C to 860 °C for a low density polyethylene (LDPE pyrolysis reaction at pressure = −0.95, temperature = 550 °C with τ = 30 min at a constant heating rate of 7.8 °C/min. The experimental setup consists of a vacuum pump, closed system vessel, direct current (DC plasma circuit, and a k-type thermocouple placed a few millimeters from the reactant sample. The hydrocarbon products are condensed to diesel oil and analyzed using flame ionization detector (FID gas chromatography. The analysis shows 87.5% diesel oil, 1,4-dichlorobenzene (Surr, benzene, ethylbenzene and traces of toluene and xylene. The direct current (DC thermal plasma achieves 56.9 wt. % of diesel range oil (DRO, 37.8 wt. % gaseous products and minimal tar production. The direct current (DC thermal plasma shows reliability, better temperature control, and high thermal performance as well as the ability to work for long operation periods.

Refinery Upgrading of Hydropyrolysis Oil From Biomass

Energy Technology Data Exchange (ETDEWEB)

Roberts, Michael [Gas Technology Inst., Des Plaines, IL (United States); Marker, Terry [Gas Technology Inst., Des Plaines, IL (United States); Ortiz-Toral, Pedro [Gas Technology Inst., Des Plaines, IL (United States); Linck, Martin [Gas Technology Inst., Des Plaines, IL (United States); Felix, Larry [Gas Technology Inst., Des Plaines, IL (United States); Wangerow, Jim [Gas Technology Inst., Des Plaines, IL (United States); Swanson, Dan [Gas Technology Inst., Des Plaines, IL (United States); McLeod, Celeste [CRI Catalyst, Houston, TX (United States); Del Paggio, Alan [CRI Catalyst, Houston, TX (United States); Urade, Vikrant [CRI Catalyst, Houston, TX (United States); Rao, Madhusudhan [CRI Catalyst, Houston, TX (United States); Narasimhan, Laxmi [CRI Catalyst, Houston, TX (United States); Gephart, John [Johnson Timber, Hayward, WI (United States); Starr, Jack [Cargill, Wayzata, MN (United States); Hahn, John [Cargill, Wayzata, MN (United States); Stover, Daniel [Cargill, Wayzata, MN (United States); Parrish, Martin [Valero, San Antonio, TX (United States); Maxey, Carl [Valero, San Antonio, TX (United States); Shonnard, David [MTU, Friedrichshafen (Germany); Handler, Robert [MTU, Friedrichshafen (Germany); Fan, Jiquig [MTU, Friedrichshafen (Germany)

2015-08-31

hydropyrolysis oils had low acidity and caused almost no corrosion in comparison to pyrolysis oils, which had high acidity and caused significant levels of corrosion.

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.

Hydrotreatment of pyrolysis oils from biomass. Reactivity of the various categories of oxygenated compounds and preliminary techno-economical study

Energy Technology Data Exchange (ETDEWEB)

Grange, P.; Laurent, E.; Maggi, R.; Centeno, A.; Delmon, B. [Unite de Catalyse et Chimie des Materiaux Divises, Universite Catholique de Louvain, Louvain-la-Neuve (Belgium)

1996-05-31

This paper describes essential aspects of the hydrotreatment of pyrolytic oils in the light of results obtained until now at the Universite Catholique de Louvain. Stability of pyrolysis oils necessitates a two-step processing. A low temperature hydrotreatment enables stabilization through reactions like olefin, carbonyl and carboxylic groups reduction. Further hydrotreatment aims at hydrodeoxygenation of phenols and hydrocracking of larger molecules. Results about catalysts, reaction conditions and parameters enabling or influencing the control of the reaction are summarized. Based on these laboratory data, a preliminary techno-economical evaluation is made. 50 wt.-% yields in hydrocarbons for deep hydrorefining of pyrolysis oils can be expected. Nevertheless, a moderate hydroconversion with partial elimination of oxygen would be, economically, more advantageous

Characterization of some Jordanian oil shales by pyrolysis gas chromatography

International Nuclear Information System (INIS)

Jaradat, Q. M.

1995-01-01

Gas chromatography with flame ionization detector (GC-FID) was used to study pyrolysis of some Jordanian oil shale samples. Three sampls of different altitudes from El-Lajjun were studied. Pyrograms of solid sampls were studied at different temperature profiles. Solid-liquid extraction with water, methanol, or hexane allowed extraction of organics of different polarity. Hexane showed the highest extraction efficiency. Reproducibility of the pyrograms of the solid sample was evalualted. Relative standard deviation was 7.56%. (author). 7 refs., 8 figs

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.

Qualitative and quantitative analysis of pyrolysis oil by gas chromatography with flame ionization detection and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

Science.gov (United States)

Sfetsas, Themistoklis; Michailof, Chrysa; Lappas, Angelos; Li, Qiangyi; Kneale, Brian

2011-05-27

Pyrolysis oils have attracted a lot of interest, as they are liquid energy carriers and general sources of chemicals. In this work, gas chromatography with flame ionization detector (GC-FID) and two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS) techniques were used to provide both qualitative and quantitative results of the analysis of three different pyrolysis oils. The chromatographic methods and parameters were optimized and solvent choice and separation restrictions are discussed. Pyrolysis oil samples were diluted in suitable organic solvent and were analyzed by GC×GC-TOFMS. An average of 300 compounds were detected and identified in all three samples using the ChromaToF (Leco) software. The deconvoluted spectra were compared with the NIST software library for correct matching. Group type classification was performed by use of the ChromaToF software. The quantification of 11 selected compounds was performed by means of a multiple-point external calibration curve. Afterwards, the pyrolysis oils were extracted with water, and the aqueous phase was analyzed both by GC-FID and, after proper change of solvent, by GC×GC-TOFMS. As previously, the selected compounds were quantified by both techniques, by means of multiple point external calibration curves. The parameters of the calibration curves were calculated by weighted linear regression analysis. The limit of detection, limit of quantitation and linearity range for each standard compound with each method are presented. The potency of GC×GC-TOFMS for an efficient mapping of the pyrolysis oil is undisputable, and the possibility of using it for quantification as well has been demonstrated. On the other hand, the GC-FID analysis provides reliable results that allow for a rapid screening of the pyrolysis oil. To the best of our knowledge, very few papers have been reported with quantification attempts on pyrolysis oil samples using GC×GC-TOFMS most of which make use of the

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.

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.

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%.

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)

Method for rendering harmless sulfur dioxide-carrying gases and sulfur-carrying waste water from pyrolysis of oil shale

Energy Technology Data Exchange (ETDEWEB)

Aspegren, O E.A.; Eklund, A J

1951-03-15

A method is described for rendering harmless sulfur dioxide-carrying gases, which are formed in processes for the manufacture of solid, liquid, or gaseous products by pyrolysis of oil shale, and thereby to extract valuable products, characterized in that the sulfur dioxide-carrying gases are washed with a solution or sludge obtained by leaching wholly or partly burned-out residues from the pyrolysis.

Characteristics of activated carbon resulted from pyrolysis of the oil palm fronds powder

Science.gov (United States)

Maulina, S.; Iriansyah, M.

