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

DOEpatents

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

2013-08-27

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

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Wen-liang; Chang, Jian-min, E-mail: cjianmin@bjfu.edu.cn; Cai, Li-ping

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 themore » 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.« less

Experimental study on the heat transfer characteristics of waste printed circuit boards pyrolysis.

PubMed

Ma, Hongting; Du, Na; Lin, Xueyin; Li, Chen; Lai, Junwen; Li, Zihao

2018-08-15

In order to study the appropriate and advanced technology for recycling waste printed circuit boards (PCBs), a fixed bed pyrolysis device with stirring function has been designed and developed. The effect of rotating speed on the temperature distribution and mass change in the pyrolysis process of FR-4 PCB has been analyzed. The heat transfer and pyrolysis characteristics of different granular layers with and without stirring have been investigated. The results indicate that the stirring can change the main way of heat transfer from conduction to convection in the PCB layers. As the increase of rotating speed, the temperature rising rate of material at the bottom of the pyrolysis furnace gradually decreases, while the heating rate is increasing at the upper layer, and the temperature difference between the upper and bottom layers is gradually reduced. When the rotating speed varies from 0r/min to 18r/min, the weight loss of the material increases from 3.97% to 6.76%, and the overall pyrolysis degree is improved. During the pyrolysis process, the material layer can be divided into three zones along the vertical direction, namely complete pyrolysis zone, partial pyrolysis zone and non-pyrolysis zone. As the rotating speed is 0r/min, the thickness of each zones is 6cm, 6cm and 3cm, respectively. However, when the rotating speed is increased to 18r/min, the non-pyrolysis zone disappears, and the thickness of complete pyrolysis zone and partial pyrolysis zone increase to 9cm and 6cm, respectively. Copyright © 2018 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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.

Char yield on pyrolysis of cellulose

Treesearch

A. Broido; Maxine A. Nelson

1975-01-01

Whether the pyrolysis of cellulose is conducted in an inert medium or in air, partial pyrolysis at a lower temperature increases the char yield subsequently obtained after 1 hour at 370°C. The results are consistent with a pyrolysis scheme in which two competing sequences of cellulose pyrolysis reactions are initiated by (1) an intermolecular dehydration leading to...

Effect of Catalytic Pyrolysis Conditions Using Pulse Current Heating Method on Pyrolysis Products of Wood Biomass

PubMed Central

Honma, Sensho; Hata, Toshimitsu; Watanabe, Takashi

2014-01-01

The influence of catalysts on the compositions of char and pyrolysis oil obtained by pyrolysis of wood biomass with pulse current heating was studied. The effects of catalysts on product compositions were analyzed using GC-MS and TEM. The compositions of some aromatic compounds changed noticeably when using a metal oxide species as the catalyst. The coexistence or dissolution of amorphous carbon and iron oxide was observed in char pyrolyzed at 800°C with Fe3O4. Pyrolysis oil compositions changed remarkably when formed in the presence of a catalyst compared to that obtained from the uncatalyzed pyrolysis of wood meal. We observed a tendency toward an increase in the ratio of polyaromatic hydrocarbons in the pyrolysis oil composition after catalytic pyrolysis at 800°C. Pyrolysis of biomass using pulse current heating and an adequate amount of catalyst is expected to yield a higher content of specific polyaromatic compounds. PMID:25614894

A Comparative study of microwave-induced pyrolysis of lignocellulosic and algal biomass.

PubMed

Wang, Nan; Tahmasebi, Arash; Yu, Jianglong; Xu, Jing; Huang, Feng; Mamaeva, Alisa

2015-08-01

Microwave (MW) pyrolysis of algal and lignocellulosic biomass samples were studied using a modified domestic oven. The pyrolysis temperature was recorded continuously by inserting a thermocouple into the samples. Temperatures as high as 1170 and 1015°C were achieved for peanut shell and Chlorella vulgaris. The activation energy for MW pyrolysis was calculated by Coats-Redfern method and the values were 221.96 and 214.27kJ/mol for peanut shell and C. vulgaris, respectively. Bio-oil yields reached to 27.7wt.% and 11.0wt.% during pyrolysis of C. vulgaris and peanut shell, respectively. The bio-oil samples from pyrolysis were analyzed by a gas chromatography-mass spectrometry (GC-MS). Bio-oil from lignocellulosic biomass pyrolysis contained more phenolic compounds while that from microalgae pyrolysis contained more nitrogen-containing species. Fourier transform infrared spectroscopy (FTIR) analysis results showed that concentration of OH, CH, CO, OCH3, and CO functional groups in char samples decreased significantly after pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Co-pyrolysis mechanism of seaweed polysaccharides and cellulose based on macroscopic experiments and molecular simulations.

PubMed

Wang, Shuang; Xia, Zhen; Hu, Yamin; He, Zhixia; Uzoejinwa, Benjamin Bernard; Wang, Qian; Cao, Bin; Xu, Shanna

2017-03-01

Co-pyrolysis conversion of seaweed (Enteromorpha clathrat and Sargassum fusiforme) polysaccharides and cellulose has been investigated. From the Py-GC/MS results, Enteromorpha clathrata (EN) polysaccharides pyrolysis mainly forms furans; while the products of Sargassum fusiforme (SA) polysaccharides pyrolysis are mainly acid esters. The formation mechanisms of H 2 O, CO 2 , and SO 2 during the pyrolysis of seaweed polysaccharides were analyzed using the thermogravimetric-mass spectrometry. Meanwhile the pyrolysis of seaweed polysaccharide based on the Amber and the ReaxFF force fields, has also been proposed and simulated respectively. The simulation results coincided with the experimental results. During the fast pyrolysis, strong synergistic effects among cellulose and seaweed polysaccharide molecules have been simulated. By comparing the experimental and simulation value, it has been found that co-pyrolysis could increase the number of molecular fragments, increase the pyrolysis conversion rate, and increase gas production rate at the middle temperature range. Copyright © 2016 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Catalytic fast pyrolysis is the most promising approach for biofuel production, due to its simple process and versatility to handle lignocellulosic biomass feedstocks with varying and complex compositions. Compared with in situ catalytic fast pyrolysis, ex situ catalytic pyrolysis has the flexibility of optimizing the pyrolysis step and catalytic process individually to improve the quality of pyrolysis oil (stability, oxygen content, acid number, etc.) and to maximize the carbon efficiency in the conversion of biomass to pyrolysis oil. Hydrodeoxygenation is one of the key catalytic functions in ex situ catalytic fast pyrolysis. Recently, Fe-based catalysts have been reported to exhibitmore » superior catalytic properties in hydrodeoxygenation of model compounds in pyrolysis oil, which potentially makes the ex situ pyrolysis of biomass commercially viable due to the abundance and low cost of Fe. Here, we briefly summarize the recent progress on Fe-based catalysts for hydrodeoxygenation of biomass, and provide perspectives on how to further improve Fe-based catalysts (activity and stability) for their potential applications in the emerging area of biomass conversion.« less

Understanding the fast pyrolysis of lignin.

PubMed

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.

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

PubMed

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 whole recycling process. Copyright © 2012 Elsevier Ltd. All rights reserved.

Catalytic co-pyrolysis of cellulose and polypropylene over all-silica mesoporous catalyst MCM-41 and Al-MCM-41.

PubMed

Chi, Yongchao; Xue, Junjie; Zhuo, Jiankun; Zhang, Dahu; Liu, Mi; Yao, Qiang

2018-08-15

Fast pyrolysis is one of the most economical and efficient technologies to convert biomass to bio-oil and valuable chemical products. Co-pyrolysis with hydrogen rich materials such as plastics over zeolite catalysts is one of the significant solutions to various problems of bio-oil such as high oxygen content, low heat value and high acid content. This paper studied pyrolysis of cellulose and polypropylene (PP) separately and co-pyrolysis of cellulose and PP over MCM-41 and Al-MCM-41. The pyrolysis over different heating rates (10K/min, 20K/min, 30K/min) was studied by Thermogravimetry Analysis (TGA) and kinetic parameters were obtained by Coats-Redfern method and isoconversion method. TG and DTG data shows that the two catalysts advance the pyrolysis reaction of PP significantly and reduce its peak temperature of DTG curve from 458°C to 341°C. The activation energy of pyrolysis of PP also has a remarkable reduction over the two catalysts. Py-GC/MS method was used to obtain the product distribution of pyrolysis of cellulose and PP separately and co-pyrolysis of cellulose and PP over MCM-41 and Al-MCM-41 at constant temperature of 650°C. Experiment results proved that co-pyrolysis with PP bring significant changes to the product distribution of cellulose. Oxygenated compounds such as furans are decreased, while yields of olefins and aromatics increase greatly. The yield of furans increases with the catalysis of MCM-41 as for the pyrolysis of cellulose and co-pyrolysis, while the yield of olefins and aromatics both experience significant growth over Al-MCM-41, which can be explained by the abundant acid centers in Al-MCM-41. Copyright © 2018 Elsevier B.V. All rights reserved.

Artificial maturation of oil shale: The Irati Formation from the Parana Basin, Brazil

NASA Astrophysics Data System (ADS)

Gayer, James L.

Oil shale samples from the Irati Formation in Brazil were evaluated from an outcrop block, denoted Block 003. The goals of this thesis include: 1) Characterizing the Irati Formation, 2) Comparing the effects of two different types of pyrolysis, anhydrous and hydrous, and 3) Utilizing a variety of geophysical experiments to determine the changes associated with each type of pyrolysis. Primary work included determining total organic carbon, source rock analysis, mineralogy, computer tomography x-ray scans, and scanning electron microscope images before and after pyrolysis, as well as acoustic properties of the samples during pyrolysis. Two types of pyrolysis (hydrous and anhydrous) were performed on samples cored at three different orientations (0°, 45°, and 90°) with respect to the axis of symmetry, requiring six total experiments. During pyrolysis, the overall effective pressure was maintained at 800 psi, and the holding temperature was 365°C. The changes and deformation in the hydrous pyrolysis samples were greater compared to the anhydrous pyrolysis. The velocities gave the best indication of changes occurring during pyrolysis, but it was difficult to maintain the same amplitude and quality of waveforms at higher temperatures. The velocity changes were due to a combination of factors, including thermal deformation of the samples, fracture porosity development, and the release of adsorbed water and bitumen from the sample. Anhydrous pyrolysis in this study did not reduce TOC, while TOC was reduced due to hydrous pyrolysis by 5%, and velocities in the hydrous pyrolysis decreased by up to 30% at 365°C compared to room temperature. Data from this study and future data that can be acquired with the improved high-temperature, high-pressure experiment will assist in future economic production from oil shale at lower temperatures under hydrous pyrolysis conditions.

Processes for converting lignocellulosics to reduced acid pyrolysis oil

DOEpatents

Kocal, Joseph Anthony; Brandvold, Timothy A

2015-01-06

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

Adding nickel formate in alkali lignin to increase contents of alkylphenols and aromatics during fast pyrolysis.

PubMed

Geng, Jing; Wang, Wen-Liang; Yu, Yu-Xiang; Chang, Jian-Min; Cai, Li-Ping; Shi, Sheldon Q

2017-03-01

The composition of pyrolysis vapors obtained from alkali lignin pyrolysis with the additive of nickel formate was examined using the pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). Characterization of bio-chars was performed using X-ray diffraction (XRD). Results showed that the nickel formate significantly increased liquid yield, simplified the types of alkali lignin pyrolysis products and increased individual component contents. The additive of nickel formate increased contents of alkylphenols and aromatics from alkali lignin pyrolysis. With an increase in temperature, a greater amount of the relative contents can be achieved. The nickel formate was thermally decomposed to form hydrogen, resulting in hydrodeoxygenation of alkali lignin during pyrolysis. It was also found that Ni is in favor of producing alkylphenols. The analysis based on the experimental result provided evidences used to propose reaction mechanism for pyrolysis of nickel formate-assisted alkali lignin. Copyright © 2016. Published by Elsevier Ltd.

The slow and fast pyrolysis of cherry seed.

PubMed

Duman, Gozde; Okutucu, Cagdas; Ucar, Suat; Stahl, Ralph; Yanik, Jale

2011-01-01

The slow and fast pyrolysis of cherry seeds (CWS) and cherry seeds shells (CSS) was studied in fixed-bed and fluidized bed reactors at different pyrolysis temperatures. The effects of reactor type and temperature on the yields and composition of products were investigated. In the case of fast pyrolysis, the maximum bio-oil yield was found to be about 44 wt% at pyrolysis temperature of 500 °C for both CWS and CSS, whereas the bio yields were of 21 and 15 wt% obtained at 500 °C from slow pyrolysis of CWS and CSS, respectively. Both temperature and reactor type affected the composition of bio-oils. The results showed that bio-oils obtained from slow pyrolysis of CWS and CSS can be used as a fuel for combustion systems in industry and the bio-oil produced from fast pyrolysis can be evaluated as a chemical feedstock. Copyright © 2010 Elsevier Ltd. All rights reserved.

Effects of feedstock characteristics on microwave-assisted pyrolysis - A review.

PubMed

Zhang, Yaning; Chen, Paul; Liu, Shiyu; Peng, Peng; Min, Min; Cheng, Yanling; Anderson, Erik; Zhou, Nan; Fan, Liangliang; Liu, Chenghui; Chen, Guo; Liu, Yuhuan; Lei, Hanwu; Li, Bingxi; Ruan, Roger

2017-04-01

Microwave-assisted pyrolysis is an important approach to obtain bio-oil from biomass. Similar to conventional electrical heating pyrolysis, microwave-assisted pyrolysis is significantly affected by feedstock characteristics. However, microwave heating has its unique features which strongly depend on the physical and chemical properties of biomass feedstock. In this review, the relationships among heating, bio-oil yield, and feedstock particle size, moisture content, inorganics, and organics in microwave-assisted pyrolysis are discussed and compared with those in conventional electrical heating pyrolysis. The quantitative analysis of data reported in the literature showed a strong contrast between the conventional processes and microwave based processes. Microwave-assisted pyrolysis is a relatively new process with limited research compared with conventional electrical heating pyrolysis. The lack of understanding of some observed results warrant more and in-depth fundamental research. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2016-12-01

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

Rapid co-pyrolysis of rice straw and a bituminous coal in a high-frequency furnace and gasification of the residual char.

PubMed

Yuan, Shuai; Dai, Zheng-hua; Zhou, Zhi-jie; Chen, Xue-li; Yu, Guang-suo; Wang, Fu-chen

2012-04-01

Rapid pyrolysis of rice straw (RS) and Shenfu bituminous coal (SB) separately, and rapid co-pyrolysis of RS/SB blends (mass ratio 1:4, 1:4, and 4:1), were carried out in a high-frequency furnace which can ensure both high heating rate and satisfying contact of fuel particles. Synergies between RS and SB during rapid co-pyrolysis were investigated. Intrinsic and morphological structures of residual char from co-pyrolysis, and their effects on gasification characteristics were also studied. Synergies occurred during rapid co-pyrolysis of RS and SB (RS/SB=1:4) resulting in decreasing char yields and increasing volatile yields. Synergies also happened during gasification of the char derived from co-pyrolysis of RS and SB with mass ratio of 1:4. The increased mass ratio of RS to SB did not only weaken synergies during co-pyrolysis, but significantly reduced the gasification rates of the co-pyrolysis char compared to the calculated values. Results can help to optimize co-conversion process of biomass/coal. Copyright © 2012 Elsevier Ltd. All rights reserved.

Studies on thermal decomposition behaviors of polypropylene using molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Huang, Jinbao; He, Chao; Tong, Hong; Pan, Guiying

2017-11-01

Polypropylene (PP) is one of the main components of waste plastics. In order to understand the mechanism of PP thermal decomposition, the pyrolysis behaviour of PP has been simulated from 300 to 1000 K in periodic boundary conditions by molecular dynamic method, based on AMBER force field. The simulation results show that the pyrolysis process of PP can mostly be divided into three stages: low temperature pyrolysis stage, intermediate temperature stage and high temperature pyrolysis stage. PP pyrolysis is typical of random main-chain scission, and the possible formation mechanism of major pyrolysis products was analyzed.

Pyrolysis and hydrolysis of mixed polymer waste comprising polyethylene-terephthalate and polyethylene to sequentially recover [monomers

DOEpatents

Evans, R.J.; Chum, H.L.

1998-10-13

A process is described for using fast pyrolysis in a carrier gas to convert a plastic waste feed stream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feed stream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent. 83 figs.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of mixed polymer waste streams to sequentially recover monomers or other high value products

DOEpatents

Evans, Robert J.; Chum, Helena L.

1994-01-01

A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents, selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of mixed polymer waste streams to sequentially recover monomers or other high value products

DOEpatents

Evans, Robert J.; Chum, Helena L.

1994-01-01

A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of mixed polymer waste streams to sequentially recover monomers or other high value products

DOEpatents

Evans, Robert J.; Chum, Helena L.

1993-01-01

A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.

Pyrolysis and hydrolysis of mixed polymer waste comprising polyethyleneterephthalate and polyethylene to sequentially recover

DOEpatents

Evans, Robert J.; Chum, Helena L.

1998-01-01

A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.

Waste-to-Energy Plant Environmental Assessment, Dyess Air Force Base, Texas

DTIC Science & Technology

2011-09-01

pyrolysis can be defined as “ gasification minus oxygen.” Pyrolysis is the technique of heating organic matter ( biomass ) between 480 and 1,470 °F in the...provider using one of four alternative technologies: 1) gasification ; 2) pyrolysis; 3) plasma gasification /pyrolysis and 4) incineration. Under this...the solicitation to build a WTE plant based on one of the following alternative technologies: I) gasification ; 2) pyrolysis; 3) plasma gasification

Reducing the bioavailability and leaching potential of lead in contaminated water hyacinth biomass by phosphate-assisted pyrolysis.