2018-02-01

Activated carbon is the product of a charcoal impregnation process that has a higher absorption capacity and has more benefits than regular char. Therefore, this study aims to cultivate the powder of oil palm fronds into activated carbon that meets the requirements of Standard National Indonesia 06-3730-1995. To do so, the carbonization process of the powder of oil palm fronds was carried out using a pyrolysis reactor for 30 minutes at a temperature of 150 °C, 200 °C, and 250 °C in order to produce activated char. Then, the char was impregnated using Phosphoric Acid activator (H3PO4) for 24 hours. Characteristics of activated carbon indicate that the treatment of char by chemical activation of oil palm fronds powder has an effect on the properties of activated carbon. The activated carbons that has the highest absorption properties to Iodine (822.91 mg/g) were obtained from the impregnation process with 15% concentration of Phosphoric Acid (H3PO4) at pyrolysis temperature of 200 °C. Furthermore, the activation process resulted in activated carbon with water content of 8%, ash content of 4%, volatile matter 39%, and fixed carbon 75%, Iodine number 822.91 mg/g.

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-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.

Recent technological advances in the application of nano-catalytic technology to the enhanced recovery and upgrading of bitumen and heavy oils

Energy Technology Data Exchange (ETDEWEB)

Pereira Almao, P. [Calgary Univ., AB (Canada). Schulich School of Engineering

2013-11-01

Advances in Nanotechnology, such as manufacturing of nano-catalysts allow the online (during processing) and on site production of nano-catalysts for heavy oils upgrading. These inventions have also facilitated the development of two lines of heavy oils upgrading processes that make use of nano-catalysts for producing upgraded oil: In Situ Upgrading and Field Upgrading. Producing chemical upgrading of heavy oils is achievable and economically viable at lower temperatures and lower pressures than used in most upgraders if the use of nano-catalysts were implemented. The spontaneity of thermal, steam and hydro processing reactions for converting the different chemical families of hydrocarbons present in the heaviest fractions of heavy oils and bitumen (HO-B) into lighter products was shown recently. Spontaneity was measured by the value of the change of free energy at low pressure. These undesirable paths are spontaneous and uncontrollable under thermal cracking conditions, and require providing years of residence time for intermolecular hydrogen redistribution to minimize olefins polymerization, if at all possible. Instead, hydroprocessing in the presence of hydrogen activating catalysts would create an abundance of hydrogen radicals impeding large molecules condensation and olefins proliferation. In Situ Upgrading: performs coupled Enhanced Oil Recovery with In Reservoir Upgrading via Hot Fluid Injection (HFI). The heat handling of this HFI process and the production of transportable oil with no need of diluent from the start of operation completes the originality of it. This technology uses heavy fractions separated from produced oil to reintroduce heat into the reservoir along with suspended nano-catalysts and hydrogen. These components react in the well bore and inside the reservoir to release more heat (hydroprocessing reactions are exothermic) producing light gases and volatile hydrocarbons that contribute to increase oil detachment from the rock resulting in

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.

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

Science.gov (United States)

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

2017-05-01

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

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.

Active carbon catalyst for heavy oil upgrading

Energy Technology Data Exchange (ETDEWEB)

Fukuyama, Hidetsugu; Terai, Satoshi [Technology Research Center, Toyo Engineering Corporation, 1818 Azafujimi, Togo, Mobara-shi, Chiba 297-00017 (Japan); Uchida, Masayuki [Business Planning and Exploring Department, Overseas Business Development and Marketing Division, Toyo Engineering Corporation, 2-8-1 Akanehama, Narashino-shi, Chiba 275-0024 (Japan); Cano, Jose L.; Ancheyta, Jorge [Maya Crude Treatment Project, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas No. 152, Col. San Bartolo Atepehuacan, Mexico D.F. 07730 (Mexico)

2004-11-24

The active carbon (AC) catalyst was studied by hydrocracking of Middle Eastern vacuum residue (VR) for heavy oil upgrading. It was observed that the active carbon has the affinity to heavy hydrocarbon compounds and adsorption selectivity to asphaltenes, and exhibits better ability to restrict the coke formation during the hydrocracking reaction of VR. The mesopore of active carbon was thought to play an important role for effective conversion of heavy hydrocarbon compounds into lighter fractions restricting carbon formation. The performance of the AC catalyst was examined by continuous hydrocracking by CSTR for the removal of such impurities as sulfur and heavy metals (nickel and vanadium), which are mostly concentrated in the asphaltenes. The AC catalyst was confirmed to be very effective for the removal of heavy metals from Middle Eastern VR, Maya/Istmo VR and Maya VR. The extruded AC catalysts were produced by industrial manufacturing method. The application test of the extruded AC catalyst for ebullating-bed reactor as one of the commercially applicable reactors was carried out at the ebullating-bed pilot plant for 500h. The ebullition of the extruded AC catalyst was successfully traced and confirmed by existing {gamma}-ray density meter. The extruded AC catalyst showed stable performance with less sediment formation at an equivalent conversion by conventional alumina catalyst at commercial ebullating-bed unit. The degradation of the AC catalyst at the aging test was observed to be less than that of the conventional alumina catalyst. Thus, the AC catalyst was confirmed to be effective and suitable for upgrading of heavy oil, especially such heavy oils as Maya, which contains much heavy metals.

The vacuum pyrolysis of used tires. End-uses for oil and carbon black products

Energy Technology Data Exchange (ETDEWEB)

Roy, C.; Chaala, A.; Darmstadt, H. [Institut Pyrovac Inc., Parc Technologique du Quebec Metropolitain, rue Franquet, Sainte-Foy (Canada)

1999-07-01

By vacuum pyrolysis, the rubber portion of used tires is transformed into oil and gas and the carbon black filler is recovered as pyrolytic carbon black (CB{sub P}). Several commercial applications for the different products have been investigated and are reported in this article. CB{sub P} surface chemistry and activity are similar to those of commercial carbon blacks. Therefore, CB{sub P} has the potential to replace commercial carbon black grades in certain rubber applications. CB{sub P} was successfully tested as a filler in road pavement. The total pyrolytic oil can be used as a liquid fuel. The oil can also be distilled into different fractions: a light, a middle distillate and a heavy fraction. The light fraction was positively tested as a gasoline additive. Furthermore, this fraction contains valuable chemicals such as d,l-limonene. The middle fraction was successfully tested as a plasticizer in rubbers. The heavy fraction represents a good-quality feedstock for the production of coke and can also be used in road pavements. The pyrolytic gas can be used as a make-up heat source for the pyrolysis process

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.

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).

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

Energy Technology Data Exchange (ETDEWEB)

Lin, Kuo-Hsiung [Department of Environmental Engineering and Science, Fooyin University, Kaohsiung, Taiwan (China); Chiang, Hung-Lung, E-mail: hlchiang@mail.cmu.edu.tw [Department of Health Risk Management, China Medical University, Taichung, Taiwan (China)

2014-04-01

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

Development and Application of a Life Cycle-Based Model to Evaluate Greenhouse Gas Emissions of Oil Sands Upgrading Technologies.

Science.gov (United States)

Pacheco, Diana M; Bergerson, Joule A; Alvarez-Majmutov, Anton; Chen, Jinwen; MacLean, Heather L

2016-12-20

A life cycle-based model, OSTUM (Oil Sands Technologies for Upgrading Model), which evaluates the energy intensity and greenhouse gas (GHG) emissions of current oil sands upgrading technologies, is developed. Upgrading converts oil sands bitumen into high quality synthetic crude oil (SCO), a refinery feedstock. OSTUM's novel attributes include the following: the breadth of technologies and upgrading operations options that can be analyzed, energy intensity and GHG emissions being estimated at the process unit level, it not being dependent on a proprietary process simulator, and use of publicly available data. OSTUM is applied to a hypothetical, but realistic, upgrading operation based on delayed coking, the most common upgrading technology, resulting in emissions of 328 kg CO 2 e/m 3 SCO. The primary contributor to upgrading emissions (45%) is the use of natural gas for hydrogen production through steam methane reforming, followed by the use of natural gas as fuel in the rest of the process units' heaters (39%). OSTUM's results are in agreement with those of a process simulation model developed by CanmetENERGY, other literature, and confidential data of a commercial upgrading operation. For the application of the model, emissions are found to be most sensitive to the amount of natural gas utilized as feedstock by the steam methane reformer. OSTUM is capable of evaluating the impact of different technologies, feedstock qualities, operating conditions, and fuel mixes on upgrading emissions, and its life cycle perspective allows easy incorporation of results into well-to-wheel analyses.

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

Renewable glycolaldehyde isolation from pyrolysis oil-derived aqueous solution by reactive extraction with primary amines

NARCIS (Netherlands)

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

2012-01-01

Glycolaldehyde can be separated from a pyrolysis oil-derived aqueous phase by reactive extraction employing primary amines dissolved in organic diluents. This work investigates the occurrence of solid imine formation from glycolaldehyde and amines and the competitive reactions in the organic extract

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.

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.

Evaluation of the properties of tyre pyrolysis oils obtained in a conical spouted bed reactor

International Nuclear Information System (INIS)

Alvarez, J.; Lopez, G.; Amutio, M.; Mkhize, N.M.; Danon, B.; Gryp, P. van der; Görgens, J.F.; Bilbao, J.; Olazar, M.

2017-01-01

Waste truck tyre valorization by fast pyrolysis has been performed in a conical spouted bed reactor in the 425–575 °C range. The tyre pyrolysis oil (TPO) yield was found to decrease with increasing temperature whilst the yield of gas increased. The effect of temperature on TPO properties has been studied in order to establish the best possible valorization route. FTIR and chromatographic analysis revealed the presence of some undesired compounds with sulphur, nitrogen or oxygen functionalities (benzotiatholes, nitriles and carboxylic acids amongst others) and an increase of TPO aromaticity with increasing temperature. The carbon and sulphur content and the heating value of the TPO increased with temperature. The simulated distillation showed that approximately 70% of the TPOs produced at 425 and 475 °C correspond to diesel range, whereas that TPO obtained at 575 °C is between diesel and gasoline range. The properties of the TPOs evidenced their potential to substitute conventional fuels. However, some of them need to be improved, i.e., by reduction of the sulphur, nitrogen and aromatic content. Additionally, the TPO obtained at 425 and 475 °C could be an important source of limonene and that at 575 °C of xylenes, although current removal methods present some limitations. - Highlights: • The conical spouted bed reactor is suitable for truck tyre fast pyrolysis. • The highest oil yields are attained between 425 and 475 °C (≈58 wt %). • Tyre oil is a mixture of water, aromatic, aliphatic and heteroaromatic compounds. • Limonene is the major compound with a maximum yield of 13.30 wt % at 475 °C. • 425 and 475 °C oils share similarities with diesel and 575 °C one with gasoline.

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.

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 during difficult times

International Nuclear Information System (INIS)

Tiefenbach, K.

1993-01-01

The Co-op Upgrader is part of an integrated refinery and upgrader complex in Regina, Saskatchewan. The upgrader processes 50,000 bbl/d heavy sour crude oil, mostly Fosterton and dilute Lloydminster crude, via hydrogen addition and carbon rejection, desulfurization, demetallization, and denitrification to yield a synthetic crude blend. The synthetic crude is refined to produce gasoline and diesel fuel. Byproducts from the integrated operation include 100,000 tonnes/y of petroleum coke, 65,000 tonnes/y of sulfur, propane, butane, fuel oil, and metals (Ni and V) in the form of spent catalysts. Recent operational and economic challenges faced by the upgrader are reviewed. Technical challenges include operating the upgrader's high-temperature high-pressure heavy oil hydrotreating unit and distillate hydrogenation unit, removal and replacement of the desulfurization catalyst, waste management, and producing coke of sufficient quality. Economic challenges include the shrinking differential between light and heavy oil, higher prices for natural gas (the main raw material for hydrogen production for upgrading), seasonal changes in product specifications, and lower prices for sulfur and metal byproducts. The upgrader is also affected by interest rates since borrowing costs are the single largest expenditure after crude oil purchases. 4 figs

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

Bi-Provincial Upgrader

International Nuclear Information System (INIS)

1997-01-01

Husky Oil's Bi-Provincial Upgrader is located in the rural municipality of Wilton, east of Lloydminster, Saskatchewan. It is jointly owned by Husky Oil and the Saskatchewan government. The upgrader is designed to produce 7.300 m 3 /cd of synthetic crude from 8.440 m 3 /cd of diluted Lloyd blend and distillates from the existing Lloydminster refinery. The designed coke and sulphur production is 415 t/day and 240 t/day respectively. Chronology of the Bi-Provincial Upgrader project was presented, along with details of the heavy oil feedstock properties for Cold Lake, Lloydminster and Lloyd Blend. Upgrader production history since start-up, synthetic crude oil customers, and the evolution of prices for Edmonton light vs. Husky LLB at Hardisty were also reviewed. 3 tabs., 9 figs

Effects of smectite on the oil-expulsion efficiency of the Kreyenhagen Shale, San Joaquin Basin, California, based on hydrous-pyrolysis experiments

Science.gov (United States)

Lewan, Michael D.; Dolan, Michael P.; Curtis, John B.