PubMed

Shi, Lingna; Wang, Lijun; Zhang, Tao; Li, Jianfa; Huang, Xiaoyi; Cai, Jing; Lü, Jinhong; Wang, Yue

2017-10-01

For the purpose of safe disposal of biomass contaminated by biosorption of heavy metals, phosphate-assisted pyrolysis of water hyacinth biomass contaminated by lead (Pb) was tried to reduce the bioavailability and leaching potential of Pb, using direct pyrolysis without additive as a control method. Direct pyrolysis of the contaminated biomass at low temperatures (300 and 400°C) could reduce the bioavailability of Pb, but the leaching potential of Pb was increased with the rising pyrolysis temperature. While phosphate-assisted pyrolysis significantly enhanced the recovery and stability of Pb in the char. Specifically, the percentages of bioavailable Pb and leachable Pb in the chars obtained by phosphate-assisted pyrolysis at low temperatures were reduced to less than 5% and 7%, respectively. The sequential extraction test indicated the transformation of Pb into more stable fractions after phosphate-assisted pyrolysis, which was related to the formation of Pb phosphate minerals including pyromorphite and lead-substituted hydroxyapatite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mass spectrometric studies of fast pyrolysis of cellulose

DOE Office of Scientific and Technical Information (OSTI.GOV)

Degenstein, John; Hurt, Matt; Murria, Priya

2015-01-01

A fast pyrolysis probe/linear quadrupole ion trap mass spectrometer combination was used to study the primary fast pyrolysis products (those that first leave the hot pyrolysis surface) of cellulose, cellobiose, cellotriose, cellotetraose, cellopentaose, and cellohexaose, as well as of cellobiosan, cellotriosan, and cellopentosan, at 600°C. Similar products with different branching ratios were found for the oligosaccharides and cellulose, as reported previously. However, identical products (with the exception of two) with similar branching ratios were measured for cellotriosan (and cellopentosan) and cellulose. This result demonstrates that cellotriosan is an excellent small-molecule surrogate for studies of the fast pyrolysis of cellulose andmore » also that most fast pyrolysis products of cellulose do not originate from the reducing end. Based on several observations, the fast pyrolysis of cellulose is suggested to initiate predominantly via two competing processes: the formation of anhydro-oligosaccharides, such as cellobiosan, cellotriosan, and cellopentosan (major route), and the elimination of glycolaldehyde (or isomeric) units from the reducing end of oligosaccharides formed from cellulose during fast pyrolysis.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mukarakate, C.; Robichaud, D.; Donohoe, B.

2012-01-01

We have constructed a captive sample reactor (CSR) to study fast pyrolysis of biomass. The reactor uses a stainless steel wire mesh to surround biomass materials with an isothermal environment by independent controlling of heating rates and pyrolysis temperatures. The vapors produced during pyrolysis are immediately entrained and transported in He carrier gas to a molecular beam mass spectrometer (MBMS). Formation of secondary products is minimized by rapidly quenching the sample support with liquid nitrogen. A range of alkali and alkaline earth metal (AAEM) and transition metal salts were tested to study their effect on composition of primary pyrolysis products.more » Multivariate curve resolution (MCR) analysis of the MBMS data shows that transition metal salts enhance pyrolysis of carbohydrates and AAEM salts enhances pyrolysis of lignin. This was supported by performing similar separate studies on cellulose, hemicellulose and extracted lignin. The effect of salts on char formation is also discussed.« less

Thermal and catalytic slow pyrolysis of Calophyllum inophyllum fruit shell.

PubMed

Alagu, R M; Sundaram, E Ganapathy; Natarajan, E

2015-10-01

Pyrolysis of Calophyllum inophyllum shell was performed in a fixed bed pyrolyser to produce pyrolytic oil. Both thermal (without catalysts) and catalytic pyrolysis process were conducted to investigate the effect of catalysts on pyrolysis yield and pyrolysis oil characteristics. The yield of pyrolytic oil through thermal pyrolysis was maximum (41% wt) at 425 °C for particle size of 1.18 mm and heating rate of 40 °C/min. In catalytic pyrolysis the pyrolytic oil yield was maximum (45% wt) with both zeolite and kaolin catalysts followed by Al2O3 catalyst (44% wt). The functional groups and chemical components present in the pyrolytic oil are identified by Fourier Transform Infrared Spectroscopy (FT-IR) and Gas Chromatography-Mass Spectrometry (GC-MS) techniques. This study found that C. inophyllum shell is a potential new green energy source and that the catalytic pyrolysis process using zeolite catalyst improves the calorific value and acidity of the pyrolytic oil. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of hydrothermal carbonization on migration and environmental risk of heavy metals in sewage sludge during pyrolysis.

PubMed

Liu, Tingting; Liu, Zhengang; Zheng, Qingfu; Lang, Qianqian; Xia, Yu; Peng, Nana; Gai, Chao

2018-01-01

The heavy metals distribution during hydrothermal carbonization (HTC) of sewage sludge, and pyrolysis of the resultant hydrochar was investigated and compared with raw sludge pyrolysis. The results showed that HTC reduced exchangeable/acid-soluble and reducible fraction of heavy metals and lowered the potential risk of heavy metals in sewage sludge. The pyrolysis favored the transformation of extracted/mobile fraction of heavy metals to residual form especially at high temperature, immobilizing heavy metals in the chars. Compared to the chars from raw sludge pyrolysis, the chars derived from hydrochar pyrolysis was more alkaline and had lower risk and less leachable heavy metals, indicating that pyrolysis imposed more positive effect on immobilization of heavy metals for the hydrochar than for sewage sludge. The present study demonstrated that HTC is a promising pretreatment prior to pyrolysis from the perspective of immobilization of heavy metals in sewage sludge. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pyrolysis characteristics and kinetics of microalgae via thermogravimetric analysis (TGA): A state-of-the-art review.

PubMed

Bach, Quang-Vu; Chen, Wei-Hsin

2017-12-01

Pyrolysis is a promising route for biofuels production from microalgae at moderate temperatures (400-600°C) in an inert atmosphere. Depending on the operating conditions, pyrolysis can produce biochar and/or bio-oil. In practice, knowledge for thermal decomposition characteristics and kinetics of microalgae during pyrolysis is essential for pyrolyzer design and pyrolysis optimization. Recently, the pyrolysis kinetics of microalgae has become a crucial topic and received increasing interest from researchers. Thermogravimetric analysis (TGA) has been employed as a proven technique for studying microalgae pyrolysis in a kinetic control regime. In addition, a number of kinetic models have been applied to process the TGA data for kinetic evaluation and parameters estimation. This paper aims to provide a state-of-the art review on recent research activities in pyrolysis characteristics and kinetics of various microalgae. Common kinetic models predicting the thermal degradation of microalgae are examined and their pros and cons are illustrated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of torrefaction on the properties of rice straw high temperature pyrolysis char: Pore structure, aromaticity and gasification activity.

PubMed

Chen, Handing; Chen, Xueli; Qin, Yueqiang; Wei, Juntao; Liu, Haifeng

2017-03-01

The influence of torrefaction on the physicochemical characteristics of char during raw and water washed rice straw pyrolysis at 800-1200°C is investigated. Pore structure, aromaticity and gasification activity of pyrolysis chars are compared between raw and torrefied samples. For raw straw, BET specific surface area decreases with the increased torrefaction temperature at the same pyrolysis temperature and it approximately increases linearly with weight loss during pyrolysis. The different pore structure evolutions relate to the different volatile matters and pore structures between raw and torrefied straw. Torrefaction at higher temperature would bring about a lower graphitization degree of char during pyrolysis of raw straw. Pore structure and carbon crystalline structure evolutions of raw and torrefied water washed straw are different from these of raw straw during pyrolysis. For both raw and water washed straw, CO 2 gasification activities of pyrolysis chars are different between raw and torrefied samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pyrolysis of tyre powder using microwave thermogravimetric analysis: Effect of microwave power.

PubMed

Song, Zhanlong; Yang, Yaqing; Zhou, Long; Zhao, Xiqiang; Wang, Wenlong; Mao, Yanpeng; Ma, Chunyuan

2017-02-01

The pyrolytic characteristics of tyre powder treated under different microwave powers (300, 500, and 700 W) were studied via microwave thermogravimetric analysis. The product yields at different power levels were studied, along with comparative analysis of microwave pyrolysis and conventional pyrolysis. The feedstock underwent preheating, intense pyrolysis, and final pyrolysis in sequence. The main and secondary weight loss peaks observed during the intense pyrolysis stage were attributed to the decomposition of natural rubbers and synthetic rubbers, respectively. The total mass loss rates, bulk temperatures, and maximum temperatures were distinctively higher at higher powers. However, the maximum mass loss rate (0.005 s -1 ), the highest yields of liquid product (53%), and the minimum yields of residual solid samples (43.83%) were obtained at 500 W. Compared with conventional pyrolysis, microwave pyrolysis exhibited significantly different behaviour with faster reaction rates, which can decrease the decomposition temperatures of both natural and synthetic rubber by approximately 110 °C-140 °C.

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

PubMed

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

2017-05-01

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

Integration of pyrolysis and anaerobic digestion--use of aqueous liquor from digestate pyrolysis for biogas production.

PubMed

Hübner, Tobias; Mumme, Jan

2015-05-01

Anaerobic digestion of aqueous pyrolysis liquor derived from pyrolysis of solid digestate was tested in batch mode using an un-adapted inoculum. Three pyrolysis liquors produced at 330°C, 430°C and 530°C in four COD-based concentrations of 3, 6, 12 and 30 g L(-1) were investigated. The three lower concentrations showed considerable biogas production, whereas the 30 g L(-1) dosage caused process inhibition. The highest methane yield of 199.1±18.5 mL g(COD)(-1) (COD removal: 56.9±5.3%) was observed for the 330°C pyrolysis liquor, followed by the 430°C sample with only slightly lower values. The 530°C sample dropped to a yield of 129.3±19.7 mL g(COD)(-1) (COD removal: 36.9±5.6%). Most VOCs contained in the pyrolysis liquor (i.e. furfural, phenol, catechol, guaiacol, and levoglucosan) were reduced below detection limit (cresol by 10-60%). Consequently, integrated pyrolysis and anaerobic digestion in addition to thermochemical conversion of digestate also promises bioconversion of pyrolysis liquors. Copyright © 2015 Elsevier Ltd. All rights reserved.

Publications - GMC 127 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 127 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite information. Bibliographic Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and vitrinite ) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of Page Department

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

USDA-ARS?s Scientific Manuscript database

Zeolites have been shown to effectively promote cracking reactions during pyrolysis resulting in highly deoxygenated and hydrocarbon-rich compounds and stable pyrolysis oil product. Py/GC-MS was employed to study the catalytic fast pyrolysis of lignocellulosic biomass samples comprising oak, corn...

Structural analysis of pyrolytic lignins isolated from switchgrass fast pyrolysis oil

USDA-ARS?s Scientific Manuscript database

Structural characterization of lignin extracted from the bio-oil produced by fast pyrolysis of switchgrass (Panicum virgatum) is reported. This new information is important to understanding the utility of lignin as a chemical feedstock in a pyrolysis based biorefinery. Pyrolysis induces a variety of...

Microwave-assisted pyrolysis of Mississippi coal: A comparative study with conventional pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abdelsayed, Victor; Shekhawat, Dushyant; Smith, Mark W.

Pyrolysis conditions greatly affect the structure-reactivity relationship of char during coal gasification. Here, this work investigated the effect of temperature and microwave heating on the structural properties of the chars generated during pyrolysis, as well as gaseous and tar products. Results showed that microwave pyrolysis of Mississippi coal produced more gaseous products and less tars compared to conventional pyrolysis. Higher CO/CO 2 ratio (>1) was observed under microwave pyrolysis compared to conventional pyrolysis (CO/CO2 < 1), which may be explained by a greater extent of gasification between solid carbon and the CO 2 formed during microwave pyrolysis. Additionally, in microwavemore » pyrolysis, the oil tars generated exhibited lower concentrations of polar oxygenates, while the wax tars showed higher concentrations of non-polar alkanes, as observed from the intensity of CH vibrations in FTIR. The product compositions and FTIR analysis of the tars (oils and waxes) suggest that the microwave interacted preferentially with these polar species, which have relatively higher dielectric properties compared to alkanes. The structure–reactivity relationship of the chars produced was also investigated using a variety of characterization tools such as XRD, BET, SEM, EDS, and FTIR. Finally, the char reactivity towards combustion suggested that microwave-produced chars have a higher thermal stability, likely due to lower O/C ratios, and could be utilized in the metallurgical industry.« less

Microwave-assisted pyrolysis of Mississippi coal: A comparative study with conventional pyrolysis

DOE PAGES

Abdelsayed, Victor; Shekhawat, Dushyant; Smith, Mark W.; ...

2018-01-13

Pyrolysis conditions greatly affect the structure-reactivity relationship of char during coal gasification. Here, this work investigated the effect of temperature and microwave heating on the structural properties of the chars generated during pyrolysis, as well as gaseous and tar products. Results showed that microwave pyrolysis of Mississippi coal produced more gaseous products and less tars compared to conventional pyrolysis. Higher CO/CO 2 ratio (>1) was observed under microwave pyrolysis compared to conventional pyrolysis (CO/CO2 < 1), which may be explained by a greater extent of gasification between solid carbon and the CO 2 formed during microwave pyrolysis. Additionally, in microwavemore » pyrolysis, the oil tars generated exhibited lower concentrations of polar oxygenates, while the wax tars showed higher concentrations of non-polar alkanes, as observed from the intensity of CH vibrations in FTIR. The product compositions and FTIR analysis of the tars (oils and waxes) suggest that the microwave interacted preferentially with these polar species, which have relatively higher dielectric properties compared to alkanes. The structure–reactivity relationship of the chars produced was also investigated using a variety of characterization tools such as XRD, BET, SEM, EDS, and FTIR. Finally, the char reactivity towards combustion suggested that microwave-produced chars have a higher thermal stability, likely due to lower O/C ratios, and could be utilized in the metallurgical industry.« less

Reprint of: Pyrolysis technologies for municipal solid waste: a review.

PubMed

Chen, Dezhen; Yin, Lijie; Wang, Huan; He, Pinjing

2015-03-01

Pyrolysis has been examined as an attractive alternative to incineration for municipal solid waste (MSW) disposal that allows energy and resource recovery; however, it has seldom been applied independently with the output of pyrolysis products as end products. This review addresses the state-of-the-art of MSW pyrolysis in regards to its technologies and reactors, products and environmental impacts. In this review, first, the influence of important operating parameters such as final temperature, heating rate (HR) and residence time in the reaction zone on the pyrolysis behaviours and products is reviewed; then the pyrolysis technologies and reactors adopted in literatures and scale-up plants are evaluated. Third, the yields and main properties of the pyrolytic products from individual MSW components, refuse-derived fuel (RDF) made from MSW, and MSW are summarised. In the fourth section, in addition to emissions from pyrolysis processes, such as HCl, SO2 and NH3, contaminants in the products, including PCDD/F and heavy metals, are also reviewed, and available measures for improving the environmental impacts of pyrolysis are surveyed. It can be concluded that the single pyrolysis process is an effective waste-to-energy convertor but is not a guaranteed clean solution for MSW disposal. Based on this information, the prospects of applying pyrolysis technologies to dealing with MSW are evaluated and suggested. Copyright © 2015 Elsevier Ltd. All rights reserved.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of mixed polymer waste streams to sequentially recover monomers or other high value products

DOEpatents

Evans, R.J.; Chum, H.L.

1994-10-25

A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent. 83 figs.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of polymer waste comprising nylon 6 and a polyolefin or mixtures of polyolefins to sequentially recover monomers or other high value products

DOEpatents

Evans, Robert J.; Chum, Helena L.

1994-01-01

A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of mixed polymer waste streams to sequentially recover monomers or other high value products

DOEpatents

Evans, R.J.; Chum, H.L.

1994-04-05

A process is described for using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents, selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent. 87 figures.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of polymer waste comprising nylon 6 and a polyolefin or mixtures of polyolefins to sequentially recover monomers or other high value products

DOEpatents

Evans, R.J.; Chum, H.L.

1994-10-25

A process of using fast pyrolysis in a carrier gas to convert a plastic waste feedstream having a mixed polymeric composition in a manner such that pyrolysis of a given polymer to its high value monomeric constituent occurs prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of said given polymer to its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and support for treating said feed streams with said catalyst to effect acid or base catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said temperature program range; differentially heating said feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituent prior to pyrolysis of other plastic components; separating the high value monomeric constituents; selecting a second higher temperature range to cause pyrolysis of a different high value monomeric constituent of said plastic waste and differentially heating the feedstream at the higher temperature program range to cause pyrolysis of the different high value monomeric constituent; and separating the different high value monomeric constituent. 83 figs.

Rapid habitability assessment of Mars samples by pyrolysis-FTIR

NASA Astrophysics Data System (ADS)

Gordon, Peter R.; Sephton, Mark A.

2016-02-01

Pyrolysis Fourier transform infrared spectroscopy (pyrolysis FTIR) is a potential sample selection method for Mars Sample Return missions. FTIR spectroscopy can be performed on solid and liquid samples but also on gases following preliminary thermal extraction, pyrolysis or gasification steps. The detection of hydrocarbon and non-hydrocarbon gases can reveal information on sample mineralogy and past habitability of the environment in which the sample was created. The absorption of IR radiation at specific wavenumbers by organic functional groups can indicate the presence and type of any organic matter present. Here we assess the utility of pyrolysis-FTIR to release water, carbon dioxide, sulfur dioxide and organic matter from Mars relevant materials to enable a rapid habitability assessment of target rocks for sample return. For our assessment a range of minerals were analyzed by attenuated total reflectance FTIR. Subsequently, the mineral samples were subjected to single step pyrolysis and multi step pyrolysis and the products characterised by gas phase FTIR. Data from both single step and multi step pyrolysis-FTIR provide the ability to identify minerals that reflect habitable environments through their water and carbon dioxide responses. Multi step pyrolysis-FTIR can be used to gain more detailed information on the sources of the liberated water and carbon dioxide owing to the characteristic decomposition temperatures of different mineral phases. Habitation can be suggested when pyrolysis-FTIR indicates the presence of organic matter within the sample. Pyrolysis-FTIR, therefore, represents an effective method to assess whether Mars Sample Return target rocks represent habitable conditions and potential records of habitation and can play an important role in sample triage operations.

Publications - GMC 137 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 137 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of Report Report Information gmc137.pdf (47.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic

Publications - GMC 100 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 100 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch cuttings Information gmc100.pdf (317.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

Publications - GMC 144 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 144 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite for more information. Bibliographic Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis gmc144.pdf (104.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance

Publications - GMC 30 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 30 Publication Details Title: Geochemical analysis (total organic carbon, rock-eval pyrolysis , Geochemical analysis (total organic carbon, rock-eval pyrolysis, vitrinite reflectance and gc/ms chromato (1.3 M) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of

Publications - GMC 141 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 141 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of Report Report Information gmc141.pdf (70.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic

Publications - GMC 101 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 101 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch cuttings Information gmc101.pdf (201.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

Publications - GMC 60 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 60 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite , Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance geochemical data for the Nechelik (125.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of

Publications - GMC 27 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 27 Publication Details Title: Geochemical analysis (total organic carbon, rock-eval pyrolysis . Bibliographic Reference Unknown, 1995, Geochemical analysis (total organic carbon, rock-eval pyrolysis, and ; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of Page Department of

Publications - GMC 103 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 103 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch cuttings Information gmc103.pdf (57.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

Publications - GMC 23 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 23 Publication Details Title: Total organic carbon, rock-eval pyrolysis, visual kerogen Unknown, [n.d.], Total organic carbon, rock-eval pyrolysis, visual kerogen/vitrinite reflectance for Information gmc023.pdf (199.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon

Publications - GMC 22 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 22 Publication Details Title: Total organic carbon, rock-eval pyrolysis, visual kerogen Unknown, 1984, Total organic carbon, rock-eval pyrolysis, visual kerogen/vitrinite reflectance for the gmc022.pdf (247.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

Publications - GMC 102 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 102 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch cuttings Information gmc102.pdf (81.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

Publications - GMC 124 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 124 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data from the Report Information gmc124.pdf (278.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon

Publications - GMC 68 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 68 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1987, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance geochemical Report Report Information gmc068.pdf (48.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic

40 CFR 721.10579 - Carbon black derived from the pyrolysis of rubber tire shreds (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... pyrolysis of rubber tire shreds (generic). 721.10579 Section 721.10579 Protection of Environment... pyrolysis of rubber tire shreds (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as carbon black derived from the pyrolysis of...