2014-01-01

The amount of oil that maturing source rocks expel is expressed as their expulsion efficiency, which is usually stated in milligrams of expelled oil per gram of original total organic carbon (TOCO). Oil-expulsion efficiency can be determined by heating thermally immature source rocks in the presence of liquid water (i.e., hydrous pyrolysis) at temperatures between 350°C and 365°C for 72 hr. This pyrolysis method generates oil that is compositionally similar to natural crude oil and expels it by processes operative in the subsurface. Consequently, hydrous pyrolysis provides a means to determine oil-expulsion efficiencies and the rock properties that influence them. Smectite in source rocks has previously been considered to promote oil generation and expulsion and is the focus of this hydrous-pyrolysis study involving a representative sample of smectite-rich source rock from the Eocene Kreyenhagen Shale in the San Joaquin Basin of California. Smectite is the major clay mineral (31 wt. %) in this thermally immature sample, which contains 9.4 wt. % total organic carbon (TOC) comprised of type II kerogen. Compared to other immature source rocks that lack smectite as their major clay mineral, the expulsion efficiency of the Kreyenhagen Shale was significantly lower. The expulsion efficiency of the Kreyenhagen whole rock was reduced 88% compared to that of its isolated kerogen. This significant reduction is attributed to bitumen impregnating the smectite interlayers in addition to the rock matrix. Within the interlayers, much of the bitumen is converted to pyrobitumen through crosslinking instead of oil through thermal cracking. As a result, smectite does not promote oil generation but inhibits it. Bitumen impregnation of the rock matrix and smectite interlayers results in the rock pore system changing from water wet to bitumen wet. This change prevents potassium ion (K+) transfer and dissolution and precipitation reactions needed for the conversion of smectite to

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

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

Heavy fuel oil pyrolysis and combustion: kinetics and evolved gases investigated by TGA-FTIR

KAUST Repository

Abdul Jameel, Abdul Gani

2017-08-24

Heavy fuel oil (HFO) obtained from crude oil distillation is a widely used fuel in marine engines and power generation technologies. In the present study, the pyrolysis and combustion of a Saudi Arabian HFO in nitrogen and in air, respectively, were investigated using non-isothermal thermo-gravimetric analysis (TGA) coupled with a Fourier-transform infrared (FTIR) spectrometer. TG and DTG (differential thermo-gravimetry) were used for the kinetic analysis and to study the mass loss characteristics due to the thermal degradation of HFO at temperatures up to 1000°C and at various heating rates of 5, 10 and 20°C/min, in air and N2 atmospheres. FTIR analysis was then performed to study the composition of the evolved gases. The TG/DTG curves during HFO combustion show the presence of three distinct stages: the low temperature oxidation (LTO); fuel decomposition (FD); and high temperature oxidation (HTO) stages. The TG/DTG curves obtained during HFO pyrolysis show the presence of two devolatilization stages similar to that seen in the LTO stage of HFO combustion. Apart from this, the TG/DTG curves obtained during HFO combustion and pyrolysis differ significantly. Kinetic analysis was also performed using the distributed activation energy model, and the kinetic parameter (E) was determined for the different stages of HFO combustion and pyrolysis processes, yielding a good agreement with the measured TG profiles. FTIR analysis showed the signal of CO2 as approximately 50 times more compared to the other pollutant gases under combustion conditions. Under pyrolytic conditions, the signal intensity of alkane functional groups was the highest followed by alkenes. The TGA-FTIR results provide new insights into the overall HFO combustion processes, which can be used to improve combustor designs and control emissions.

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.

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 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.

New technology for producing petrochemical feedstock from heavy oils derived from Alberta oil sands

International Nuclear Information System (INIS)

Oballa, M.; Simanzhenkov, V.; Clark, P.; Laureshen, C.; Plessis du, D.

2006-01-01

This paper presented the results of a study demonstrating the feasibility of producing petrochemical feedstock or petrochemicals from vacuum gas oils derived from oil sands. A typical bitumen upgrader flow scheme was integrated with several new technologies and coupled with an ethane/propane cracker. Technologies included steam cracking, fluid catalytic cracking (FCC); and the catalytic pyrolysis process (CPP). The scheme was then integrated with the Nova Heavy Oil Cracking (NHC) technology. The NHC process uses a reactor to perform catalytic cracking followed by a main tower that separates gas and liquid products. Aromatic ring cleavage (ARORINCLE) technology was explored as a method of catalytic treatment. Experimental runs were conducted in a laboratory scale fixed bed reactor. A stacked catalyst bed was used, followed by a zeolite-based noble metal catalyst. Examples from process run results were presented. Results indicated that the NHC technology should be used on an FCC unit technology platform. The ARORINCLE technology was considered for use on a hydrotreating unit technology platform. Once the catalysts are fully developed and demonstrated, the economics of the technologies will be enhanced through the construction of world-scale complexes integrating upgrading, refining and petrochemical plants. refs., tabs., figs

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.

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.

Atmospheric Hydrodeoxygenation of Biomass Fast Pyrolysis Vapor by MoO₃

DEFF Research Database (Denmark)

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

2016-01-01

was not significant at temperatures below 400 °C. At 450 °C catalyst temperature and 93 vol % H2 concentration, the wood pyrolysis vapor was more active toward cracking forming gas species instead of performing the desired HDO forming hydrocarbons. The lignin pyrolysis vapor was more resistant to cracking and yielded...... 16.2 wt %daf organic liquid, while achieving 52% degree of deoxygenation at 450 °C catalyst temperature under 89 vol % H2 concentration. The corresponding energy recovery in the liquid phase was 23.5%. The spent catalyst showed two deactivation routes, coke formation and reduction of MoO3 to MoO2......, which is inactive in HDO. The catalyst experienced severe reduction at temperatures higher than 400 °C. The yields of coke relative to the fed biomass were in the range of 3–4 wt %daf for lignin and 5–6 wt %daf for wood. Compared to untreated bio-oil the upgraded lignin organic liquid showed improved...

Pipeline transportation of emerging partially upgraded bitumen

International Nuclear Information System (INIS)

Luhning, R.W.; Anand, A.; Blackmore, T.; Lawson, D.S.

2002-01-01

The recoverable reserves of Canada's vast oil deposits is estimated to be 335 billion barrels (bbl), most of which are in the Alberta oil sands. Canada was the largest import supplier of crude oil to the United States in 2001, followed by Saudi Arabia. By 2011, the production of oil sands is expected to increase to 50 per cent of Canada's oil, and conventional oil production will decline as more production will be provided by synthetic light oil and bitumen. This paper lists the announced oil sands projects. If all are to proceed, production would reach 3,445,000 bbl per day by 2011. The three main challenges regarding the transportation and marketing of this new production were described. The first is to expand the physical capacity of existing pipelines. The second is the supply of low viscosity diluent (such as natural gas condensate or synthetic diluent) to reduce the viscosity and density of the bitumen as it passes through the pipelines. The current pipeline specifications and procedures to transport partially upgraded products are presented. The final challenge is the projected refinery market constraint to process the bitumen and synthetic light oil into consumer fuel products. These challenges can be addressed by modifying refineries and increasing Canadian access in Petroleum Administration Defense District (PADD) II and IV. The technology for partial upgrading of bitumen to produce pipeline specification oil, reduce diluent requirements and add sales value, is currently under development. The number of existing refineries to potentially accept partially upgraded product is listed. The partially upgraded bitumen will be in demand for additional upgrading to end user products, and new opportunities will be presented as additional pipeline capacity is made available to transport crude to U.S. markets and overseas. The paper describes the following emerging partial upgrading methods: the OrCrude upgrading process, rapid thermal processing, CPJ process for

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.

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

Potential for using a tyre pyrolysis oil-biodiesel blend in a diesel engine at different compression ratios

International Nuclear Information System (INIS)

Sharma, Abhishek; Murugan, S.

2015-01-01

Highlights: • The possibility of operating a compression ignition engine with a non petroleum diesel fuel. • A possible solution to replace certain amount of biodiesel by tyre pyrolysis oil in a biodiesel fueled diesel engine. • The optimum compression ratio for engine fueled with biodiesel-tyre pyrolysis oil blend. - Abstract: This study is aimed at investigating effects of varying the compression ratio at optimum injection timing and nozzle opening pressure on the behaviour of a diesel engine, using a non-petroleum fuel, i.e. a blend of 80% biodiesel, and 20% oil obtained from pyrolysis of waste tyres. The engine was subjected to one lower (16.5) and one higher (18.5) compression ratio in addition to the standard compression ratio of 17.5. At the higher compression ratio of 18.5 and full load, shorter ignition delay, maximum cylinder pressure and higher heat release rate were found for the blend, compared to those of the original compression ratio. The increase in the compression ratio from 17.5 to 18.5 for the blend improved the brake thermal efficiency by about 8% compared to that of the original compression ratio at full load. The experimental results indicated that for the blend at a higher compression ratio of 18.5, the brake specific carbon monoxide (BSCO), brake specific hydrocarbon emission (BSHC) and smoke opacity were reduced by about 10.5%, 32%, and 17.4% respectively, than those of the original compression ratio at full load

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)

Low-temperature pyrolysis of oily sludge: roles of Fe/Al-pillared bentonites

Directory of Open Access Journals (Sweden)

Jia Hanzhong

2017-09-01

Full Text Available Pyrolysis is potentially an effective treatment of oily sludge for oil recovery, and the addition of a catalyst is expected to affect its pyrolysis behavior. In the present study, Fe/Al-pillared bentonite with various Fe/Al ratios as pyrolysis catalyst is prepared and characterized by XRD, N2 adsorption, and NH3-TPD. The integration of Al and Fe in the bentonite interlayers to form pillared clay is evidenced by increase in the basal spacing. As a result, a critical ratio of Fe/Al exists in the Fe/Al-pillared bentonite catalytic pyrolysis for oil recovery from the sludge. The oil yield increases with respect to increase in Fe/Al ratio of catalysts, then decreases with further increasing of Fe/Al ratio. The optimum oil yield using 2.0 wt% of Fe/Al 0.5-pillared bentonite as catalyst attains to 52.46% compared to 29.23% without catalyst addition in the present study. In addition, the addition of Fe/Al-pillared bentonite catalyst also improves the quality of pyrolysis-produced oil and promotes the formation of CH4. Fe/Al-pillared bentonite provides acid center in the inner surface, which is beneficial to the cracking reaction of oil molecules in pyrolysis process. The present work implies that Fe/Al-pillared bentonite as addictive holds great potential in industrial pyrolysis of oily sludge.

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.

Review of Heterogeneous Catalysts for Catalytically Upgrading Vegetable Oils into Hydrocarbon Biofuels

OpenAIRE

Xianhui Zhao; Lin Wei; Shouyun Cheng; James Julson

2017-01-01

To address the issues of greenhouse gas emissions associated with fossil fuels, vegetable oilseeds, especially non-food oilseeds, are used as an alternative fuel resource. Vegetable oil derived from these oilseeds can be upgraded into hydrocarbon biofuel. Catalytic cracking and hydroprocessing are two of the most promising pathways for converting vegetable oil to hydrocarbon biofuel. Heterogeneous catalysts play a critical role in those processes. The present review summarizes current progres...

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

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...

Co-pyrolysis of rice straw and Polyethylene Terephthalate (PET) using a fixed bed drop type pyrolyzer

Science.gov (United States)

Izzatie, N. I.; Basha, M. H.; Uemura, Y.; Hashim, M. S. M.; Amin, N. A. M.; Hamid, M. F.

2017-10-01

In this work, co-pyrolysis of rice straw and polyethylene terephthalate (PET) was carried out at different temperatures (450,500,550, and 600°C) at ratio 1:1 by using fixed bed drop-type pyrolyzer. The purpose of this work is to determine the effect of pyrolysis temperature on the product yield. As the temperature increased, the pyrolysis oil increased until it reaches certain high temperature (600°C), the pyrolysis oil decreased as of more NCG were produced. The temperature 550°C is considered as the optimum pyrolysis temperature since it produced the highest amount of pyrolysis oil with 36 wt.%. In pyrolysis oil, the calorific value (13.98kJ/g) was low because of the presence of high water content (52.46 wt.%). Main chemicals group from pyrolysis oil were an aldehyde, ketones, acids, aromatics, and phenol and all compound have abundant of hydrogen and carbon were identified. Co-pyrolysis of rice straw and PET produced a higher amount of carbon oxides and recycling back the NCG could increase liquid and char yields.

Hot char-catalytic reforming of volatiles from MSW pyrolysis

International Nuclear Information System (INIS)

Wang, Na; Chen, Dezhen; Arena, Umberto; He, Pinjing

2017-01-01

Highlights: • Volatile from MSW pyrolysis is reformed with hot char from the same pyrolysis process. • The yields of syngas increase evidently with H 2 being the main contributor and the major component of the syngas. • Pyrolysis oil becomes light and its composition distribution is narrowed. • The HHV, volatile elements and alkali metals contents in the char decrease. • The emissions including SO 2 , NO, NO 2 and HCN changed after reforming process. - Abstract: Volatile products obtained from pyrolysis of municipal solid waste (MSW), including syngas and pyrolysis oil, were forced to contact the hot char from the same pyrolysis process at 500–600 °C in a fixed bed reactor to be reformed. The yields and properties of syngas, char and pyrolysis liquid were investigated; and the energy re-distribution among the products due to char reforming was quantified. The preliminary investigation at lab scale showed that hot char-catalytic reforming of the volatiles leads to an increase in the dry syngas yield from 0.25 to 0.37 N m 3 kg −1 MSW at 550 °C. Accordingly, the carbon conversion ratio into syngas increases from 29.6% to 35.0%; and the MSW chemical energy transferred into syngas increased from 41.8% to 47.4%. The yield of pyrolysis liquid products, including pyrolysis oil and water, decreased from 27.3 to 16.5 wt%, and the molecular weight of the oil becoming lighter. Approximately 60% of the water vapour contained in the volatiles converted into syngas. After reforming, the concentrations of SO 2 and HCN in the syngas decreases, while those of NO and NO 2 increase. The char concentrations of N, H, C and alkali metal species decreased and its higher heating value decreased too.