Analysis of Low-Pressure Gas-Phase Pyrolytic Reactions by Mass Spectrometric Techniques,

DTIC Science & Technology

1989-01-01

temperatures and pressures known only as a polymeric substance, is similarly obtained in high purity by heating the polymer to its melting point (105-110’ C...filaments for Curie- point pyrolysis’ J.Anal.Appl.Pyrolysis. 5 (1983) 1-7 (with Helge Egsgaard) 4) ’Heterogeneous catalysis in gas phase reactions studied...by Curie- point pyrolysis. Gas phase pyrolysis of methyl dithio- acetat’ J.Anal.Appl.Pyrolysis. 5 (1983) 257-259 (with Helge Egsgaard) 5) ’Continuous

Small-scale hydrous pyrolysis of macromolecular material in meteorites

NASA Astrophysics Data System (ADS)

Sephton, M. A.; Pillinger, C. T.; Gilmour, I.

1998-12-01

The hydrous pyrolysis method, usually performed on several hundred grams of terrestrial rock sample, has been scaled down to accommodate less than two grams of meteorite sample. This technique makes full use of the high yields associated with hydrous pyrolysis experiments and permits the investigation of the meteorite macromolecular material, the major organic component in carbonaceous meteorites. The hydrous pyrolysis procedure transforms the high molecular weight macromolecular material into low molecular weight fragments. The released entities can then be extracted with supercritical fluid extraction. In contrast to the parent structure, the pyrolysis products are amenable for analysis by gas chromatography-based techniques. When subjected to hydrous pyrolysis, two carbonaceous chondrites (Orgueil and Cold Bokkeveld) released generally similar products, which consisted of abundant volatile aromatic and alkyl-substituted aromatic compounds. These results revealed the ability of small-scale hydrous pyrolysis to dissect extraterrestrial macromolecular material and thereby reveal its organic constitution.

Effects of torrefaction and densification on switchgrass pyrolysis products

DOE PAGES

Yang, Zixu; Sarkar, Madhura; Kumar, Ajay; ...

2014-12-01

Abstract The pyrolysis behaviors of four types of pretreated switchgrass (torrefied at 230 and 270 °C, densification, and torrefaction at 270 ºC followed by densification) were studied at three temperatures (500, 600, 700 ºC) using a pyroprobe attached to a gas chromatogram mass spectroscopy (Py-GC/MS). The torrefaction of switchgrass improved its oxygen to carbon ratio and energy content. Contents of anhydrous sugars and phenols in pyrolysis products of torrefied switchgrass were higher than those in pyrolysis products of raw switchgrass. As the torrefaction temperature increased from 230 to 270 °C, the contents of anhydrous sugars and phenols in pyrolysis productsmore » increased whereas content of guaiacols decreased. High pyrolysis temperature (600 and 700 °C as compared to 500 °C) enhanced decomposition of lignin and anhydrous sugars, leading to increase in phenols, aromatics and furans. Densification enhanced depolymerization of cellulose and hemicellulose during pyrolysis.« less

Publications - GMC 242 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 242 Publication Details Title: Total organic carbon and rock-eval pyrolysis evaluation of 21 Core Laboratories, 1995, Total organic carbon and rock-eval pyrolysis evaluation of 21 hand-picked coal Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon Top of Page Department of Natural Resources, Division

Publications - GMC 136 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 136 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and some vitrinite Unknown, 1989, Total organic carbon, rock-eval pyrolysis, and some vitrinite reflectance data of cuttings Report Information gmc136.pdf (39.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon

Publications - GMC 99 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 99 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Unknown, 1988, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance data of ditch Report Report Information gmc099.pdf (383.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic

Publications - GMC 12 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

- 11,850 feet; total organic carbon, rock-eval pyrolysis and visual kerogen/vitrinite reflectance Authors River #1 well 10,255 - 11,850 feet; total organic carbon, rock-eval pyrolysis and visual kerogen gmc012.pdf (384.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

Publications - GMC 20 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

, rock-eval/pyrolysis, total organic carbon) and core logs for the David River USA #1-A, Hoodoo Lake Unit , 1969, Geochemical analysis (vitrinite reflectance, visual kerogen, rock-eval/pyrolysis, total organic gmc020.pdf (3.2 M) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite

Publications - GMC 24 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 24 Publication Details Title: Total organic carbon, rock-eval pyrolysis, visual kerogen Unknown, [n.d.], Total organic carbon, rock-eval pyrolysis, visual kerogen/vitrinite reflectance of the Information gmc024.pdf (79.0 K) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon

Publications - GMC 123 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 123 Publication Details Title: Total organic carbon and rock-eval pyrolysis data of select organic carbon and rock-eval pyrolysis data of select cuttings from the Chevron USA Akulik #1 well: Alaska Pyrolysis; Rock-Eval Pyrolysis Top of Page Department of Natural Resources, Division of Geological &

Publications - GMC 83 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 83 Publication Details Title: Rock-eval pyrolysis data and interpretation for the Alaska and Ruth Laboratories, Inc., 1988, Rock-eval pyrolysis data and interpretation for the Alaska Information gmc083.pdf (274.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis Top of Page Department of Natural

Publications - GMC 284 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 284 Publication Details Title: TOC/rock-eval pyrolysis geochemical data for 26 Alaska North for more information. Bibliographic Reference Unknown, 1999, TOC/rock-eval pyrolysis geochemical data Information gmc284.pdf (1.8 M) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon Top of Page

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

PubMed

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

2017-01-01

The magnetic biochars were easily fabricated by thermal pyrolysis of Fe(NO 3 ) 3 and distillation residue derived from rice straw pyrolysis oil at 400, 600 and 800°C. The effects of pyrolysis temperature on characteristics of magnetic biochars as well as adsorption capacity for aromatic contaminants (i.e., anisole, phenol and guaiacol) were investigated carefully. The degree of carbonization of magnetic biochars become higher as pyrolysis temperature increasing. The magnetic biochar reached the largest surface area and pore volume at the pyrolysis temperature of 600°C due to pores blocking in biochar during pyrolysis at 800°C. Based on batch adsorption experiments, the used adsorbent could be magnetically separated and the adsorption capacity of anisole on magnetic biochars was stronger than that of phenol and guaiacol. The properties of magnetic biochar, including surface area, pore volume, aromaticity, grapheme-like-structure and iron oxide (γ-Fe 2 O 3 ) particles, showed pronounced effects on the adsorption performance of aromatic contaminants. Copyright © 2016 Elsevier Ltd. All rights reserved.

A comparison of fast and reactive pyrolysis with insitu derivatisation of fructose, inulin and Jerusalem artichoke (Helianthus tuberosus).

PubMed

Mattonai, Marco; Ribechini, Erika

2018-08-09

Reactive pyrolysis is a technique that provides mechanistic information by performing pyrolysis of the substrate in a sealed glass capsule at elevated temperature and pressure for relatively long time. This technique has already shown great potential for the analysis of biomass, favouring the formation of only the most thermostable compounds. In this work, both fast and reactive pyrolysis with on-line gas chromatography-mass spectrometry analysis (Py-GC/MS) are used to study fructose, inulin and Jerusalem artichoke tubers (Heliantus tuberosus). Interesting differences were found between the two systems, and became even more evident as the reaction time was increased. The most striking result was the formation of di-fructose dianhydrides (DFAs), a class of compounds with interesting biological activities. DFAs were obtained in high yields from reactive pyrolysis, but not from fast pyrolysis. Hypotheses on the pyrolysis mechanisms were made based upon the composition of the pyrolysates. This work describes for the first time the behaviour of fructans under reactive pyrolysis. Copyright © 2018 Elsevier B.V. All rights reserved.

High-resolution mass spectrometric analysis of biomass pyrolysis vapors

DOE PAGES

Christensen, Earl; Evans, Robert J.; Carpenter, Daniel

2017-01-19

Vapors generated from the pyrolysis of lignocellulosic biomass are made up of a complex mixture of oxygenated compounds. Direct analysis of these vapors provides insight into the mechanisms of depolymerization of cellulose, hemicellulose, and lignin as well as insight into reactions that may occur during condensation of pyrolysis vapors into bio-oil. Studies utilizing pyrolysis molecular beam mass spectrometry have provided valuable information regarding the chemical composition of pyrolysis vapors. Mass spectrometers generally employed with these instruments have low mass resolution of approximately a mass unit. The presence of chemical species with identical unit mass but differing elemental formulas cannot bemore » resolved with these instruments and are therefore detected as a single ion. In this study we analyzed the pyrolysis vapors of several biomass sources using a high-resolution double focusing mass spectrometer. High-resolution analysis of pyrolysis vapors allowed for speciation of several compounds that would be detected as a single ion with unit mass resolution. Lastly, these data not only provide greater detail into the composition of pyrolysis vapors but also highlight differences between vapors generated from multiple biomass feedstocks.« less

A pyrolysis study for the thermal and kinetic characteristics of an agricultural waste with two different plastic wastes.

PubMed

Çepelioğullar, Özge; Pütün, Ayşe E

2014-10-01

In this study, thermochemical conversion of plastic wastes (PET and PVC) together with an agricultural waste (hazelnut shell) was investigated. In order to determine the thermal and kinetic behaviours, pyrolysis experiments were carried out from room temperature to 800 °C, with a heating rate of 10 °C min(-1) in the presence of a N2 atmosphere in a thermogravimetric analyzer. With the obtained thermogravimetric data, an appropriate temperature was specified for the pyrolysis of biomass-plastic wastes in a fixed-bed reactor. At the second step, pyrolysis experiments were carried out at the same conditions with the thermogravimetric analyzer, except the final temperature which was up to 500 °C in this case. After pyrolysis experiments, pyrolysis yields were calculated and characterization studies for bio-oil were investigated. Experimental results showed that co-pyrolysis has an important role in the determination of the pyrolysis mechanism and the process conditions while designing/implementing a thermochemical conversion method where biomass-plastic materials were preferred as raw materials. © The Author(s) 2014.

Comparison of the pyrolysis behavior of lignins from different tree species.

PubMed

Wang, Shurong; Wang, Kaige; Liu, Qian; Gu, Yueling; Luo, Zhongyang; Cen, Kefa; Fransson, Torsten

2009-01-01

Despite the increasing importance of biomass pyrolysis, little is known about the pyrolysis behavior of lignin--one of the main components of biomass--due to its structural complexity and the difficulty in its isolation. In the present study, we extracted lignins from Manchurian ash (Fraxinus mandschurica) and Mongolian Scots pine (Pinus sylvestris var. mongolica) using the Bjorkman procedure, which has little effect on the structure of lignin. Fourier transform infrared (FTIR) spectrometry was used to characterize the microstructure of the Bjorkman lignins, i.e., milled wood lignins (MWLs), from the different tree species. The pyrolysis characteristics of MWLs were investigated using a thermogravimetric analyzer, and the release of the main volatile and gaseous products of pyrolysis were detected by FTIR spectroscopy. During the pyrolysis process, MWLs underwent thermo-degradation over a wide temperature range. Manchurian ash MWL showed a much higher thermal degradation rate than Mongolian Scots pine MWL in the temperature range from 290-430 degrees C. High residue yields were achieved at 37 wt.% for Mongolian Scots pine MWL and 26 wt.% for Manchurian ash MWL. In order to further investigate the mechanisms of lignin pyrolysis, we also analyzed the FTIR profiles for the main pyrolysis products (CO(2), CO, methane, methanol, phenols and formaldehyde) and investigated the variation in pyrolysis products between the different MWLs.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of polycarbonate and plastic waste to recover monomers

DOEpatents

Evans, R.J.; Chum, H.L.

1994-06-14

A process is described using fast pyrolysis to convert a plastic waste feed stream containing polycarbonate and ABS to high value monomeric constituents prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of a given polymer to its high value monomeric constituents prior to a temperature range that causes pyrolysis of other plastic components; selecting an acid or base catalysts and an oxide or carbonate support for treating the feed stream to affect acid or base catalyzed reaction pathways to maximize yield or enhance separation of the high value monomeric constituents of polycarbonate and ABS in the first temperature program range; differentially heating the feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituents prior to pyrolysis or other plastic components; separating the high value monomeric constituents from the polycarbonate to cause pyrolysis to a different high value monomeric constituent of the plastic waste and differentially heating the feed stream at the second higher temperature program range to cause pyrolysis of different high value monomeric constituents; and separating the different high value monomeric constituents. 68 figs.

Pyrolysis of polystyrene - polyphenylene oxide to recover styrene and useful products

DOEpatents

Evans, Robert J.; Chum, Helena L.

1995-01-01

A process of using fast pyrolysis in a carrier gas to convert a polystyrene and polyphenylene oxide plastic waste to a given polystyrene and polyphenylene oxide prior to pyrolysis of other plastic components therein comprising: selecting a first temperature range to cause pyrolysis of given polystyrene and polyphenylene oxide and its high value monomeric constituent prior to a temperature range that causes pyrolysis of other plastic components; selecting a catalyst and a support and treating the feed stream with the catalyst to affect acid or base catalyzed reaction pathways to maximize yield or enhance separation of high value monomeric constituent of styrene from polystyrene and polyphenylene oxide in the first temperature range; differentially heating the feed stream at a heat rate within the first temperature range to provide differential pyrolysis for selective recovery of the high value monomeric constituent of styrene from polystyrene and polyphenylene oxide prior to pyrolysis of other plastic components; separating the high value monomer constituent of styrene; selecting a second higher temperature range to cause pyrolysis to a different derived high value product of polyphenylene oxide from the plastic waste and differentially heating the feed stream at the higher temperature range to cause pyrolysis of the plastic into a polyphenylene oxide derived product; and separating the different derived high value polyphenylene oxide product.

Controlled catalystic and thermal sequential pyrolysis and hydrolysis of polycarbonate and plastic waste to recover monomers

DOEpatents

Evans, Robert J.; Chum, Helena L.

1994-01-01

A process of using fast pyrolysis to convert a plastic waste feed stream containing polycarbonate and ABS to high value monomeric constituents prior to pyrolysis of other plastic components therein comprising: selecting a first temperature program range to cause pyrolysis of a given polymer to its high value monomeric constituents prior to a temperature range that causes pyrolysis of other plastic components; selecting an acid or base catalysts and an oxide or carbonate support for treating the feed stream to affect acid or base catalyzed reaction pathways to maximize yield or enhance separation of the high value monomeric constituents of polycarbonate and ABS in the first temperature program range; differentially heating the feed stream at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantities of the high value monomeric constituents prior to pyrolysis or other plastic components; separating the high value monomeric constituents from the polycarbonate to cause pyrolysis to a different high value monomeric constituent of the plastic waste and differentially heating the feed stream at the second higher temperature program range to cause pyrolysis of different high value monomeric constituents; and separating the different high value monomeric constituents.

Vacuum pyrolysis of waste tires with basic additives.

PubMed

Zhang, Xinghua; Wang, Tiejun; Ma, Longlong; Chang, Jie

2008-11-01

Granules of waste tires were pyrolyzed under vacuum (3.5-10 kPa) conditions, and the effects of temperature and basic additives (Na2CO3, 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 degrees C to 600 degrees 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 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50 wt% was achieved at 480 degrees 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) approximately 205 degrees 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 Na2CO3 addition. Pyrolysis gas was mainly composed of H2, CO, CH4, CO2, C2H4 and C2H6. Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5 wt%) was much higher.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of phenolic resin containing waste streams to sequentially recover monomers and chemicals

DOEpatents

Chum, H.L.; Evans, R.J.

1992-08-04

A process is described for using fast pyrolysis in a carrier gas to convert a waste phenolic resin containing feedstreams in a manner such that pyrolysis of said resins and a given high value monomeric constituent occurs prior to pyrolyses of the resins in other monomeric components therein comprising: selecting a first temperature program range to cause pyrolysis of said resin and a given high value monomeric constituent prior to a temperature range that causes pyrolysis of other monomeric components; selecting, if desired, a catalyst and a support and treating said feedstreams with said catalyst to effect acid or basic catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said first temperature program range to utilize reactive gases such as oxygen and steam in the pyrolysis process to drive the production of specific products; differentially heating said feedstreams at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantity of said high value monomeric constituent prior to pyrolysis of other monomeric components therein; separating said high value monomeric constituent; selecting a second higher temperature program range to cause pyrolysis of a different high value monomeric constituent of said phenolic resins waste and differentially heating said feedstreams at said higher temperature program range to cause pyrolysis of said different high value monomeric constituent; and separating said different high value monomeric constituent. 11 figs.

Controlled catalytic and thermal sequential pyrolysis and hydrolysis of phenolic resin containing waste streams to sequentially recover monomers and chemicals

DOEpatents

Chum, Helena L.; Evans, Robert J.

1992-01-01

A process of using fast pyrolysis in a carrier gas to convert a waste phenolic resin containing feedstreams in a manner such that pyrolysis of said resins and a given high value monomeric constituent occurs prior to pyrolyses of the resins in other monomeric components therein comprising: selecting a first temperature program range to cause pyrolysis of said resin and a given high value monomeric constituent prior to a temperature range that causes pyrolysis of other monomeric components; selecting, if desired, a catalyst and a support and treating said feedstreams with said catalyst to effect acid or basic catalyzed reaction pathways to maximize yield or enhance separation of said high value monomeric constituent in said first temperature program range to utilize reactive gases such as oxygen and steam in the pyrolysis process to drive the production of specific products; differentially heating said feedstreams at a heat rate within the first temperature program range to provide differential pyrolysis for selective recovery of optimum quantity of said high value monomeric constituent prior to pyrolysis of other monomeric components therein; separating said high value monomeric constituent; selecting a second higher temperature program range to cause pyrolysis of a different high value monomeric constituent of said phenolic resins waste and differentially heating said feedstreams at said higher temperature program range to cause pyrolysis of said different high value monomeric constituent; and separating said different high value monomeric constituent.

Self-activation of biochar from furfural residues by recycled pyrolysis gas.