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

Energy Technology Data Exchange (ETDEWEB)

Lawal, Adeniyi [Stevens Institute of Technology, Castle Point Hoboken NJ 07030

2012-09-29

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

Pyrolysis of rubber gloves in integral pyrolysis test plant

International Nuclear Information System (INIS)

Norasalwa Zakaria; Mohd Noor Muhd Yunus; Mohd Annuar Assadat Husain; Farid Nasir Ani

2010-01-01

Previously, pyrolysis of rubber gloves in laboratory study was described. In order to visualize the practical application of rubber gloves pyrolysis in terms of treating rubber gloves in medical waste, a new test plant was designed and constructed. The semi-continuous test plant was designed to accommodate rubber gloves that were not cut or shredded. The test plant has a capacity of 2kg/ hr and employed auxiliary fuel instead of the conventional electrical power for heating. The concept was based on moving bed reactor, but additional feature of sand jacket feature was also introduced in the design. Pyrolysis of the gloves was conducted at three temperatures, namely 350 degree Celsius, 400 degree Celsius and 450 degree Celsius. Oxygen presents inside of the reactor due to the combined effect of imperfect sealing and suction effect. This study addresses the performance of this test plant covering the time temperature profile, gas evolution profile and product yield. Comparison between the yield of the liquid, gas and char pyrolyzate was made against the laboratory study. It was found that the oil yield was less than the one obtained from bench scale study. Water formation was more pronounced. The presence of the oxygen also altered the tail gas composition but eliminate the sticky nature of solid residue, making it easier to handle. The chemical composition of the oil was determined and the main compounds in the oil were esters and phtalic acid. (author)

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

Science.gov (United States)

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

2017-05-01

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

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...

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...

PIROLISIS LIGNIN DARI LIMBAH INDUSTRI KELAPA SAWIT UNTUK PENGEMBANGAN SURFAKTAN DALAM PROSES ENHANCE OIL RECOVERY (EOR (Pyrolysis of Lignin From Waste of Palm Oil Industries for The Development of Surfactants for Enhance Oil Recovery (EOR

Directory of Open Access Journals (Sweden)

Suryo Purwono

2001-12-01

Full Text Available ABSTRAK Pirolisis dari lignin yang berasal dari limbah industri kelapa sawit dapat menghasilkan alkohol dan derivatif lainnyd yang dapat digunakan sehagai surfaktan. Prosedur penelitian proses pirolisis ini odalah sebagai berikut: I serabut atau tandan sisa pengolahon kelapa sawit yang sudah dikeringkan dimasukkan kedalam reaktor dengan berat tertentu dan dipanaskan sampai suhu yang diinginkan, 2 produk pirolisis yang keluar dari reoktor kemudian didinginkan sampoi mencapai suhu kamor, 3 hasil cair ditampung didalam gelas ukur dan hasil gasnya ditampung di suatu botol tertentu. Suhu paling baik yang dicapai adalah 4A0 "C untuk lignin yong berasal dari serabut dan 350'C untuk lignin yang berasal dari tandan kelapa sawit. Surfaktan yang dihasilkan sekitar j4 sampai 38% dari produk pirolisis. Pada penelitian ini kecepatan reaksi dianggap order satu. Hasil penelitian menunjukkan bahwa surfakton yang dihasilkan dapat membentuk emulsi dengan minyak menta.h. Hal ini menunjukkon bahwa surfaktan yang dihasilkan dapat digunakan sebagai bahan untuk proses EOR.   ABSTRACT Pyrolysis of lignin from waste of palm oil industries produces alcohol and its derivatives which can be sulfonated to become surfactant. The experimental procedures for the pyrolysis process were as follows: 1 dried palm oil husks at a certain weight were put into the pyrolysis reactor and heated up to a certain temperafure; 2 the product leaving the reactor was cooled down to room temperature; and 3 the liquid product was collected in a flask while the gas product was put into a big bottle. The best temperature obtained for producing liquid product was 400 oC for lignin from palm oil fruit fibers and 350 oC for lignin from palm oil fruit stems. The surfactant developed was in the range between 34 and 38% from the pyrolysis product. In this experiment, the reaction rate was assumed to be in first order. The result showed that the surfactant obtained from the experiment could form emulsion

Auto shredder residue recycling: Mechanical separation and pyrolysis

International Nuclear Information System (INIS)

Santini, Alessandro; Passarini, Fabrizio; Vassura, Ivano; Serrano, David; Dufour, Javier; Morselli, Luciano

2012-01-01

Highlights: ► In this work, we exploited mechanical separation and pyrolysis to recycle ASR. ► Pyrolysis of the floating organic fraction is promising in reaching ELV Directive targets. ► Zeolite catalyst improve pyrolysis oil and gas yield. - Abstract: sets a goal of 85% material recycling from end-of-life vehicles (ELVs) by the end of 2015. The current ELV recycling rate is around 80%, while the remaining waste is called automotive shredder residue (ASR), or car fluff. In Europe, this is mainly landfilled because it is extremely heterogeneous and often polluted with car fluids. Despite technical difficulties, in the coming years it will be necessary to recover materials from car fluff in order to meet the ELV Directive requirement. This study deals with ASR pretreatment and pyrolysis, and aims to determine whether the ELV material recycling target may be achieved by car fluff mechanical separation followed by pyrolysis with a bench scale reactor. Results show that flotation followed by pyrolysis of the light, organic fraction may be a suitable ASR recycling technique if the oil can be further refined and used as a chemical. Moreover, metals are liberated during thermal cracking and can be easily separated from the pyrolysis char, amounting to roughly 5% in mass. Lastly, pyrolysis can be a good starting point from a “waste-to-chemicals” perspective, but further research should be done with a focus on oil and gas refining, in order both to make products suitable for the chemical industry and to render the whole recycling process economically feasible.

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.

Torrefaction reduction of coke formation on catalysts used in esterification and cracking of biofuels from pyrolysed lignocellulosic feedstocks

Science.gov (United States)

Kastner, James R; Mani, Sudhagar; Hilten, Roger; Das, Keshav C

2015-11-04

A bio-oil production process involving torrefaction pretreatment, catalytic esterification, pyrolysis, and secondary catalytic processing significantly reduces yields of reactor char, catalyst coke, and catalyst tar relative to the best-case conditions using non-torrefied feedstock. The reduction in coke as a result of torrefaction was 28.5% relative to the respective control for slow pyrolysis bio-oil upgrading. In fast pyrolysis bio-oil processing, the greatest reduction in coke was 34.9%. Torrefaction at 275.degree. C. reduced levels of acid products including acetic acid and formic acid in the bio-oil, which reduced catalyst coking and increased catalyst effectiveness and aromatic hydrocarbon yields in the upgraded oils. The process of bio-oil generation further comprises a catalytic esterification of acids and aldehydes to generate such as ethyl levulinate from lignified biomass feedstock.

Liquid fuels from Canadian peat by the Waterloo fast pyrolysis process

Energy Technology Data Exchange (ETDEWEB)

Piskorz, J.; Majerski, P.; Scott, D.S. (Univ. of Waterloo, ON (Canada))

1990-06-01

Two Quebec peats were pyrolyzed in the Waterloo fast pyrolysis process with the objective of maximizing liquid yields. A young sphagnum peat gave maximum organic liquid yields of 45-47% in an optimum range of 450-550{degree}C and 1 atm pressure. Char yields varied from 35% to 26% and gas yields from 12% to 17% over the range. The character of the liquid product changed significantly over the optimum temperature range, with the ratio of water soluble to water insoluble components decreasing from 2.3 to 0.6 as temperature increased, with an accompanying decrease in oxygen content. Pyrolytic oil yields from an old black peat gave similar results, although with somewhat lower yields of organic liquids. Char yield was somewhat higher (33%) at optimum conditions, but gas yield was nearly identical. Upgrading tests of the peat oil obtained a yield of ca 33% of the liquid feed as a gasoline-like liquid under hydrodeoxygenation conditions. 7 refs., 11 figs., 6 tabs.