PubMed

Yin, Yulei; Gao, Yuan; Li, Aimin

2018-04-17

Biochar samples with controllable specific surface area and mesopore ratio were self-activated from furfural residues by recycled pyrolysis gas. The objective of this study was to develop a new cyclic utilization method for the gas produced by pyrolysis. The influences of preparation parameters on the resulting biochar were studied by varying the pyrolysis-gas flow rate, activation time and temperature. Structural characterization of the produced biochar was performed by analysis of nitrogen adsorption isotherms at 77 K and scanning electron microscope (SEM). The pyrolysis gas compositions before and after activation were determined by a gas chromatograph. The results indicated that the surface area of the biochar was increased from 167 m 2 /g to 567 m 2 /g, the total pore volume increased from 0.121 cm 3 /g to 0.380 cm 3 /g, and the ratio of the mesopore pore volume to the total pore volume increased 17-39.7%. The CO volume fraction of the pyrolysis gas changed from 34.66 to 62.29% and the CO 2 volume fraction decreased from 48.26% to 12.17% under different conditions of pyrolysis-gas flow rate, activation time and temperature. The calorific values of pyrolysis gas changed from 8.82 J/cm 3 to 14.00 J/cm 3 , which were higher than those of conventional pyrolysis gases. The slower pyrolysis-gas flow rate and higher activation time increased the efficiency of the reaction between carbon and pyrolysis gas. These results demonstrated the feasibility of treatment of the furfural residues to produce microporous and mesoporous biochar. The pyrolysis gas that results from the activation process could be used as fuel. Overall, this new self-activation method meets the development requirements of cyclic economy and cleaner production. Copyright © 2018. Published by Elsevier Ltd.

Catalytic and non-catalytic pyrolysis of biomass in non-inert environments for production of deoxygenated bio-oil and chemicals

USDA-ARS?s Scientific Manuscript database

Fast pyrolysis processes are among the most effective methods for liquefaction of lignocellulosic biomass. Catalytic fast pyrolysis (CFP) over HZSM-5 or other zeolites and/or utilization of reactive atmospheres such as in the non-catalytic Tail Gas Reactive Pyrolysis (TRGP) process, a recent patent...

Publications - GMC 114 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 114 Publication Details Title: Total organic carbon and rock eval pyrolysis data and analysis and Ruth Laboratories, Inc., 1989, Total organic carbon and rock eval pyrolysis data and analysis for gmc114.pdf (171.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis Top of Page Department of Natural Resources

Publications - GMC 290 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 290 Publication Details Title: Organic carbon and rock-eval pyrolysis data of cuttings from Reference Unknown, 1999, Organic carbon and rock-eval pyrolysis data of cuttings from the Husky Oil NPR Products Report Report Information gmc290.pdf (177.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis Top of Page

Publications - GMC 130 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 130 Publication Details Title: Total organic carbon and rock-eval pyrolysis data of cuttings Reference Unknown, 1989, Total organic carbon and rock-eval pyrolysis data of cuttings and core from the Report Report Information gmc130.pdf (208.0 K) Keywords Pyrolysis; Rock-Eval Pyrolysis Top of Page

Chapter 8: Pyrolysis of Biomass for Aviation Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robichaud, David J; Jenkins, Rhodri W.; Sutton, Andrew D.

2016-07-15

Pyrolysis, the breaking down of organic material using heat and the absence of oxygen, is a method that has been widely researched for the production of liquid fuels. In this chapter, we review the feedstocks typically used for pyrolysis, the properties and the composition of the liquid fraction (termed 'bio-oil') obtained, the studies in which pyrolysis has been used in an attempt to increase the bio-oil yield, and how the bio-oil has been upgraded to fuel-like molecules. We also discuss the viability of pyrolysis to produce jet fuel hydrocarbons.

Pyrolysis system evaluation study

NASA Technical Reports Server (NTRS)

1974-01-01

An evaluation of two different pyrolysis concepts which recover energy from solid waste was conducted in order to determine the merits of each concept for integration into a Integrated Utility System (IUS). The two concepts evaluated were a Lead Bath Furnace Pyrolysis System and a Slagging Vertical Shaft, Partial Air Oxidation Pyrolysis System. Both concepts will produce a fuel gas from the IUS waste and sewage sludge which can be used to offset primary fuel consumption in addition to the sanitary disposal of the waste. The study evaluated the thermal integration of each concept as well as the economic impact on the IUS resulting from integrating each pyrolysis concepts. For reference, the pyrolysis concepts were also compared to incineration which was considered the baseline IUS solid waste disposal system.

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

DOE PAGES

Carpenter, Daniel; Westover, Tyler; Howe, Daniel; ...

2016-12-01

Here, we report here on an experimental study to produce refinery-ready fuel blendstocks via catalytic hydrodeoxygenation (upgrading) of pyrolysis oil using several biomass feedstocks and various blends. Blends were tested along with the pure materials to determine the effect of blending on product yields and qualities. Within experimental error, oil yields from fast pyrolysis and upgrading are shown to be linear functions of the blend components. Switchgrass exhibited lower fast pyrolysis and upgrading yields than the woody samples, which included clean pine, oriented strand board (OSB), and a mix of pinon and juniper (PJ). The notable exception was PJ, formore » which the poor upgrading yield of 18% was likely associated with the very high viscosity of the PJ fast pyrolysis oil (947 cp). The highest fast pyrolysis yield (54% dry basis) was obtained from clean pine, while the highest upgrading yield (50%) was obtained from a blend of 80% clean pine and 20% OSB (CP 8OSB 2). For switchgrass, reducing the fast pyrolysis temperature to 450 degrees C resulted in a significant increase to the pyrolysis oil yield and reduced hydrogen consumption during hydrotreating, but did not directly affect the hydrotreating oil yield. The water content of fast pyrolysis oils was also observed to increase linearly with the summed content of potassium and sodium, ranging from 21% for clean pine to 37% for switchgrass. Multiple linear regression models demonstrate that fast pyrolysis is strongly dependent upon the contents lignin and volatile matter as well as the sum of potassium and sodium.« less

Co-pyrolysis of sewage sludge and manure.

PubMed

Ruiz-Gómez, Nadia; Quispe, Violeta; Ábrego, Javier; Atienza-Martínez, María; Murillo, María Benita; Gea, Gloria

2017-01-01

The management and valorization of residual organic matter, such as sewage sludge and manure, is gaining interest because of the increasing volume of these residues, their localized generation and the related problems. The anaerobic digestion of mixtures of sewage sludge and manure could be performed due to the similarities between both residues. The purpose of this study is to evaluate the feasibility of the co-pyrolysis of sewage sludge (SS) and digested manure (DM) as a potential management technology for these residues. Pyrolysis of a sewage sludge/manure blend (50:50%) was performed at 525°C in a stirred batch reactor under N 2 atmosphere. The product yields and some characteristics of the product were analyzed and compared to the results obtained in the pyrolysis of pure residues. Potential synergetic and antagonist effects during the co-pyrolysis process were evaluated. Although sewage sludge and manure seem similar in nature, there are differences in their pyrolysis product properties and distribution due to their distinct ash and organic matter composition. For the co-pyrolysis of SS and DM, the product yields did not show noticeable synergistic effects with the exception of the yields of organic compounds, being slightly higher than the predicted average, and the H 2 yield, being lower than expected. Co-pyrolysis of SS and DM could be a feasible management alternative for these residues in locations where both residues are generated, since the benefits and the drawbacks of the co-pyrolysis are similar to those of the pyrolysis of each residue. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fates of Chemical Elements in Biomass during Its Pyrolysis.

PubMed

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

2017-05-10

Biomass is increasingly perceived as a renewable resource rather than as an organic solid waste today, as it can be converted to various chemicals, biofuels, and solid biochar using modern processes. In the past few years, pyrolysis has attracted growing interest as a promising versatile platform to convert biomass into valuable resources. However, an efficient and selective conversion process is still difficult to be realized due to the complex nature of biomass, which usually makes the products complicated. Furthermore, various contaminants and inorganic elements (e.g., heavy metals, nitrogen, phosphorus, sulfur, and chlorine) embodied in biomass may be transferred into pyrolysis products or released into the environment, arousing environmental pollution concerns. Understanding their behaviors in biomass pyrolysis is essential to optimizing the pyrolysis process for efficient resource recovery and less environmental pollution. However, there is no comprehensive review so far about the fates of chemical elements in biomass during its pyrolysis. Here, we provide a critical review about the fates of main chemical elements (C, H, O, N, P, Cl, S, and metals) in biomass during its pyrolysis. We overview the research advances about the emission, transformation, and distribution of elements in biomass pyrolysis, discuss the present challenges for resource-oriented conversion and pollution abatement, highlight the importance and significance of understanding the fate of elements during pyrolysis, and outlook the future development directions for process control. The review provides useful information for developing sustainable biomass pyrolysis processes with an improved efficiency and selectivity as well as minimized environmental impacts, and encourages more research efforts from the scientific communities of chemistry, the environment, and energy.

Effect of dry torrefaction on kinetics of catalytic pyrolysis of sugarcane bagasse

NASA Astrophysics Data System (ADS)

Daniyanto, Sutijan, Deendarlianto, Budiman, Arief

2015-12-01

Decreasing world reserve of fossil resources (i.e. petroleum oil, coal and natural gas) encourage discovery of renewable resources as subtitute for fossil resources. Biomass is one of the main natural renewable resources which is promising resource as alternate resources to meet the world's energy needs and raw material to produce chemical platform. Conversion of biomass, as source of energy, fuel and biochemical, is conducted using thermochemical process such as pyrolysis-gasification process. Pyrolysis step is an important step in the mechanism of pyrolysis - gasification of biomass. The objective of this study is to obtain the kinetic reaction of catalytic pyrolysis of dry torrified sugarcane bagasse which used Ca and Mg as catalysts. The model of kinetic reaction is interpreted using model n-order of single reaction equation of biomass. Rate of catalytic pyrolysis reaction depends on the weight of converted biomass into char and volatile matters. Based on TG/DTA analysis, rate of pyrolysis reaction is influenced by the composition of biomass (i.e. hemicellulose, cellulose and lignin) and inorganic component especially alkali and alkaline earth metallic (AAEM). From this study, it has found two equations rate of reaction of catalytic pyrolysis in sugarcane bagasse using catalysts Ca and Mg. First equation is equation of pyrolysis reaction in rapid zone of decomposition and the second equation is slow zone of decomposition. Value of order reaction for rapid decomposition is n > 1 and for slow decomposition is n<1. Constant and order of reactions for catalytic pyrolysis of dry-torrified sugarcane bagasse with presence of Ca tend to higher than that's of presence of Mg.

Comparison of petroleum generation kinetics by isothermal hydrous and nonisothermal open-system pyrolysis

USGS Publications Warehouse

Lewan, M.D.; Ruble, T.E.

2002-01-01

This study compares kinetic parameters determined by open-system pyrolysis and hydrous pyrolysis using aliquots of source rocks containing different kerogen types. Kinetic parameters derived from these two pyrolysis methods not only differ in the conditions employed and products generated, but also in the derivation of the kinetic parameters (i.e., isothermal linear regression and non-isothermal nonlinear regression). Results of this comparative study show that there is no correlation between kinetic parameters derived from hydrous pyrolysis and open-system pyrolysis. Hydrous-pyrolysis kinetic parameters determine narrow oil windows that occur over a wide range of temperatures and depths depending in part on the organic-sulfur content of the original kerogen. Conversely, open-system kinetic parameters determine broad oil windows that show no significant differences with kerogen types or their organic-sulfur contents. Comparisons of the kinetic parameters in a hypothetical thermal-burial history (2.5 ??C/my) show open-system kinetic parameters significantly underestimate the extent and timing of oil generation for Type-US kerogen and significantly overestimate the extent and timing of petroleum formation for Type-I kerogen compared to hydrous pyrolysis kinetic parameters. These hypothetical differences determined by the kinetic parameters are supported by natural thermal-burial histories for the Naokelekan source rock (Type-IIS kerogen) in the Zagros basin of Iraq and for the Green River Formation (Type-I kerogen) in the Uinta basin of Utah. Differences in extent and timing of oil generation determined by open-system pyrolysis and hydrous pyrolysis can be attributed to the former not adequately simulating natural oil generation conditions, products, and mechanisms.

Recycling WEEE: Polymer characterization and pyrolysis study for waste of crystalline silicon photovoltaic modules.

PubMed

Dias, Pablo; Javimczik, Selene; Benevit, Mariana; Veit, Hugo

2017-02-01

Photovoltaic (PV) modules contain both valuable and hazardous materials, which makes its recycling meaningful economically and environmentally. In general, the recycling of PV modules starts with the removal of the polymeric ethylene-vinyl acetate (EVA) resin using pyrolysis, which assists in the recovery of materials such as silicon, copper and silver. The pyrolysis implementation, however, needs improvement given its importance. In this study, the polymers in the PV modules were characterized by Fourier transform infrared spectroscopy (FTIR) and the removal of the EVA resin using pyrolysis has been studied and optimized. The results revealed that 30min pyrolysis at 500°C removes >99% of the polymers present in photovoltaic modules. Moreover, the behavior of different particle size milled modules during the pyrolysis process was evaluated. It is shown that polymeric materials tend to remain at a larger particle size and thus, this fraction has the greatest mass loss during pyrolysis. A thermo gravimetric analysis (TGA) performed in all polymeric matter revealed the optimum pyrolysis temperature is around 500°C. Temperatures above 500°C continue to degrade matter, but mass loss rate is 6.25 times smaller. This study demonstrates the use of pyrolysis can remove >99% of the polymeric matter from PV modules, which assists the recycling of this hazardous waste and avoids its disposal. Copyright © 2016 Elsevier Ltd. All rights reserved.

National Aerospace Fuels Research Complex

DTIC Science & Technology

2010-03-01

supercritical pyrolysis. 7 6. Representative chromatogram of low conversion stressed S-8 liquid product from supercritical pyrolysis on ECAT. 7 7...Representative chromatogram of very high conversion stressed S-8 liquid product from supercritical pyrolysis at UTRC. 9 8. Representative chromatogram...of stressed S-8 liquid product from supercritical pyrolysis at Louisiana State University. 9 9. GC-MS scanning total ion chromatograms of fuels

Catalytic pyrolysis characteristics of scrap printed circuit boards by TG-FTIR.

PubMed

Zhao, Chunhu; Zhang, Xiaoping; Shi, Lin

2017-03-01

In the present work, pyrolysis and catalytic pyrolysis of waste printed circuit boards (WPCBs) was carried out in the coupling of Thermo Gravimetric Analysis and Fourier Transform Infrared Spectroscopy (TG-FTIR) under nitrogen atmosphere. The reaction temperature was increased from 30 to 700°C, while the heating rates were varied from 10 to 40°C/min. Experimental results show that the effect of catalyst on the WPCBs particles pyrolysis was significance. Compared with another two combustion-supporting agents (MgO, CaO), the whole pyrolysis process was optimized when the catalyst ZSM-5 was added into the WPCBs particles. The distributed activation energy model (DAEM) was used to analyze the kinetic parameters of the WPCBs pyrolysis. It was found that values of frequency factor (k 0 ) changed with different activation energy (E) values during pyrolysis process. The activation energy values range from 129.15 to 280.53kJ/mol, and the frequency factor values range from 9.02×10 10 to 4.21×10 22 s -1 . The generated major products for the catalytic pyrolysis of WPCBs were H 2 , CO 2 , CO, H 2 O, phenols and aromatics. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparative assessment of municipal sewage sludge incineration, gasification and pyrolysis for a sustainable sludge-to-energy management in Greece

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samolada, M.C.; Zabaniotou, A.A., E-mail: azampani@auth.gr

2014-02-15

Highlights: • The high output of MSS highlights the need for alternative routes of valorization. • Evaluation of 3 sludge-to-energy valorisation methods through SWOT analysis. • Pyrolysis is an energy and material recovery process resulting to ‘zero waste’. • Identification of challenges and barriers for MSS pyrolysis in Greece was investigated. • Adopters of pyrolysis systems face the challenge of finding new product markets. - Abstract: For a sustainable municipal sewage sludge management, not only the available technology, but also other parameters, such as policy regulations and socio-economic issues should be taken in account. In this study, the current statusmore » of both European and Greek Legislation on waste management, with a special insight in municipal sewage sludge, is presented. A SWOT analysis was further developed for comparison of pyrolysis with incineration and gasification and results are presented. Pyrolysis seems to be the optimal thermochemical treatment option compared to incineration and gasification. Sewage sludge pyrolysis is favorable for energy savings, material recovery and high added materials production, providing a ‘zero waste’ solution. Finally, identification of challenges and barriers for sewage sludge pyrolysis deployment in Greece was investigated.« less

Pressurized entrained-flow pyrolysis of microalgae: Enhanced production of hydrogen and nitrogen-containing compounds.

PubMed

Maliutina, Kristina; Tahmasebi, Arash; Yu, Jianglong

2018-05-01

Pressurized entrained-flow pyrolysis of Chlorella vulgaris microalgae was investigated. The impact of pressure on the yield and composition of pyrolysis products were studied. The results showed that the concentration of H 2 in bio-gas increased sharply with increasing pyrolysis pressure, while those of CO, CO 2 , CH 4 , and C 2 H 6 were dramatically decreased. The concentration of H 2 reached 88.01 vol% in bio-gas at 900 °C and 4 MPa. Higher pressures promoted the hydrogen transfer to bio-gas. The bio-oils derived from pressurized pyrolysis were rich in nitrogen-containing compounds and PAHs. The highest concentration of nitrogen-containing compounds in bio-oil was achieved at 800 °C and 1 MPa. Increasing pyrolysis pressure promoted the formation of nitrogen-containing compounds such as indole, quinoline, isoquinoline and phenanthridine. Higher pyrolysis pressures led to increased sphericity, enhanced swelling, and higher carbon order of bio-chars. Pressurized pyrolysis of biomass has a great potential for poly-generation of H 2 , nitrogen containing compounds and bio-char. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

PubMed

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

2015-11-01

This study evaluates the techno-economic uncertainty in cost estimates for two emerging technologies for biofuel production: in situ and ex situ catalytic pyrolysis. The probability distributions for the minimum fuel-selling price (MFSP) indicate that in situ catalytic pyrolysis has an expected MFSP of $1.11 per liter with a standard deviation of 0.29, while the ex situ catalytic pyrolysis has a similar MFSP with a smaller deviation ($1.13 per liter and 0.21 respectively). These results suggest that a biorefinery based on ex situ catalytic pyrolysis could have a lower techno-economic uncertainty than in situ pyrolysis compensating for a slightly higher MFSP cost estimate. Analysis of how each parameter affects the NPV indicates that internal rate of return, feedstock price, total project investment, electricity price, biochar yield and bio-oil yield are parameters which have substantial impact on the MFSP for both in situ and ex situ catalytic pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

PubMed

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

2014-01-01

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

Physicochemical evolution during rice straw and coal co-pyrolysis and its effect on co-gasification reactivity.