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.

Proceedings of the 3. NCUT meeting on upgrading and refining of heavy oil, bitumen and synthetic crude oil and the 2. symposium on stability and compatibility during the production, transportation and refining of petroleum

International Nuclear Information System (INIS)

2003-01-01

This conference highlights new developments in refining processes for heavy oil, bitumen, and synthetic crudes. The oil sands/heavy oil industry in Canada has grown significantly in the last decade and could triple by 2012 to reach 2.6 million barrels per day. Experts from the petroleum industry, government organizations and technology providers attended this conference which identified technology gaps and areas where improvements are needed. The presentations demonstrated that many new technologies associated with heavy oil bitumen upgrading and refining have posed compatibility and stability challenges for pipeliners, upgraders and refiners. One of the issues addressed at the conference was the effect of upgrading technologies on market price due to the expected increase in production. Another important issue is how production of bitumen can be increased without significantly increasing greenhouse gas emissions from the refineries and upgrading facilities. The sessions of the conference were entitled: new technology developments in bitumen upgrading; secondary upgrading developments and expanded product opportunities; environmental issues and expanded oil sands development; and, stability and compatibility during the production, transportation and refining of petroleum. Twenty six presentations were indexed separately for inclusion in this database. tabs., figs

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.

Laboratory scale conceptual process development for the isolation of renewable glycolaldehyde from pyrolysis oil to produce fermentation feedstock

NARCIS (Netherlands)

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

2012-01-01

A laboratory-based separation sequence has been developed to produce an aqueous glycolaldehyde solution as fermentation feedstock. It consists of water extraction of pyrolysis oil, acid removal, water removal, octanol extraction, phenolic removal, back-extraction, and washing. The octanol-free

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)

Hydrocarbon upgrading demonstration program (HUDP): an investment in the future of the oil sands

Energy Technology Data Exchange (ETDEWEB)

Du Plessis, Duke; Isaacs, Eddy [AI-EES (Canada); Hill, Rich; McPhee, Anne; Keesom, Bill; Arnold, Ed [Jacobs Consultancy (Canada)

2011-07-01

Alberta Innovates Energy and Environment Solutions (AIEES), the technology arm of the Alberta Government in terms of energy and the environment, has initiated the hydrocarbon upgrading demonstration program (HUDP). Since lighter products have a better market value, this program aims to develop technologies for upgrading heavy oil into light, transportable fuel. The program also aims to improve SAGD efficiency while reducing greenhouse gas emissions. To do so, the gaps between typical and ideal operations were identified and quantified, life cycle analyses were performed, current studies were reviewed and future issues and opportunities were assessed. With the HUDP program, AIEES is supporting the industry through investment and technology support to develop innovative technologies which will improve margins and the sustainability of oil sands operations.

[Influence of impurities on waste plastics pyrolysis: products and emissions].

Science.gov (United States)

Zhao, Lei; Wang, Zhong-Hui; Chen, De-Zhen; Ma, Xiao-Bo; Luan, Jian

2012-01-01

The study is aimed to evaluate the impact of impurities like food waste, paper, textile and especially soil on the pyrolysis of waste plastics. For this purpose, emissions, gas and liquid products from pyrolysis of waste plastics and impurities were studied, as well as the transfer of element N, Cl, S from the substrates to the pyrolysis products. It was found that the presence of food waste would reduce the heat value of pyrolysis oil to 27 MJ/kg and increase the moisture in the liquid products, therefore the food residue should be removed from waste plastics; and the soil, enhance the waste plastics' pyrolysis by improving the quality of gas and oil products. The presence of food residue, textile and paper leaded to higher gas emissions.

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.

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}.

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.

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

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.

Upgrading of waste oils into transportation fuels using hydrotreating technologies

OpenAIRE

Sudipta De; Rafael Luque

2014-01-01

The generation of organic waste continues to increase, causing severe environmental pollution. Waste valorization is currently an emerging technology that can address this problem with an extra benefit of producing a range of valued products. In this contribution, we report the current developments in hydrotreating technologies for upgrading waste oil fractions into usable transportation fuels. Particular focus is given on the catalysts selection for a general hydroprocessing technique as wel...

Effect of acid washing on pyrolysis of Cladophora socialis alga in microtubing reactor

International Nuclear Information System (INIS)

Ly, Hoang Vu; Kim, Seung-Soo; Kim, Jinsoo; Choi, Jae Hyung; Woo, Hee Chul

2015-01-01

Highlights: • Pyrolysis of macroalgae Cladophora socialis was conducted in micro tubular reactor. • Acid washing affected the pyrolysis behavior of Cladophora socialis. • Pyrolysis of raw and acid washed C. socialis produced bio-oils with different compositions. • Pyrolysis reaction pathway was from C. socialis to liquid and then to gas (C_1–C_4). - Abstract: Cladophora socialis is a unique macroalga that is widely grown in the coastal regions of Vietnam. In this work, the pyrolysis characteristics of C. socialis were evaluated using thermogravimetric analysis (TGA) and pyrolysis in a tubing reactor. Macroalgae have a high content of inorganic compounds. These compounds result in high char content during pyrolysis of the macroalgae, which degrades the quality of the product bio-oil. In order to study this effect, C. socialis was demineralized by acid washing to remove the inorganic compounds. The effect of acid washing on the pyrolysis product distribution and the selectivity of composition in pyrolysis oil was carefully investigated. The kinetic parameters and the primary reaction pathways were also determined based on experimental data using nonlinear least-squares regression assuming a first-order kinetics model.

Pyrolysis of softwood carbohydrates in a fluidized bed reactor.

Science.gov (United States)

Aho, Atte; Kumar, Narendra; Eränen, Kari; Holmbom, Bjarne; Hupa, Mikko; Salmi, Tapio; Murzin, Dmitry Yu

2008-09-01

In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood), was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5 degrees C/min) was applied to the heating until a reactor temperature of 460 degrees C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure.

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

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.

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.

Thermal and catalytic pyrolysis of plastic waste

Directory of Open Access Journals (Sweden)

Débora Almeida

2016-02-01

Full Text Available Abstract The amount of plastic waste is growing every year and with that comes an environmental concern regarding this problem. Pyrolysis as a tertiary recycling process is presented as a solution. Pyrolysis can be thermal or catalytical and can be performed under different experimental conditions. These conditions affect the type and amount of product obtained. With the pyrolysis process, products can be obtained with high added value, such as fuel oils and feedstock for new products. Zeolites can be used as catalysts in catalytic pyrolysis and influence the final products obtained.