PubMed

Wei, Juntao; Gong, Yan; Guo, Qinghua; Ding, Lu; Wang, Fuchen; Yu, Guangsuo

2017-03-01

Physicochemical evolution (i.e. pore structure variation, carbon structure change and active AAEM transformation) during rice straw (RS) and Shenfu bituminous coal (SF) co-pyrolysis was quantitatively determined in this work. Moreover, the corresponding char gasification was conducted using a thermogravimetric analyzer (TGA) and relative reactivity was proposed to quantify the co-pyrolysis impact on co-gasification reactivity. The results showed that the development of pore structure in co-pyrolyzed chars was first inhibited and then enhanced with the decrease of SF proportion. The promotion effect of co-pyrolysis on order degree of co-pyrolyzed chars gradually weakened with increasing RS proportion. Co-pyrolysis mainly enhanced active K transformation in co-pyrolyzed chars and the promotion effect was alleviated with increasing RS proportion. The inhibition effect of co-pyrolysis on co-gasification reactivity weakened with increasing RS proportion and gasification temperature, which was mainly attributed to the combination of carbon structure evolution and active AAEM transformation in co-pyrolysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigating pyrolysis characteristics of moso bamboo through TG-FTIR and Py-GC/MS.

PubMed

Liang, Fang; Wang, Ruijuan; Hongzhong, Xiang; Yang, Xiaomeng; Zhang, Tao; Hu, Wanhe; Mi, Bingbing; Liu, Zhijia

2018-05-01

This study was carried out to investigate pyrolysis characteristics of moso bamboo (Phyllostachys pubescens), including outer layer (OB), middle layer (MB) and inner layer (IB) and bamboo leaves (BL), through TG-FTIR and Py-GC/MS. The results showed that 70% of weight loss occurred at rapid pyrolysis stage with temperature of 200-400 °C. With increase in heating rate, pyrolysis process shifted toward higher temperature. IB, OB, MB and BL had a different activation energy at different conversion rates. BL had a higher activation energy than IB, OB and MB. The volatiles of bamboo was complicated with 2-30 of C atoms. IB, OB and MB mainly released benzofuran, hydroxyacetaldehyde and 2-Pentanone. BL released furan, acetic acid and phenol. The main pyrolysis products included H 2 O, CH 4 , CO 2 , CO, carboxylic acids, NO, NO 2 . Pyrolysis products of IB was the most and that of BL was the lowest. MB had the lowest pyrolysis temperature. Copyright © 2018 Elsevier Ltd. All rights reserved.

Discernment of synergism in pyrolysis of biomass blends using thermogravimetric analysis.

PubMed

Mallick, Debarshi; Poddar, Maneesh Kumar; Mahanta, Pinakeswar; Moholkar, Vijayanand S

2018-08-01

This study reports pyrolysis kinetics of biomass blends using isoconversional methods, viz. Friedman, FWO and KAS. Blends of three biomasses, viz. saw dust, bamboo dust and rice husk, were used. Extractives and volatiles in biomass and minerals in ash had marked influence on enhancement of reaction kinetics during co-pyrolysis, as indicated by reduction in activation energy and increase in decomposition intensity. Pyrolysis kinetics of saw dust and rice husk accelerated (positive synergy), while that of bamboo dust decelerated after blending (negative synergy). Predominant reaction mechanism of all biomass blends was 3-D diffusion in lower conversion range (α ≤ 0.5), while for α ≥ 0.5 pyrolysis followed random nucleation (or nucleation and growth mechanism). Higher reaction order for pyrolysis of blends of rice husk with saw dust and bamboo dust was attributed to catalytic effect of minerals in ash. Positive ΔH and ΔG was obtained for pyrolysis of all biomass blends. Copyright © 2018 Elsevier Ltd. All rights reserved.

The comparative kinetic analysis of Acetocell and Lignoboost® lignin pyrolysis: the estimation of the distributed reactivity models.

PubMed

Janković, Bojan

2011-10-01

The non-isothermal pyrolysis kinetics of Acetocell (the organosolv) and Lignoboost® (kraft) lignins, in an inert atmosphere, have been studied by thermogravimetric analysis. Using isoconversional analysis, it was concluded that the apparent activation energy for all lignins strongly depends on conversion, showing that the pyrolysis of lignins is not a single chemical process. It was identified that the pyrolysis process of Acetocell and Lignoboost® lignin takes place over three reaction steps, which was confirmed by appearance of the corresponding isokinetic relationships (IKR). It was found that major pyrolysis stage of both lignins is characterized by stilbene pyrolysis reactions, which were subsequently followed by decomposition reactions of products derived from the stilbene pyrolytic process. It was concluded that non-isothermal pyrolysis of Acetocell and Lignoboost® lignins can be best described by n-th (n>1) reaction order kinetics, using the Weibull mixture model (as distributed reactivity model) with alternating shape parameters. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

PubMed

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.

Analysis of Titan tholin pyrolysis products by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry.

PubMed

McGuigan, Megan; Waite, J Hunter; Imanaka, Hiroshi; Sacks, Richard D

2006-11-03

The reddish brown haze that surrounds Titan, Saturn's largest moon, is thought to consist of tholin-like organic aerosols. Tholins are complex materials of largely unknown structure. The very high peak capacity and structured chromatograms obtained from comprehensive two-dimensional GC (GC x GC) are attractive attributes for the characterization of tholin pyrolysis products. In this report, GC x GC with time-of-flight MS detection and a flash pyrolysis inlet is used to characterize tholin pyrolysis products. Identified pyrolysis products include low-molecular-weight nitriles, alkyl substituted pyrroles, linear and branched hydrocarbons, alkyl-substituted benzenes and PAH compounds. The pyrolysis of standards found in tholin pyrolysate showed that little alteration occurred and thus these structures are likely present in the tholin material.

Pyrolysis process for producing fuel gas

NASA Technical Reports Server (NTRS)

Serio, Michael A. (Inventor); Kroo, Erik (Inventor); Wojtowicz, Marek A. (Inventor); Suuberg, Eric M. (Inventor)

2007-01-01

Solid waste resource recovery in space is effected by pyrolysis processing, to produce light gases as the main products (CH.sub.4, H.sub.2, CO.sub.2, CO, H.sub.2O, NH.sub.3) and a reactive carbon-rich char as the main byproduct. Significant amounts of liquid products are formed under less severe pyrolysis conditions, and are cracked almost completely to gases as the temperature is raised. A primary pyrolysis model for the composite mixture is based on an existing model for whole biomass materials, and an artificial neural network models the changes in gas composition with the severity of pyrolysis conditions.

Methods for deoxygenating biomass-derived pyrolysis oil

DOEpatents

Baird, Lance Awender; Brandvold, Timothy A.

2015-06-30

Methods for deoxygenating a biomass-derived pyrolysis oil are provided. A method for deoxygenating a biomass-derived pyrolysis oil comprising the steps of combining a biomass-derived pyrolysis oil stream with a heated low-oxygen-pyoil diluent recycle stream to form a heated diluted pyoil feed stream is provided. The heated diluted pyoil feed stream has a feed temperature of about 150.degree. C. or greater. The heated diluted pyoil feed stream is contacted with a first deoxygenating catalyst in the presence of hydrogen at first hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent.

Finding the chemistry in biomass pyrolysis: Millisecond chemical kinetics and visualization

NASA Astrophysics Data System (ADS)

Krumm, Christoph

Biomass pyrolysis is a promising thermochemical method for producing fuels and chemicals from renewable sources. Development of a fundamental understanding of biomass pyrolysis chemistry is difficult due to the multi-scale and multi-phase nature of the process; biomass length scales span 11 orders of magnitude and pyrolysis phenomena include solid, liquid, and gas phase chemistry in addition to heat and mass transfer. These complexities have a significant effect on chemical product distributions and lead to variability between reactor technologies. A major challenge in the study of biomass pyrolysis is the development of kinetic models capable of describing hundreds of millisecond-scale reactions of biomass into lower molecular weight products. In this work, a novel technique for studying biomass pyrolysis provides the first- ever experimental determination of kinetics and rates of formation of the primary products from cellulose pyrolysis, providing insight into the millisecond-scale chemical reaction mechanisms. These findings highlight the importance of heat and mass transport limitations for cellulose pyrolysis chemistry and are used to identify the length scales at which transport limitations become relevant during pyrolysis. Through this technique, a transition is identified, known as the reactive melting point, between low and high temperature depolymerization. The transition between two mechanisms of cellulose decompositions unifies the mechanisms that govern low temperature char formation, intermediate pyrolysis conditions, and high temperature gas formation. The conditions under which biomass undergoes pyrolysis, including modes of heat transfer, have been shown to significantly affect the distribution of biorenewable chemical and fuel products. High-speed photography is used to observe the liftoff of initially crystalline cellulose particles when impinged on a heated surface, known as the Leidenfrost effect for room-temperature liquids. Order-of-magnitude changes in the lifetime of cellulose particles are observed as a result of changing modes in heat transfer as cellulose intermediate liquid droplets wet and de-wet polished ceramic surfaces. Introduction of surface macroporosity is shown to completely inhibit the cellulose Leidenfrost effect, providing avenues for surface modification and reactor design to control particle heat transfer in industrial pyrolysis applications. Cellulosic particles on surfaces consisting of microstructured, asymmetric ratchets were observed to spontaneously move orthogonal to ratchet wells above the cellulose reactive Leidenfrost temperature (>750 °C). Evaluation of the accelerating particles supported the mechanism of propelling viscous forces (50-200 nN) from rectified pyrolysis vapors, thus providing the first example of biomass conveyors with no moving parts driven by high temperature for biofuel reactors. Combined knowledge of pyrolysis chemistry, kinetics, and heat and mass transport effects direct the design of the next generation pyrolysis reactors for tuning bio- oil quality and design of improved catalytic upgrading technology.

Modelisation et simulation de pyrolyse de pneus usages dans des reacteurs de laboratoire et industriel

NASA Astrophysics Data System (ADS)

Lanteigne, Jean-Remi

The present thesis covers an applied study on tire pyrolysis. The main objective is to develop tools to allow predicting the production and the quality of oil from tire pyrolysis. The first research objective consisted in modelling the kinetics of tires pyrolysis in a reactor, namely an industrial rotary drum operating in batch mode. A literature review performed later demonstrated that almost all kinetics models developed to represent tire pyrolysis could not represent the actual industrial process with enough accuracy. Among the families of kinetics models for pyrolysis, three have been identified: models with one single global reaction, models with multiple combined parallel reactions, and models with multiple parallel and series reactions. It was observed that these models show limitations. In the models with one single global reaction and with multiple parallels reactions, the production of each individual pyrolytic product cannot be predicted, but only for combined volatiles. Morevoer, the mass term in the kinetics refers to the final char weight (Winfinity) that varies with pyrolysis conditions, which yields less robust models. Also, despite the fact that models with multiple parallels and series reactions can predict the rate of production for each pyrolysis product, the selectivities are determined for operating temperatures instead of real mass temperatures, giving models for which parameters tuning is not adequate when used at the industrial scale. A new kinetics model has been developed, allowing predicting the rate of production of noncondensable gas, oil, and char from tire pyrolysis. The novelty of this model is the consideration of intrinsic selectivities for each product as a function of temperature. This hypothesis has been assumed valid considering that in the industrial pyrolysis process, pyrolysis kinetics is limiting. The developed model considers individual kinetics for each of the three pyrolytic products proportional to the global decomposition kinetics of pyrolysables. The simulation with data obtained in industrial operation showed the robustness of the model to predict with accuracy in transient regime, tires pyrolysis, with the help of model parameters obtained at laboratory scale, namely in regards of the trigger of production, the residence time of tires (dynamic production) and the amount of oil produced (cumulative yield). It is a novel way to model pyrolysis that could be extrapolated to new waste materials. The second objective of this doctoral research was to determine the evolution of specific tires specific heat during pyrolysis and the enthalpy of pyrolysis. The origin of this objective comes from a primary contradiction. With few exceptions, it is acknowledged that organic materials pyrolysis is globally an endothermic phenomenon. At the opposite, all experiments led with laboratory apparatuses such as DSC (Differential Scanning Calorimetry) showed exothermic peaks during dynamic experiments (constant heating rate). It has been confirmed by results obtained at the industrial scale, where no sign of exothermicity has been observed. The Hess Law has also confirmed these results, that globally, pyrolysis is indeed a completely endothermic process. An accurate energy balance is required to predict mass temperature during pyrolysis, this parameter being unbindable from kinetics. An advanced investigation of char first allowed demonstrating that specific heat of solids during pyrolysis decreases with increasing temperature until the weight loss peak is reached, around 400°C, and then starts increasing again. This observation, combined with the fact that the sample loses weight during pyrolysis is considered as the major cause of the apparition of an exothermic peak in laboratory scale experiments. That is, the control system of these apparatuses generates a bias and an unavoidable overheat of the samples producing this exothermic behavior. It would thus be an artifact. On the base of new data on the evolution of global specific heat during pyrolysis, a model of the energy balance has been developed at the industrial scale to determine the enthalpy of pyrolysis. The simulation has shown that a major part of the heat transferred to the pyrolized mass would make its temperature increase. Next, an enthalpy of pyrolysis dependent of weight loss was obtained. Finally, two other terms of enthalpy have been found, namely an enthalpy for the breakage of sulfur bridges and an enthalpy for the stabilization of char when conversion approaches completion. This research will have allowed establishing a novel general methodology to determine the enthalpy of pyrolysis. More particularly, new clarifications hasve been obtained in regards to the evolution of specific heat of solids during pyrolysis and new enthalpies of pyrolysis, all endothermic, could be obtained, in agreement with the theoretical expectations. The third research objective concerned the behavior of sulfur during tires pyrolysis. With as a premise that sulfur is an intrinsic contaminant of many types of waste, it is critical to clarify its fate during pyrolysis, in the present case for waste tires. It has been observed in the literature that some quantitative analyses had been presented, but generally, the mechanisms for the distribution of sulfur within the pyrolytic products remain unclear. Thus, it was then not possible to predict the transfer of sulfur to each of the tire pyrolysis products. The results taken form literature have been complemented with a series of TGA experiments followed by complete elemental analyses of the residual solids. Mass balances have been performed in order to characterize the distribution of elements within the three products (noncondensable gas, oil, and char). A novel parameter has been created during this research: the sulfur loss selectivity. This intrinsic selectivity is a prediction of the distribution of sulfur within the pyrolysis products as a function of temperature. Three phenomena has been identified that could affect the sulfur loss selectivity. First, the natural devolatilization of sulfur due to pyrolysis. Next, the sulfur devolatilization due to the desulfurization of the solid matrix by hydrogen and finally, the clustering of sulfur in the solid state due to metal sulfidation (zinc and iron). The results have shown that this selectivity reach a limit value of 1 when pyrolysis is limited by the kinetics and in the absence of metal. When the mass transfer is limiting at low temperature (<500°C) the selectivity will be greater than 1. At a temperature over 350°C with the presence of metals, the selectivity will be lower than 1. It is a useful tool for industrial pyrolysis processes, being a novel indicator for the distribution of contaminants during the pyrolysis of waste. A better comprehension of these mechanisms allows elaborating a better strategy when designing these industrial processes. For example, in light of this research, it could be preferable to pre-treat the tires at lower temperature to eliminate a significant part of sulfur before pyrolyzing them at high temperature. The resulting pyrolytic products would then necessitate a lighter purification post-treatment, being more efficient and more economical.

Methods for deoxygenating biomass-derived pyrolysis oil

DOEpatents

Brandvold, Timothy A.

2015-07-14

Methods for deoxygenating a biomass-derived pyrolysis oil are provided. A method comprising the steps of diluting the biomass-derived pyrolysis oil with a phenolic-containing diluent to form a diluted pyoil-phenolic feed is provided. The diluted pyoil-phenolic feed is contacted with a deoxygenating catalyst in the presence of hydrogen at hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent.

Pyrolysis temperature affects phosphorus transformation in biochar: Chemical fractionation and (31)P NMR analysis.

PubMed

Xu, Gang; Zhang, You; Shao, Hongbo; Sun, Junna

2016-11-01

Phosphorus (P) recycling or reuse by pyrolyzing crop residue has recently elicited increased research interest. However, the effects of feedstock and pyrolysis conditions on P species have not been fully understood. Such knowledge is important in identifying the agronomic and environmental uses of biochar. Residues of three main Chinese agricultural crops and the biochars (produced at 300°C-600°C) derived from these crops were used to determine P transformations during pyrolysis. Hedley sequential fractionation and (31)P NMR analyses were used in the investigation. Our results showed that P transformation in biochar was significantly affected by pyrolysis temperature regardless of feedstock (Wheat straw, maize straw and peanut husk). Pyrolysis treatment transformed water soluble P into a labile (NaHCO3-Pi) or semi-labile pool (NaOH-Pi) and into a stable pool (Dil. HCl P and residual-P). At the same time, organic P was transformed into inorganic P fractions which was identified by the rapid decomposition of organic P detected with solution (31)P NMR. The P transformation during pyrolysis process suggested more stable P was formed at a higher pyrolysis temperature. This result was also evidenced by the presence of less soluble or stable P species, such as such as poly-P, crandallite (CaAl3(OH)5(PO4)2) and Wavellite (Al3(OH)3(PO4)2·5H2O), as detected by solid-state (31)P NMR in biochars formed at a higher pyrolysis temperature. Furthermore, a significant proportion of less soluble pyrophosphate was identified by solution (2%-35%) and solid-state (8%-53%) (31)P NMR, which was also responsible for the stable P forms at higher pyrolysis temperature although their solubility or stability requires further investigation. Results suggested that a relatively lower pyrolysis temperature retains P availability regardless of feedstock during pyrolysis process. Copyright © 2016. Published by Elsevier B.V.

Effect of temperature on pyrolysis product of empty fruit bunches

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rahman, Aizuddin Abdul; Sulaiman, Fauziah; Abdullah, Nurhayati

2015-04-24

Pyrolysis of empty fruit bunches (EFB) was performed in a fixed bed reactor equipped with liquid collecting system. Pyrolysis process was conducted by varying the terminal pyrolysis temperature from 300 to 500°C under heating rate of 10°C/min for at least 2 hours. Char yield was obtained highest at 300°C around 55.88 wt%, and started to decrease as temperature increase. The maximum yield of pyrolysis liquid was obtained around 54.75 wt% as pyrolysis temperature reach 450°C. For gas yield percentage, the yield gained as temperature was increased from 300 to 500°C, within the range between 8.44 to 19.32 wt%. The charmore » obtained at 400°C has great potential as an alternative solid fuel, due to its high heating value of 23.37 MJ/kg, low in volatile matter and ash content which are approximately around 40.32 and 11.12 wt%, respectively. The collected pyrolysis liquid within this temperature range found to have high water content of around 16.15 to 18.20 wt%. The high aqueous fraction seemed to cause the pyrolysis liquid to have low HHV which only ranging from 10.81 to 12.94 MJ/kg. These trends of results showed that necessary enhancement should be employ either on the raw biomass or pyrolysis products in order to approach at least the minimum quality of common hydrocarbon solid or liquid fuel. For energy production, both produced bio-char and pyrolysis liquid are considered as sustainable sources of bio-energy since they contained low amounts of nitrogen and sulphur, which are considered as environmental friendly solid and liquid fuel.« less

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

PubMed

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

2014-05-15

Biosludge can be pyrolyzed to produce liquid oil as an alternative fuel. The content of five major elements, 22 trace elements and 16 PAHs was investigated in oven-dried raw material, pyrolysis residues and pyrolysis liquid products. Results indicated 39% carbon, 4.5% hydrogen, 4.2% nitrogen and 1.8% sulfur were in oven dried biosludge. Biosludge pyrolysis, carried out at temperatures from 400 to 800°C, corresponded to 34-14% weight in pyrolytic residues, 32-50% weight in liquid products and 31-40% weight in the gas phase. The carbon, hydrogen and nitrogen decreased and the sulfur content increased with an increase in the pyrolysis temperature at 400-800°C. NaP (2 rings) and AcPy (3 rings) were the major PAHs, contributing 86% of PAHs in oven-dried biosludge. After pyrolysis, the PAH content increased with the increase of pyrolysis temperature, which also results in a change in the PAH species profile. In pyrolysis liquid oil, NaP, AcPy, Flu and PA were the major species, and the content of the 16 PAHs ranged from 1.6 to 19 μg/ml at pyrolysis temperatures ranging from 400 to 800°C. Ca, Mg, Al, Fe and Zn were the dominant trace elements in the raw material and the pyrolysis residues. In addition, low toxic metal (Cd, V, Co, and Pb) content was found in the liquid oil, and its heat value was 7,800-9,500 kcal/kg, which means it can be considered as an alternative fuel. Copyright © 2014 Elsevier B.V. All rights reserved.

Thermal behavior of vehicle plastic blends contained acrylonitrile-butadiene-styrene (ABS) in pyrolysis using TG-FTIR.

PubMed

Liu, Guicai; Liao, Yanfen; Ma, Xiaoqian

2017-03-01

As important plastic blends in End-of-Life vehicles (ELV), pyrolysis profiles of ABS/PVC, ABS/PA6 and ABS/PC were investigated using thermogravimetric-Fourier transform infrared spectrometer (TG-FTIR). Also, CaCO 3 was added as plastic filler to discuss its effects on the pyrolysis of these plastics. The results showed that the interaction between ABS and PVC made PVC pyrolysis earlier and HCl emission slightly accelerated. The mixing of ABS and PA6 made their decomposition temperature closer, and ketones in PA6 pyrolysis products were reduced. The presence of ABS made PC pyrolysis earlier, and phenyl compounds in PC pyrolysis products could be transferred into alcohol or H 2 O. The interaction between ABS and other polymers in pyrolysis could be attributed to the intermolecular radical transfer, and free radicals from the polymer firstly decomposed led to a fast initiation the decomposition of the other polymer. As plastic filler, CaCO 3 promoted the thermal decomposition of PA6 and PC, and had no obvious effects on ABS and PVC pyrolysis process. Also, CaCO 3 made the pyrolysis products from PA6 and PC further decomposed into small-molecule compounds like CO 2 . The kinetics analysis showed that isoconversional method like Starink method was more suitable for these polymer blends. Starink method showed the average activation energy of ABS50/PVC50, ABS50/PA50 and ABS50/PC50 was 186.63kJ/mol, 239.61kJ/mol and 248.95kJ/mol, respectively, and the interaction among them could be reflected by the activation energy variation. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2016-08-15

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

Catalytic pyrolysis of black-liquor lignin by co-feeding with different plastics in a fluidized bed reactor.

PubMed

Zhang, Huiyan; Xiao, Rui; Nie, Jianlong; Jin, Baosheng; Shao, Shanshan; Xiao, Guomin

2015-09-01

Catalytic co-pyrolysis of black-liquor lignin and waste plastics (polyethylene, PE; polypropylene PP; polystyrene, PS) was conducted in a fluidized bed. The effects of temperature, plastic to lignin ratio, catalyst and plastic types on product distributions were studied. Both aromatic and olefin yields increased with increasing PE proportion. Petrochemical yield of co-pyrolysis of PE and lignin was LOSA-1 > spent FCC > Gamma-Al2O3 > sand. The petrochemical yield with LOSA-1 is 43.9% which is more than two times of that without catalyst. The feedstock for co-pyrolysis with lignin is polystyrene > polyethylene > polypropylene. Catalytic co-pyrolysis of black-liquor lignin with PS produced the maximum aromatic yield (55.3%), while co-pyrolysis with PE produced the maximum olefin yield (13%). Copyright © 2015 Elsevier Ltd. All rights reserved.

Kinetic study of corn straw pyrolysis: comparison of two different three-pseudocomponent models.

PubMed

Li, Zhengqi; Zhao, Wei; Meng, Baihong; Liu, Chunlong; Zhu, Qunyi; Zhao, Guangbo

2008-11-01

With heating rates of 20, 50 and 100 K min(-1), the thermal decomposition of corn straw samples (corn stalks skins, corn stalks cores, corn bracts and corn leaves) were studied using thermogravimetric analysis. The maximum pyrolysis rates increased with the heating rate increasing and the temperature at the peak pyrolysis rate also increased. Assuming the addition of three independent parallel reactions, corresponding to three pseudocomponents linked to the hemicellulose, cellulose and lignin, two different three-pseudocomponent models were used to simulate the corn straw pyrolysis. Model parameters of pyrolysis were given. It was found that the three-pseudocomponent model with n-order kinetics was more accurate than the model with first-order kinetics at most cases. It showed that the model with n-order kinetics was more accurate to describe the pyrolysis of the hemicellulose.

Evaluation of Pyrolysis Oil as Carbon Source for Fungal Fermentation

PubMed Central

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

2016-01-01

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

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

PubMed Central

Windt, Michael; Ziegler, Bernhard; Appelt, Jörn; Saake, Bodo; Meier, Dietrich; Bridgwater, Anthony

2017-01-01

Abstract The transformation of lignocellulosic biomass into bio‐based commodity chemicals is technically possible. Among thermochemical processes, fast pyrolysis, a relatively mature technology that has now reached a commercial level, produces a high yield of an organic‐rich liquid stream. Despite recent efforts to elucidate the degradation paths of biomass during pyrolysis, the selectivity and recovery rates of bio‐compounds remain low. In an attempt to clarify the general degradation scheme of biomass fast pyrolysis and provide a quantitative insight, the use of fast pyrolysis microreactors is combined with spectroscopic techniques (i.e., mass spectrometry and NMR spectroscopy) and mixtures of unlabeled and 13C‐enriched materials. The first stage of the work aimed to select the type of reactor to use to ensure control of the pyrolysis regime. A comparison of the chemical fragmentation patterns of “primary” fast pyrolysis volatiles detected by using GC‐MS between two small‐scale microreactors showed the inevitable occurrence of secondary reactions. In the second stage, liquid fractions that are also made of primary fast pyrolysis condensates were analyzed by using quantitative liquid‐state 13C NMR spectroscopy to provide a quantitative distribution of functional groups. The compilation of these results into a map that displays the distribution of functional groups according to the individual and main constituents of biomass (i.e., hemicelluloses, cellulose and lignin) confirmed the origin of individual chemicals within the fast pyrolysis liquids. PMID:28644517

Evaluation of Pyrolysis Oil as Carbon Source for Fungal Fermentation.

PubMed

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

2016-01-01

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

Sulfur Transformation during Microwave and Conventional Pyrolysis of Sewage Sludge.

PubMed

Zhang, Jun; Zuo, Wei; Tian, Yu; Chen, Lin; Yin, Linlin; Zhang, Jie

2017-01-03

The sulfur distributions and evolution of sulfur-containing compounds in the char, tar and gas fractions were investigated during the microwave and conventional pyrolysis of sewage sludge. Increased accumulation of sulfur in the char and less production of H 2 S were obtained from microwave pyrolysis at higher temperatures (500-800 °C). Three similar conversion pathways were identified for the formation of H 2 S during microwave and conventional pyrolysis. The cracking of unstable mercaptan structure in the sludge contributed to the release of H 2 S below 300 °C. The decomposition of aliphatic-S compounds in the tars led to the formation of H 2 S (300-500 °C). The thermal decomposition of aromatic-S compounds in the tars generated H 2 S from 500 to 800 °C. However, the secondary decomposition of thiophene-S compounds took place only in conventional pyrolysis above 700 °C. Comparing the H 2 S contributions from microwave and conventional pyrolysis, the significant increase of H 2 S yields in conventional pyrolysis was mainly attributed to the decomposition of aromatic-S (increasing by 10.4%) and thiophene-S compounds (11.3%). Further investigation on the inhibition mechanism of H 2 S formation during microwave pyrolysis confirmed that, with the special heating characteristics and relative shorter residence time, microwave pyrolysis promoted the retention of H 2 S on CaO and inhibited the secondary cracking of thiophene-S compounds at higher temperatures.

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

PubMed

Carrier, Marion; Windt, Michael; Ziegler, Bernhard; Appelt, Jörn; Saake, Bodo; Meier, Dietrich; Bridgwater, Anthony

2017-08-24

The transformation of lignocellulosic biomass into bio-based commodity chemicals is technically possible. Among thermochemical processes, fast pyrolysis, a relatively mature technology that has now reached a commercial level, produces a high yield of an organic-rich liquid stream. Despite recent efforts to elucidate the degradation paths of biomass during pyrolysis, the selectivity and recovery rates of bio-compounds remain low. In an attempt to clarify the general degradation scheme of biomass fast pyrolysis and provide a quantitative insight, the use of fast pyrolysis microreactors is combined with spectroscopic techniques (i.e., mass spectrometry and NMR spectroscopy) and mixtures of unlabeled and 13 C-enriched materials. The first stage of the work aimed to select the type of reactor to use to ensure control of the pyrolysis regime. A comparison of the chemical fragmentation patterns of "primary" fast pyrolysis volatiles detected by using GC-MS between two small-scale microreactors showed the inevitable occurrence of secondary reactions. In the second stage, liquid fractions that are also made of primary fast pyrolysis condensates were analyzed by using quantitative liquid-state 13 C NMR spectroscopy to provide a quantitative distribution of functional groups. The compilation of these results into a map that displays the distribution of functional groups according to the individual and main constituents of biomass (i.e., hemicelluloses, cellulose and lignin) confirmed the origin of individual chemicals within the fast pyrolysis liquids. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carpenter, Daniel; Westover, Tyler; Howe, Daniel

Here, we report here on an experimental study to produce refinery-ready fuel blendstocks via catalytic hydrodeoxygenation (upgrading) of pyrolysis oil using several biomass feedstocks and various blends. Blends were tested along with the pure materials to determine the effect of blending on product yields and qualities. Within experimental error, oil yields from fast pyrolysis and upgrading are shown to be linear functions of the blend components. Switchgrass exhibited lower fast pyrolysis and upgrading yields than the woody samples, which included clean pine, oriented strand board (OSB), and a mix of pinon and juniper (PJ). The notable exception was PJ, formore » which the poor upgrading yield of 18% was likely associated with the very high viscosity of the PJ fast pyrolysis oil (947 cp). The highest fast pyrolysis yield (54% dry basis) was obtained from clean pine, while the highest upgrading yield (50%) was obtained from a blend of 80% clean pine and 20% OSB (CP 8OSB 2). For switchgrass, reducing the fast pyrolysis temperature to 450 degrees C resulted in a significant increase to the pyrolysis oil yield and reduced hydrogen consumption during hydrotreating, but did not directly affect the hydrotreating oil yield. The water content of fast pyrolysis oils was also observed to increase linearly with the summed content of potassium and sodium, ranging from 21% for clean pine to 37% for switchgrass. Multiple linear regression models demonstrate that fast pyrolysis is strongly dependent upon the contents lignin and volatile matter as well as the sum of potassium and sodium.« less

Effects of Temperature and Steam Environment on Fatigue Behavior of Three SIC/SIC Ceramic Matrix Composites

DTIC Science & Technology

2008-09-01

Infiltration (CVI), Chemical Vapor Deposition (CVD) and polymer impregnation/ pyrolysis (PIP) [5:20, 32]. The SiC fibers currently... composite was infiltrated with a mixture of polymer , filler particles and solvent. During pyrolysis under nitrogen at temperatures > 1000 °C, the...using polymer infiltration and pyrolysis (PIP) method. Polymer infiltration and pyrolysis processing method allows near-net-shape molding and

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

DOE PAGES

Xiong, Qingang; Robichaud, David J.

2017-03-23

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

Reaction mechanisms in cellulose pyrolysis: a literature review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Molton, P.M.; Demmitt, T.F.

1977-08-01

A bibliographic review of 195 references is presented outlining the history of the research into the mechanisms of cellulose pyrolysis. Topics discussed are: initial product identification, mechanism of initial formation of levoglucosan, from cellulose and from related compounds, decomposition of cellulose to other compounds, formation of aromatics, pyrolysis of levoglucosan, crosslinking of cellulose, pyrolytic reactions of cellulose derivatives, and the effects of inorganic salts on the pyrolysis mechanism. (JSR)

On-Line Analysis and Kinetic Behavior of Arsenic Release during Coal Combustion and Pyrolysis.

PubMed

Shen, Fenghua; Liu, Jing; Zhang, Zhen; Dai, Jinxin

2015-11-17

The kinetic behavior of arsenic (As) release during coal combustion and pyrolysis in a fluidized bed was investigated by applying an on-line analysis system of trace elements in flue gas. This system, based on inductively coupled plasma optical emission spectroscopy (ICP-OES), was developed to measure trace elements concentrations in flue gas quantitatively and continuously. Obvious variations of arsenic concentration in flue gas were observed during coal combustion and pyrolysis, indicating strong influences of atmosphere and temperature on arsenic release behavior. Kinetic laws governing the arsenic release during coal combustion and pyrolysis were determined based on the results of instantaneous arsenic concentration in flue gas. A second-order kinetic law was determined for arsenic release during coal combustion, and the arsenic release during coal pyrolysis followed a fourth-order kinetic law. The results showed that the arsenic release rate during coal pyrolysis was faster than that during coal combustion. Thermodynamic calculations were carried out to identify the forms of arsenic in vapor and solid phases during coal combustion and pyrolysis, respectively. Ca3(AsO4)2 and Ca(AsO2)2 are the possible species resulting from As-Ca interaction during coal combustion. Ca(AsO2)2 is the most probable species during coal pyrolysis.

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

PubMed

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

2015-02-06

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

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

PubMed Central

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

2015-01-01

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

Chemical Characterization and Water Content Determination of Bio-Oils Obtained from Various Biomass Species using 31P NMR Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

David, K.; Ben, H.; Muzzy, J.

2012-03-01

Pyrolysis is a promising approach to utilize biomass for biofuels. One of the key challenges for this conversion is how to analyze complicated components in the pyrolysis oils. Water contents of pyrolysis oils are normally analyzed by Karl Fischer titration. The use of 2-chloro-4,4,5,5,-tetramethyl-1,3,2-dioxaphospholane followed by {sup 31}P NMR analysis has been used to quantitatively analyze the structure of hydroxyl groups in lignin and whole biomass. Results: {sup 31}P NMR analysis of pyrolysis oils is a novel technique to simultaneously characterize components and analyze water contents in pyrolysis oils produced from various biomasses. The water contents of various pyrolysis oilsmore » range from 16 to 40 wt%. The pyrolysis oils obtained from Loblolly pine had higher guaiacyl content, while that from oak had a higher syringyl content. Conclusion: The comparison with Karl Fischer titration shows that {sup 31}P NMR could also reliably be used to measure the water content of pyrolysis oils. Simultaneously with analysis of water content, quantitative characterization of hydroxyl groups, including aliphatic, C-5 substituted/syringyl, guaiacyl, p-hydroxyl phenyl and carboxylic hydroxyl groups, could also be provided by {sup 31}P NMR analysis.« less

A novel approach of solid waste management via aromatization using multiphase catalytic pyrolysis of waste polyethylene.

PubMed

Gaurh, Pramendra; Pramanik, Hiralal

2018-01-01

A new and innovative approach was adopted to increase the yield of aromatics like, benzene, toluene and xylene (BTX) in the catalytic pyrolysis of waste polyethylene (PE). The BTX content was significantly increased due to effective interaction between catalystZSM-5 and target molecules i.e., lower paraffins within the reactor. The thermal and catalytic pyrolysis both were performed in a specially designed semi-batch reactor at the temperature range of 500 °C-800 °C. Catalytic pyrolysis were performed in three different phases within the reactor batch by batch systematically, keeping the catalyst in A type- vapor phase, B type- liquid phase and C type- vapor and liquid phase (multiphase), respectively. Total aromatics (BTX) of 6.54 wt% was obtained for thermal pyrolysis at a temperature of 700 °C. In contrary, for the catalytic pyrolysis A, B and C types reactor arrangement, the aromatic (BTX) contents were progressively increased, nearly 6 times from 6.54 wt% (thermal pyrolysis) to 35.06 wt% for C-type/multiphase (liquid and vapor phase). The pyrolysis oil were characterized using GC-FID, FT-IR, ASTM distillation and carbon residue test to evaluate its end use and aromatic content. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pyrolysis processing for solid waste resource recovery

NASA Technical Reports Server (NTRS)

Wojtowicz, Marek A. (Inventor); Serio, Michael A. (Inventor); Kroo, Erik (Inventor); Suuberg, Eric M. (Inventor)

2007-01-01

Solid waste resource recovery in space is effected by pyrolysis processing, to produce light gases as the main products (CH.sub.4, H.sub.2, CO.sub.2, CO, H.sub.2O, NH.sub.3) and a reactive carbon-rich char as the main byproduct. Significant amounts of liquid products are formed under less severe pyrolysis conditions, and are cracked almost completely to gases as the temperature is raised. A primary pyrolysis model for the composite mixture is based on an existing model for whole biomass materials, and an artificial neural network models the changes in gas composition with the severity of pyrolysis conditions.

Concentration-response data on toxicity of pyrolysis gases from some natural and synthetic polymers

NASA Technical Reports Server (NTRS)

Hilado, C. J.; Huttlinger, N. V.

1978-01-01

Concentration-response data are presented on the toxic effects of the pyrolysis gases from some natural and synthetic polymers, using the toxicity screening test method developed at the University of San Francisco. The pyrolysis gases from wool, red oak, Douglas fir, polycaprolactam, polyether sulfone, polyaryl sulfone, and polyphenylene sulfide appeared to exhibit the concentration-response relationships commonly encountered in toxicology. Carbon monoxide seemed to be an important toxicant in the pyrolysis gases from red oak, Douglas fir, and polycaprolactam, but did not appear to have been the principal toxicant in the pyrolysis gases from polyether sulfone and polyphenylene sulfide.

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

PubMed

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.