Yields from pyrolysis of refinery residue using a batch process

Directory of Open Access Journals (Sweden)

S. Prithiraj

2017-12-01

Full Text Available Batch pyrolysis was a valuable process of assessing the potential of recovering and characterising products from hazardous waste materials. This research explored the pyrolysis of hydrocarbon-rich refinery residue, from crude oil processes, in a 1200 L electrically-heated batch retort. Furthermore, the off-gases produced were easily processed in compliance with existing regulatory emission standards. The methodology offers a novel, cost-effective and environmentally compliant method of assessing recovery potential of valuable products. The pyrolysis experiments yielded significant oil (70% with high calorific value (40 MJ/kg, char (14% with carbon content over 80% and non-condensable gas (6% with significant calorific value (240 kJ/mol. The final gas stream was subjected to an oxidative clean-up process with continuous on-line monitoring demonstrating compliance with South African emission standards. The gas treatment was overall economically optimal as only a smaller portion of the original residue was subjected to emission-controlling steps. Keywords: Batch pyrolysis, Volatiles, Oil yields, Char, Emissions, Oil recovery

Co-pyrolysis of waste propylene and gas oil from Campos Basin: a case study; Tecnologia de co-pirolise de polipropileno pos-consumo com gasoleo da Bacia de Campos: um estudo de caso

Energy Technology Data Exchange (ETDEWEB)

Assumpcao, Luiz Carlos F.N. de; Aguiar, Monica Regina M.P. de [Universidade do Estado do Rio de Janeiro (UERJ), RJ (Brazil); Carbonell, Montserrat Motas [PETROBRAS, Rio de Janeiro, RJ (Brazil)

2008-07-01

In this study the process of co-pyrolysis of plastic polypropylene residues with gas-oil was evaluated, varying the temperature and the amount of polypropylene. The co-pyrolysis is a promising route to minimize the environmental impact caused by the inadequate plastic disposal, preventing its accumulation and giving a better use of the not renewable raw material (oil). The polypropylene samples and gas-oil were submitted to the thermal co-pyrolysis in inert atmosphere, varying the temperature from 400 deg C to 500 deg C and the amount of PP from 0,1 to 1,0 g. The influence of gas-oil was evaluated carrying the co-pyrolysis in the absence of PP. The pyrolyzed liquids produced by this thermal treatment had been characterized by modified gaseous chromatography objectifying the evaluation of the diesel fractions generation. As a result, the increase of PP amount lead to a reduction in the income of the pyrolytic liquid and to increase of the amount of solid generated. The effect of the increase of temperature showed an inverse result. The addition of PP in the reactor showed little interference in diesel range of distillation in the co-pyrolysis. On the other hand, an increase in temperature favors the increase of products in this range of distillation. The results show that plastic residue co-pyrolysis is a potential method of chemical recycling. (author)

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)

Desulfurized gas production from vertical kiln pyrolysis

Science.gov (United States)

Harris, Harry A.; Jones, Jr., John B.

1978-05-30

A gas, formed as a product of a pyrolysis of oil shale, is passed through hot, retorted shale (containing at least partially decomposed calcium or magnesium carbonate) to essentially eliminate sulfur contaminants in the gas. Specifically, a single chambered pyrolysis vessel, having a pyrolysis zone and a retorted shale gas into the bottom of the retorted shale zone and cleaned product gas is withdrawn as hot product gas near the top of such zone.

Pyrolysis of Softwood Carbohydrates in a Fluidized Bed Reactor

Directory of Open Access Journals (Sweden)

Dmitry Yu. Murzin

2008-09-01

Full Text Available In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood, was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5°C/min was applied to the heating until a reactor temperature of 460 °C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure.

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.

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.

Co-production of activated carbon, fuel-gas, and oil from the pyrolysis of corncob mixtures with wet and dried sewage sludge.

Science.gov (United States)

Shao, Linlin; Jiang, Wenbo; Feng, Li; Zhang, Liqiu

2014-06-01

This study explored the amount and composition of pyrolysis gas and oil derived from wet material or dried material during the preparation of sludge-corncob activated carbon, and evaluated the physicochemical and surface properties of the obtained two types of sludge-corncob-activated carbons. For wet material, owing to the presence of water, the yields of sludge-corncob activated carbon and the oil fraction slightly decreased while the yield of gases increased. The main pyrolysis gas compounds were H2 and CO2, and more H2 was released from wet material than dried material, whereas the opposite holds for CO2 Heterocyclics, nitriles, organic acids, and steroids were the major components of pyrolysis oil. Furthermore, the presence of water in wet material reduced the yield of polycyclic aromatic hydrocarbons from 6.76% to 5.43%. The yield of furfural, one of heterocyclics, increased sharply from 3.51% to 21.4%, which could be explained by the enhanced hydrolysis of corncob. In addition, the surface or chemical properties of the two sludge-corncob activated carbons were almost not affected by the moisture content of the raw material, although their mesopore volume and diameter were different. In addition, the adsorption capacities of the two sludge-corncob activated carbons towards Pb and nitrobenzene were nearly identical. © The Author(s) 2014.

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.

Comparative study on microwave and conventional hydrothermal pretreatment of bamboo sawdust: Hydrochar properties and its pyrolysis behaviors

International Nuclear Information System (INIS)

Dai, Leilei; He, Chao; Wang, Yunpu; Liu, Yuhuan; Yu, Zhenting; Zhou, Yue; Fan, Liangliang; Duan, Dengle

2017-01-01

Highlights: • Two pretreatments affect differently the hydrochar properties and its pyrolysis behaviors. • Hydrochar by conventional hydrothermal pretreatment shows higher thermal stability. • Microwave hydrothermal pretreatment removes more acetyl. • Hydrochar by microwave hydrothermal pretreatment produces more glucopyranose and less acids. - Abstract: Comparative study on microwave and conventional hydrothermal pretreatment of bamboo sawdust was carried out in this study. Microwave and conventional hydrothermal pretreatment both improved the hydrochar properties and its pyrolysis behaviors. Proximate and elemental analyses show that the properties of hydrochar from microwave hydrothermal pretreatment are better than conventional hydrothermal pretreatment in terms of calorific value and oxygen content except for 150 °C. Microwave hydrothermal pretreatment removes more acetyl groups in hemicellulose compared to conventional hydrothermal pretreatment, which may be attributed to the hot spot effect of microwave irradiation. The peaks of thermogravimetric and derivative thermogravimetric curves of pretreated samples always shifted to higher temperature region. Also, the conventional hydrothermal pretreated samples are more thermally stable than those by microwave heating. In addition, the glucopyranose content in pyrolysis vapors of microwave hydrothermal pretreated bamboo sawdust (190 °C) was 9.82% higher than that from conventional hydrothermal pretreated bamboo sawdust. However, the acids content from microwave hydrothermal pretreated bamboo sawdust (150 °C) was 4.12% lower. In this regard, microwave hydrothermal pretreatment is more suitable for upgrading the pyrolysis oil quality than conventional hydrothermal pretreatment.

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

Directory of Open Access Journals (Sweden)

Qingwen Wang

2013-09-01

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

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).

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.

Promotion of hydrogen-rich gas and phenolic-rich bio-oil production from green macroalgae Cladophora glomerata via pyrolysis over its bio-char.