Online study on the co-pyrolysis of coal and corn with vacuum ultraviolet photoionization mass spectrometry.

PubMed

Weng, Jun-Jie; Liu, Yue-Xi; Zhu, Ya-Nan; Pan, Yang; Tian, Zhen-Yu

2017-11-01

With the aim to support the experimental tests in a circulating fluidized bed pilot plant, the pyrolysis processes of coal, corn, and coal-corn blend have been studied with an online pyrolysis photoionization time-of-flight mass spectrometry (Py-PI-TOFMS). The mass spectra at different temperatures (300-800°C) as well as time-evolved profiles of selected species were measured. The pyrolysis products such as alkanes, alkenes, phenols, aromatics, as well as nitrogen- and sulfur-containing species were detected. As temperature rises, the relative ion intensities of high molecular weight products tend to decrease, while those of aromatics increase significantly. During the co-pyrolysis, coal can promote the reaction temperature of cellulose in corn. Time-evolved profiles demonstrate that coal can affect pyrolysis rate of cellulose, hemicellulose, and lignin of corn in blend. This work shows that Py-PI-TOFMS is a powerful approach to permit a better understanding of the mechanisms underlying the co-pyrolysis of coal and biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Boyan; Ou, Longwen; Dang, Qi

This study evaluates the techno-economic uncertainty in cost estimates for two emerging biorefinery technologies for biofuel production: in situ and ex situ catalytic pyrolysis. Stochastic simulations based on process and economic parameter distributions are applied to calculate biorefinery performance and production costs. The probability distributions for the minimum fuel-selling price (MFSP) indicate that in situ catalytic pyrolysis has an expected MFSP of $4.20 per gallon with a standard deviation of 1.15, while the ex situ catalytic pyrolysis has a similar MFSP with a smaller deviation ($4.27 per gallon and 0.79 respectively). These results suggest that a biorefinery based on exmore » situ catalytic pyrolysis could have a lower techno-economic risk than in situ pyrolysis despite a slightly higher MFSP cost estimate. Analysis of how each parameter affects the NPV indicates that internal rate of return, feedstock price, total project investment, electricity price, biochar yield and bio-oil yield are significant parameters which have substantial impact on the MFSP for both in situ and ex situ catalytic pyrolysis.« less

In situ upgrading of whole biomass to biofuel precursors with low average molecular weight and acidity by the use of zeolite mixture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ben, Haoxi; Huang, Fang; Li, Liwei

2015-09-09

The pyrolysis of whole biomass—pine wood and bark—with mordenite (M), beta (β) and Y zeolites has been examined at 600°C. The GPC results indicated that the pyrolysis oils upgraded by Y and β zeolites have a very low average molecular weight range (70–170 g mol –1). Several NMR methods have been employed to characterize the whole portion of pyrolysis products. After the use of these two zeolites (Y and β), the two main products from the pyrolysis of cellulose—levoglucosan and HMF—were eliminated; this indicates a significant deoxygenation process. When a mixture of zeolites (Y and M) was used, the upgradedmore » pyrolysis oil exhibited advantages provided by both zeolites; this pyrolysis oil represents a biofuel precursor that has a very low average molecular weight and a relatively low acidity. Finally, this study opens up a new way to upgrade pyrolysis oils by employing mixtures of different functional zeolites to produce biofuel/biochemical precursors from whole biomass.« less

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

PubMed

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

2012-03-01

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

Pyrolysis and reutilization of plant residues after phytoremediation of heavy metals contaminated sediments: For heavy metals stabilization and dye adsorption.

PubMed

Gong, Xiaomin; Huang, Danlian; Liu, Yunguo; Zeng, Guangming; Wang, Rongzhong; Wei, Jingjing; Huang, Chao; Xu, Piao; Wan, Jia; Zhang, Chen

2018-04-01

This study aimed to investigate the effect of pyrolysis on the stabilization of heavy metals in plant residues obtained after phytoremediation. Ramie residues, being collected after phytoremediation of metal contaminated sediments, were pyrolyzed at different temperatures (300-700 °C). Results indicated that pyrolysis was effective in the stabilization of Cd, Cr, Zn, Cu, and Pb in ramie residues by converting the acid-soluble fraction of metals into residual form and decreasing the TCLP-leachable metal contents. Meanwhile, the reutilization potential of using the pyrolysis products generated from ramie residues obtained after phytoremediation as sorbents was investigated. Adsorption experiments results revealed that the pyrolysis products presented excellent ability to adsorb methylene blue (MB) with a maximum adsorption capacity of 259.27 mg/g. This study demonstrated that pyrolysis could be used as an efficient alternative method for stabilizing heavy metals in plant residues obtained after phytoremediation, and their pyrolysis products could be reutilized for dye adsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of torrefaction pretreatment on the pyrolysis of rubber wood sawdust analyzed by Py-GC/MS.

PubMed

Chen, Wei-Hsin; Wang, Chao-Wen; Kumar, Gopalakrishnan; Rousset, Patrick; Hsieh, Tzu-Hsien

2018-07-01

The aim of this study was to investigate the effect of torrefaction on the pyrolysis of rubber wood sawdust (RWS) using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Three typical torrefaction temperatures (200, 250, and 300 °C) and pyrolysis temperatures (450, 500, and 550 °C) were considered. The results suggested that only diethyl phthalate, belonging to esters, was detected at the torrefaction temperatures of 200 and 250 °C, revealing hemicellulose degradation. With the torrefaction temperature of 300 °C, esters, aldehydes, and phenols were detected, suggesting the predominant decomposition of hemicellulose and lignin. The double-shot pyrolysis indicated that the contents of oxy-compounds such as acids and aldehydes in pyrolysis bio-oil decreased with rising torrefaction temperature, implying that increasing torrefaction severity abated oxygen content in the bio-oil. With the torrefaction temperature of 300 °C, relatively more cellulose was retained in the biomass because the carbohydrate content in the pyrolysis bio-oil increased significantly. Copyright © 2018 Elsevier Ltd. All rights reserved.

Potential of genetically engineered hybrid poplar for pyrolytic production of bio-based phenolic compounds.

PubMed

Toraman, Hilal E; Vanholme, Ruben; Borén, Eleonora; Vanwonterghem, Yumi; Djokic, Marko R; Yildiz, Guray; Ronsse, Frederik; Prins, Wolter; Boerjan, Wout; Van Geem, Kevin M; Marin, Guy B

2016-05-01

Wild-type and two genetically engineered hybrid poplar lines were pyrolyzed in a micro-pyrolysis (Py-GC/MS) and a bench scale setup for fast and intermediate pyrolysis studies. Principal component analysis showed that the pyrolysis vapors obtained by micro-pyrolysis from wood of caffeic acid O-methyltransferase (COMT) and caffeoyl-CoA O-methyltransferase (CCoAOMT) down-regulated poplar trees differed significantly from the pyrolysis vapors obtained from non-transgenic control trees. Both fast micro-pyrolysis and intermediate pyrolysis of transgenic hybrid poplars showed that down-regulation of COMT can enhance the relative yield of guaiacyl lignin-derived products, while the relative yield of syringyl lignin-derived products was up to a factor 3 lower. This study indicates that lignin engineering via genetic modifications of genes involved in the phenylpropanoid and monolignol biosynthetic pathways can help to steer the pyrolytic production of guaiacyl and syringyl lignin-derived phenolic compounds such as guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-vinylguaiacol, syringol, 4-vinylsyringol, and syringaldehyde present in the bio-oil. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diebold, J P

1997-04-01

The scaleup of biomass fast pyrolysis systems to large pilot and commercial scales will expose an increasingly large number of personnel to potential health hazards, especially during the evaluation of the commercial use of the pyrolysis condensates. Although the concept of fast pyrolysis to optimize liquid products is relatively new, low-temperature pyrolysis processes have been used over the aeons to produce charcoal and liquid by-products, e.g., smoky food flavors, food preservatives, and aerosols containing narcotics, e.g., nicotine. There are a number of studies in the historical literature that concern the hazards of acute and long-term exposure to smoke and tomore » the historical pyrolysis liquids formed at low temperatures. The reported toxicity of smoke, smoke food flavors, and fast pyrolysis oils is reviewed. The data found for these complex mixtures suggest that the toxicity may be less than that of the individual components. It is speculated that there may be chemical reactions that take place that serve to reduce the toxicity during aging. 81 refs.« less

Effect of torrefaction pretreatment and catalytic pyrolysis on the pyrolysis poly-generation of pine wood.

PubMed

Chen, Dengyu; Li, Yanjun; Deng, Minsi; Wang, Jiayang; Chen, Miao; Yan, Bei; Yuan, Qiqiang

2016-08-01

Torrefaction of pine wood was performed in a tube furnace at three temperatures (220, 250, and 280°C) for 30min. Then catalytic pyrolysis of raw and torrefied pine wood was performed using HZSM-5 catalyst in a fixed-bed pyrolysis reactor at 550°C for 15min. Torrefaction pretreatment and catalytic pyrolysis have an very important effect on the yield, property, and energy distribution of pyrolysis products. The results showed that the yield of biochar rapidly increased, while that of bio-oil decreased with increasing torrefaction temperature. The oxy-compound content of bio-oil, such as acids and aldehydes, sharply decreased. However, the aromatic hydrocarbon content not only increased but also further promoted by HZSM-5 catalyst. With highest mass yields and energy yields, biochar was also the very important product of pyrolysis. The oxygen content in biomass was mainly removed in the form of CO2 and H2O, leading to increasing CO2 content in non-condensable gas. Copyright © 2016 Elsevier Ltd. All rights reserved.

Flash Vacuum Pyrolysis: Techniques and Reactions.

PubMed

Wentrup, Curt

2017-11-20

Flash vacuum pyrolysis (FVP) had its beginnings in the 1940s and 1950s, mainly through mass spectrometric detection of pyrolytically formed free radicals. In the 1960s many organic chemists started performing FVP experiments with the purpose of isolating new and interesting compounds and understanding pyrolysis processes. Meanwhile, many different types of apparatus and techniques have been developed, and it is the purpose of this review to present the most important methods as well as a survey of typical reactions and observations that can be achieved with the various techniques. This includes preparative FVP, chemical trapping reactions, matrix isolation, and low temperature spectroscopy of reactive intermediates and unstable molecules, the use of online mass, photoelectron, microwave, and millimeterwave spectroscopies, gas-phase laser pyrolysis, pulsed pyrolysis with supersonic jet expansion, very low pressure pyrolysis for kinetic investigations, solution-spray and falling-solid FVP for involatile compounds, and pyrolysis over solid supports and reagents. Moreover, the combination of FVP with matrix isolation and photochemistry is a powerful tool for investigations of reaction mechanism. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of co-pyrolysis petrochemical wastewater sludge with lignite in a thermogravimetric analyzer and a packed-bed reactor: Pyrolysis characteristics, kinetics, and products analysis.

PubMed

Mu, Lin; Chen, Jianbiao; Yao, Pikai; Zhou, Dapeng; Zhao, Liang; Yin, Hongchao

2016-12-01

Co-pyrolysis characteristics of petrochemical wastewater sludge and Huolinhe lignite were investigated using thermogravimetric analyzer and packed-bed reactor coupled with Fourier transform infrared spectrometer and gas chromatography. The pyrolysis characteristics of the blends at various sludge blending ratios were compared with those of the individual materials. Thermogravimetric experiments showed that the interactions between the blends were beneficial to generate more residues. In packed-bed reactor, synergetic effects promoted the release of gas products and left less liquid and solid products than those calculated by additive manner. Fourier transform infrared spectrometer analysis showed that main functional groups in chars gradually disappeared with pyrolysis temperatures increasing, and H 2 O, CH 4 , CO, and CO 2 appeared in volatiles during pyrolysis. Gas compositions analysis indicated that, the yields of H 2 and CO clearly increased as the pyrolysis temperature and sludge blending ratio increasing, while the changes of CH 4 and CO 2 yields were relatively complex. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pyrolysis polygeneration of poplar wood: Effect of heating rate and pyrolysis temperature.

PubMed

Chen, Dengyu; Li, Yanjun; Cen, Kehui; Luo, Min; Li, Hongyan; Lu, Bin

2016-10-01

The pyrolysis of poplar wood were comprehensively investigated at different pyrolysis temperatures (400, 450, 500, 550, and 600°C) and at different heating rates (10, 30, and 50°C/min). The results showed that BET surface area of biochar, the HHV of non-condensable gas and bio-oil reached the maximum values of 411.06m(2)/g, 14.56MJ/m(3), and 14.39MJ/kg, under the condition of 600°C and 30°C/min, 600°C and 50°C/min, and 550°C and 50°C/min, respectively. It was conducive to obtain high mass and energy yield of bio-oil at 500°C and higher heating rate, while lower pyrolysis temperature and heating rate contributed towards obtaining both higher mass yield and energy yield of biochar. However, higher pyrolysis temperature and heating rate contributed to obtain both higher mass yield and energy yield of the non-condensable gas. In general, compared to the heating rate, the pyrolysis temperature had more effect on the product properties. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, J.; Elgowainy, A.; Palou-Rivera, I.

The pyrolysis of biomass can help produce liquid transportation fuels with properties similar to those of petroleum gasoline and diesel fuel. Argonne National Laboratory conducted a life-cycle (i.e., well-to-wheels [WTW]) analysis of various pyrolysis pathways by expanding and employing the Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (GREET) model. The WTW energy use and greenhouse gas (GHG) emissions from the pyrolysis pathways were compared with those from the baseline petroleum gasoline and diesel pathways. Various pyrolysis pathway scenarios with a wide variety of possible hydrogen sources, liquid fuel yields, and co-product application and treatment methods were considered. Atmore » one extreme, when hydrogen is produced from natural gas and when bio-char is used for process energy needs, the pyrolysis-based liquid fuel yield is high (32% of the dry mass of biomass input). The reductions in WTW fossil energy use and GHG emissions relative to those that occur when baseline petroleum fuels are used, however, is modest, at 50% and 51%, respectively, on a per unit of fuel energy basis. At the other extreme, when hydrogen is produced internally via reforming of pyrolysis oil and when bio-char is sequestered in soil applications, the pyrolysis-based liquid fuel yield is low (15% of the dry mass of biomass input), but the reductions in WTW fossil energy use and GHG emissions are large, at 79% and 96%, respectively, relative to those that occur when baseline petroleum fuels are used. The petroleum energy use in all scenarios was restricted to biomass collection and transportation activities, which resulted in a reduction in WTW petroleum energy use of 92-95% relative to that found when baseline petroleum fuels are used. Internal hydrogen production (i.e., via reforming of pyrolysis oil) significantly reduces fossil fuel use and GHG emissions because the hydrogen from fuel gas or pyrolysis oil (renewable sources) displaces that from fossil fuel natural gas and the amount of fossil natural gas used for hydrogen production is reduced; however, internal hydrogen production also reduces the potential petroleum energy savings (per unit of biomass input basis) because the fuel yield declines dramatically. Typically, a process that has a greater liquid fuel yield results in larger petroleum savings per unit of biomass input but a smaller reduction in life-cycle GHG emissions. Sequestration of the large amount of bio-char co-product (e.g., in soil applications) provides a significant carbon dioxide credit, while electricity generation from bio-char combustion provides a large energy credit. The WTW energy and GHG emissions benefits observed when a pyrolysis oil refinery was integrated with a pyrolysis reactor were small when compared with those that occur when pyrolysis oil is distributed to a distant refinery, since the activities associated with transporting the oil between the pyrolysis reactors and refineries have a smaller energy and emissions footprint than do other activities in the pyrolysis pathway.« less

Desulfurized gas production from vertical kiln pyrolysis

DOEpatents

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.

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

PubMed

Miskolczi, Norbert; Ateş, Funda; Borsodi, Nikolett

2013-09-01

Pyrolysis of real wastes (MPW and MSW) has been investigated at 500°C, 550°C and 600°C using Y-zeolite, β-zeolite, equilibrium FCC, MoO3, Ni-Mo-catalyst, HZSM-5 and Al(OH)3 as catalysts. The viscosity of pyrolysis oils could be decreased by the using of catalysts, especially by β-zeolite and MoO3. Both carbon frame and double bound isomerization was found in case of thermo-catalytic pyrolysis. Char morphology and texture analysis showed more coke deposits on the catalyst surface using MSW raw material. Pyrolysis oils had K, S, P Cl, Ca, Zn, Fe, Cr, Br and Sb as contaminants; and the concentrations of K, S, P, Cl and Br could be decreased by the using of catalysts. Copyright © 2013 Elsevier Ltd. All rights reserved.

Mathematical modeling of the heat transfer during pyrolysis process used for end-of-life tires treatment

NASA Astrophysics Data System (ADS)

Zheleva, I.; Georgiev, I.; Filipova, M.; Menseidov, D.

2017-10-01

Mathematical modeling of the heat transfer during the pyrolysis process used for the treatment of the End-of-Lifetires (EOLT) is presented in this paper. The pyrolysis process is 3D and non-stationary and because of this it is very complicated for modeling and studying. To simplify the modeling here a hierarchy of 2D models for the temperature which describe the non-stationary heat transfer in such a pyrolysis station is created. An algorithm for solving the model equations, based on MATLAB software is developed. The results for the temperature for some characteristic periods of operation of pyrolysis station are presented and commented in the paper. The results from this modeling can be used in the real pyrolysis station for more precise displacement of measurement devices and for designing of automated management of the process.

Effect of rate of pyrolysis on the textural properties of naturally-templated porous carbons from alginic acid.

PubMed

Marriott, Andrew S; Hunt, Andrew J; Bergström, Ed; Thomas-Oates, Jane; Clark, James H

2016-09-01

The effect of pyrolysis rate on the properties of alginic acid-derived carbonaceous materials, termed Starbon ® , was investigated. Thermal Gravimetry-IR was used to prepare porous carbons up to 800 °C at several rates and highlighted increased CO 2 production at higher pyrolysis rates. N 2 porosimetry of the resultant carbons shows how pyrolysis rate affects both the mesopore structure and thus surface area and surface energy. Surface capacity of these carbons was analysed by methylene blue dye adsorption. In general, as the rate of pyrolysis increased, the mesopore content and adsorbent capacity decreased. It is considered here that the rapid production of volatiles at these higher rates causes structural collapse of the non-templated pore network. The work here demonstrates that pyrolysis rate is a key variable which needs to be controlled to maximise the textural properties of Starbon ® required for adsorption applications.

Aromatics and phenols from catalytic pyrolysis of Douglas fir pellets in microwave with ZSM-5 as a catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lu; Lei, Hanwu; Ren, Shoujie

Microwave assisted catalytic pyrolysis was investigated to convert Douglas fir pellets to bio-oils by a ZSM-5 Zeolite catalyst. A central composite experimental design (CCD) was used to optimize the catalytic pyrolysis process. The effects of reaction time, temperature and catalyst to biomass ratio on the bio-oil, syngas, and biochar yields were determined. GC/MS analysis results showed that the bio-oil contained a series of important and useful chemical compounds. Phenols, guaiacols, and aromatic hydrocarbons were the most abundant compounds which were about 50-82 % in bio-oil depending on the pyrolysis conditions. Comparison between the bio-oils from microwave pyrolysis with and withoutmore » catalyst showed that the catalyst increased the content of aromatic hydrocarbons and phenols. A reaction pathway was proposed for microwave assisted catalyst pyrolysis of Douglas fir pellets.« less

Kinetics and evolved gas analysis for pyrolysis of food processing wastes using TGA/MS/FT-IR.

PubMed

Özsin, Gamzenur; Pütün, Ayşe Eren

2017-06-01

The objective of this study was to identify the pyrolysis of different bio-waste produced by food processing industry in a comprehensible manner. For this purpose, pyrolysis behaviors of chestnut shells (CNS), cherry stones (CS) and grape seeds (GS) were investigated by thermogravimetric analysis (TGA) combined with a Fourier-transform infrared (FT-IR) spectrometer and a mass spectrometer (MS). In order to make available theoretical groundwork for biomass pyrolysis, activation energies were calculated with the help of four different model-free kinetic methods. The results are attributed to the complex reaction schemes which imply parallel, competitive and complex reactions during pyrolysis. During pyrolysis, the evolution of volatiles was also characterized by FT-IR and MS. The main evolved gases were determined as H 2 O, CO 2 and hydrocarbons such as CH 4 and temperature dependent profiles of the species were obtained. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

Hassan, H; Lim, J K; Hameed, B H

2016-12-01

Co-pyrolysis of biomass with abundantly available materials could be an economical method for production of bio-fuels. However, elimination of oxygenated compounds poses a considerable challenge. Catalytic co-pyrolysis is another potential technique for upgrading bio-oils for application as liquid fuels in standard engines. This technique promotes the production of high-quality bio-oil through acid catalyzed reduction of oxygenated compounds and mutagenic polyaromatic hydrocarbons. This work aims to review and summarize research progress on co-pyrolysis and catalytic co-pyrolysis, as well as their benefits on enhancement of bio-oils derived from biomass. This review focuses on the potential of plastic wastes and coal materials as co-feed in co-pyrolysis to produce valuable liquid fuel. This paper also proposes future directions for using this technique to obtain high yields of bio-oils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermogravimetric and calorimetric characteristics during co-pyrolysis of municipal solid waste components.

PubMed

Ansah, Emmanuel; Wang, Lijun; Shahbazi, Abolghasem

2016-10-01

The thermogravimetric and calorimetric characteristics during pyrolysis of wood, paper, textile and polyethylene terephthalate (PET) plastic in municipal solid wastes (MSW), and co-pyrolysis of biomass-derived and plastic components with and without torrefaction were investigated. The active pyrolysis of the PET plastic occurred at a much higher temperature range between 360°C and 480°C than 220-380°C for the biomass derived components. The plastic pyrolyzed at a heating rate of 10°C/min had the highest maximum weight loss rate of 18.5wt%/min occurred at 420°C, followed by 10.8wt%/min at 340°C for both paper and textile, and 9.9wt%/min at 360°C for wood. At the end of the active pyrolysis stage, the final mass of paper, wood, textile and PET was 28.77%, 26.78%, 21.62% and 18.31%, respectively. During pyrolysis of individual MSW components at 500°C, the wood required the least amount of heat at 665.2J/g, compared to 2483.2J/g for textile, 2059.4J/g for paper and 2256.1J/g for PET plastic. The PET plastic had much higher activation energy of 181.86kJ/mol, compared to 41.47kJ/mol for wood, 50.01kJ/mol for paper and 36.65kJ/mol for textile during pyrolysis at a heating rate of 10°C/min. H2O and H2 peaks were observed on the MS curves for the pyrolysis of three biomass-derived materials but there was no obvious H2O and H2 peaks on the MS curves of PET plastic. There was a significant interaction between biomass and PET plastic during co-pyrolysis if the biomass fraction was dominant. The amount of heat required for the co-pyrolysis of the biomass and plastic mixture increased with the increase of plastic mass fraction in the mixture. Torrefaction at a proper temperature and time could improve the grindability of PET plastic. The increase of torrefaction temperature and time did not affect the temperature where the maximum pyrolytic rates occurred for both biomass and plastic but decreased the maximum pyrolysis rate of biomass and increased the maximum pyrolysis rate of PET plastic. The amount of heat for the pyrolysis of biomass and PET mixture co-torrefied at 280°C for 30min was 4365J/g at 500°C, compared to 1138J/g for the pyrolysis of raw 50% wood and 50% PET mixture at the same condition. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemistry of decomposition of freshwater wetland sedimentary organic material during ramped pyrolysis

NASA Astrophysics Data System (ADS)

Williams, E. K.; Rosenheim, B. E.

2011-12-01

Ramped pyrolysis methodology, such as that used in the programmed-temperature pyrolysis/combustion system (PTP/CS), improves radiocarbon analysis of geologic materials devoid of authigenic carbonate compounds and with low concentrations of extractable authochthonous organic molecules. The approach has improved sediment chronology in organic-rich sediments proximal to Antarctic ice shelves (Rosenheim et al., 2008) and constrained the carbon sequestration potential of suspended sediments in the lower Mississippi River (Roe et al., in review). Although ramped pyrolysis allows for separation of sedimentary organic material based upon relative reactivity, chemical information (i.e. chemical composition of pyrolysis products) is lost during the in-line combustion of pyrolysis products. A first order approximation of ramped pyrolysis/combustion system CO2 evolution, employing a simple Gaussian decomposition routine, has been useful (Rosenheim et al., 2008), but improvements may be possible. First, without prior compound-specific extractions, the molecular composition of sedimentary organic matter is unknown and/or unidentifiable. Second, even if determined as constituents of sedimentary organic material, many organic compounds have unknown or variable decomposition temperatures. Third, mixtures of organic compounds may result in significant chemistry within the pyrolysis reactor, prior to introduction of oxygen along the flow path. Gaussian decomposition of the reaction rate may be too simple to fully explain the combination of these factors. To relate both the radiocarbon age over different temperature intervals and the pyrolysis reaction thermograph (temperature (°C) vs. CO2 evolved (μmol)) obtained from PTP/CS to chemical composition of sedimentary organic material, we present a modeling framework developed based upon the ramped pyrolysis decomposition of simple mixtures of organic compounds (i.e. cellulose, lignin, plant fatty acids, etc.) often found in sedimentary organic material to account for changes in thermograph shape. The decompositions will be compositionally verified by 13C NMR analysis of pyrolysis residues from interrupted reactions. This will allow for constraint of decomposition temperatures of individual compounds as well as chemical reactions between volatilized moieties in mixtures of these compounds. We will apply this framework with 13C NMR analysis of interrupted pyrolysis residues and radiocarbon data from PTP/CS analysis of sedimentary organic material from a freshwater marsh wetland in Barataria Bay, Louisiana. We expect to characterize the bulk chemical composition during pyrolysis and as well as diagenetic changes with depth. Most importantly, we expect to constrain the potential and the limitations of this modeling framework for application to other depositional environments.

Recovery of materials from waste printed circuit boards by vacuum pyrolysis and vacuum centrifugal separation.

PubMed

Zhou, Yihui; Wu, Wenbiao; Qiu, Keqiang

2010-11-01

In this research, a two-step process consisting of vacuum pyrolysis and vacuum centrifugal separation was employed to treat waste printed circuit boards (WPCBs). Firstly, WPCBs were pyrolysed under vacuum condition at 600 °C for 30 min in a lab-scale reactor. Then, the obtained pyrolysis residue was heated under vacuum until the solder was melted, and then the molten solder was separated from the pyrolysis residue by the centrifugal force. The results of vacuum pyrolysis showed that the type-A of WPCBs (the base plates of which was made from cellulose paper reinforced phenolic resin) pyrolysed to form an average of 67.97 wt.% residue, 27.73 wt.% oil, and 4.30 wt.% gas; and pyrolysis of the type-B of WPCBs (the base plates of which was made from glass fiber reinforced epoxy resin) led to an average mass balance of 72.20 wt.% residue, 21.45 wt.% oil, and 6.35 wt.% gas. The results of vacuum centrifugal separation showed that the separation of solder was complete when the pyrolysis residue was heated at 400 °C, and the rotating drum was rotated at 1200 rpm for 10 min. The pyrolysis oil and gas can be used as fuel or chemical feedstock after treatment. The pyrolysis residue after solder separation contained various metals, glass fibers and other inorganic materials, which could be recycled for further processing. The recovered solder can be reused directly and it can also be a good resource of lead and tin for refining. Copyright © 2010 Elsevier Ltd. All rights reserved.

Extent of pyrolysis impacts on fast pyrolysis biochar properties.

PubMed

Brewer, Catherine E; Hu, Yan-Yan; Schmidt-Rohr, Klaus; Loynachan, Thomas E; Laird, David A; Brown, Robert C

2012-01-01

A potential concern about the use of fast pyrolysis rather than slow pyrolysis biochars as soil amendments is that they may contain high levels of bioavailable C due to short particle residence times in the reactors, which could reduce the stability of biochar C and cause nutrient immobilization in soils. To investigate this concern, three corn ( L.) stover fast pyrolysis biochars prepared using different reactor conditions were chemically and physically characterized to determine their extent of pyrolysis. These biochars were also incubated in soil to assess their impact on soil CO emissions, nutrient availability, microorganism population growth, and water retention capacity. Elemental analysis and quantitative solid-state C nuclear magnetic resonance spectroscopy showed variation in O functional groups (associated primarily with carbohydrates) and aromatic C, which could be used to define extent of pyrolysis. A 24-wk incubation performed using a sandy soil amended with 0.5 wt% of corn stover biochar showed a small but significant decrease in soil CO emissions and a decrease in the bacteria:fungi ratios with extent of pyrolysis. Relative to the control soil, biochar-amended soils had small increases in CO emissions and extractable nutrients, but similar microorganism populations, extractable NO levels, and water retention capacities. Corn stover amendments, by contrast, significantly increased soil CO emissions and microbial populations, and reduced extractable NO. These results indicate that C in fast pyrolysis biochar is stable in soil environments and will not appreciably contribute to nutrient immobilization. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

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

PubMed

Uçar, Suat; Karagöz, Selhan

2017-05-01

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

Kapton pyrolysis, the space environment and wiring requirements

NASA Technical Reports Server (NTRS)

Ferguson, Dale C.

1994-01-01

New Low Earth Orbit (LEO) requirements of space environment wiring are compared with traditional requirements. The pyrolysis of Kapton is reviewed for the LeRc vacuum chamber and the 1989 SSF. SEEB modeling of Kapton pyrolysis is also presented.

Influence of mineral matter on pyrolysis of palm oil wastes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Haiping; Chen, Hanping; Zheng, Chuguang

2006-09-15

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

Process for minimizing solids contamination of liquids from coal pyrolysis

DOEpatents

Wickstrom, Gary H.; Knell, Everett W.; Shaw, Benjamin W.; Wang, Yue G.

1981-04-21

In a continuous process for recovery of liquid hydrocarbons from a solid carbonaceous material by pyrolysis of the carbonaceous material in the presence of a particulate source of heat, particulate contamination of the liquid hydrocarbons is minimized. This is accomplished by removing fines from the solid carbonaceous material feed stream before pyrolysis, removing fines from the particulate source of heat before combining it with the carbonaceous material to effect pyrolysis of the carbonaceous material, and providing a coarse fraction of reduced fines content of the carbon containing solid residue resulting from the pyrolysis of the carbonaceous material before oxidizing carbon in the carbon containing solid residue to form the particulate source of heat.

Method and apparatus for producing pyrolysis oil having improved stability

DOEpatents

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

2016-12-27

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

Toxicity of thermal degradation products of spacecraft materials

NASA Technical Reports Server (NTRS)

Lawrence, W. H.; Turner, J. E.; Sanford, C.; Foster, S.; Baldwin, E.; Oconnor, J.

1982-01-01

Three polymeric materials were evaluated for relative toxicity of their pyrolysis products to rats by inhalation: Y-7683 (LS 200), Y-7684 (Vonar 3 on Fiberglass), and Y-7685 (Vonar 3 on N W Polyester). Criteria employed for assessing relative toxicity were (1) lethality from in-chamber pyrolysis, (2) lethality from an outside-of-chamber pyrolysis MSTL Procedure, and (3) disruption of trained rats' shock-avoidance performance during sub-lethal exposures to in-chamber pyrolysis of the materials.

An Environmental and Economic Evaluation of Pyrolysis for Energy Generation in Taiwan with Endogenous Land Greenhouse Gases Emissions

PubMed Central

Kung, Chih-Chun; McCarl, Bruce A.; Chen, Chi-Chung

2014-01-01

Taiwan suffers from energy insecurity and the threat of potential damage from global climate changes. Finding ways to alleviate these forces is the key to Taiwan’s future social and economic development. This study examines the economic and environmental impacts when ethanol, conventional electricity and pyrolysis-based electricity are available alternatives. Biochar, as one of the most important by-product from pyrolysis, has the potential to provide significant environmental benefits. Therefore, alternative uses of biochar are also examined in this study. In addition, because planting energy crops would change the current land use pattern, resulting in significant land greenhouse gases (GHG) emissions, this important factor is also incorporated. Results show that bioenergy production can satisfy part of Taiwan’s energy demand, but net GHG emissions offset declines if ethanol is chosen. Moreover, at high GHG price conventional electricity and ethanol will be driven out and pyrolysis will be a dominant technology. Fast pyrolysis dominates when ethanol and GHG prices are low, but slow pyrolysis is dominant at high GHG price, especially when land GHG emissions are endogenously incorporated. The results indicate that when land GHG emission is incorporated, up to 3.8 billion kWh electricity can be produced from fast pyrolysis, while up to 2.2 million tons of CO2 equivalent can be offset if slow pyrolysis is applied. PMID:24619159

Pyrolysis and catalytic pyrolysis as a recycling method of waste CDs originating from polycarbonate and HIPS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antonakou, E.V.; Kalogiannis, K.G.; Stephanidis, S.D.

Highlights: • Thermal and catalytic pyrolysis is a powerful method for recycling of WEEEs. • Liquid products obtained from the pyrolysis of PC or HIPS found in waste CDs are very different. • Mainly phenols are obtained from pyrolysis PC based wastes while aromatics from HIPS. • Use of MgO catalyst increases the amount of phenols from CD recycling compared to ZSM-5. • Use of MgO or ZSM-5 catalysts reduces the amount of styrene recovered from HIPS. - Abstract: Pyrolysis appears to be a promising recycling process since it could convert the disposed polymers to hydrocarbon based fuels or variousmore » useful chemicals. In the current study, two model polymers found in WEEEs, namely polycarbonate (PC) and high impact polystyrene (HIPS) and their counterparts found in waste commercial Compact Discs (CDs) were pyrolysed in a bench scale reactor. Both, thermal pyrolysis and pyrolysis in the presence of two catalytic materials (basic MgO and acidic ZSM-5 zeolite) was performed for all four types of polymers. Results have shown significant recovery of the monomers and valuable chemicals (phenols in the case of PC and aromatic hydrocarbons in the case of HIPS), while catalysts seem to decrease the selectivity towards the monomers and enhance the selectivity towards other desirable compounds.« less

An environmental and economic evaluation of pyrolysis for energy generation in Taiwan with endogenous land greenhouse gases emissions.

PubMed

Kung, Chih-Chun; McCarl, Bruce A; Chen, Chi-Chung

2014-03-11

Taiwan suffers from energy insecurity and the threat of potential damage from global climate changes. Finding ways to alleviate these forces is the key to Taiwan's future social and economic development. This study examines the economic and environmental impacts when ethanol, conventional electricity and pyrolysis-based electricity are available alternatives. Biochar, as one of the most important by-product from pyrolysis, has the potential to provide significant environmental benefits. Therefore, alternative uses of biochar are also examined in this study. In addition, because planting energy crops would change the current land use pattern, resulting in significant land greenhouse gases (GHG) emissions, this important factor is also incorporated. Results show that bioenergy production can satisfy part of Taiwan's energy demand, but net GHG emissions offset declines if ethanol is chosen. Moreover, at high GHG price conventional electricity and ethanol will be driven out and pyrolysis will be a dominant technology. Fast pyrolysis dominates when ethanol and GHG prices are low, but slow pyrolysis is dominant at high GHG price, especially when land GHG emissions are endogenously incorporated. The results indicate that when land GHG emission is incorporated, up to 3.8 billion kWh electricity can be produced from fast pyrolysis, while up to 2.2 million tons of CO2 equivalent can be offset if slow pyrolysis is applied.

Upgrading biomass pyrolysis bio-oil to renewable fuels.

DOT National Transportation Integrated Search

2015-01-01

Fast pyrolysis is a process that can convert woody biomass to a crude bio-oil (pyrolysis oil). However, some of these compounds : contribute to bio-oil shelf life instability and difficulty in refining. Catalytic hydrodeoxygenation (HDO) of the bio-o...

Economic assessment of flash co-pyrolysis of short rotation coppice and biopolymer waste streams.

PubMed

Kuppens, T; Cornelissen, T; Carleer, R; Yperman, J; Schreurs, S; Jans, M; Thewys, T

2010-12-01

The disposal problem associated with phytoextraction of farmland polluted with heavy metals by means of willow requires a biomass conversion technique which meets both ecological and economical needs. Combustion and gasification of willow require special and costly flue gas treatment to avoid re-emission of the metals in the atmosphere, whereas flash pyrolysis mainly results in the production of (almost) metal free bio-oil with a relatively high water content. Flash co-pyrolysis of biomass and waste of biopolymers synergistically improves the characteristics of the pyrolysis process: e.g. reduction of the water content of the bio-oil, more bio-oil and less char production and an increase of the HHV of the oil. This research paper investigates the economic consequences of the synergistic effects of flash co-pyrolysis of 1:1 w/w ratio blends of willow and different biopolymer waste streams via cost-benefit analysis and Monte Carlo simulations taking into account uncertainties. In all cases economic opportunities of flash co-pyrolysis of biomass with biopolymer waste are improved compared to flash pyrolysis of pure willow. Of all the biopolymers under investigation, polyhydroxybutyrate (PHB) is the most promising, followed by Eastar, Biopearls, potato starch, polylactic acid (PLA), corn starch and Solanyl in order of decreasing profits. Taking into account uncertainties, flash co-pyrolysis is expected to be cheaper than composting biopolymer waste streams, except for corn starch. If uncertainty increases, composting also becomes more interesting than flash co-pyrolysis for waste of Solanyl. If the investment expenditure is 15% higher in practice than estimated, the preference for flash co-pyrolysis compared to composting biopolymer waste becomes less clear. Only when the system of green current certificates is dismissed, composting clearly is a much cheaper processing technique for disposing of biopolymer waste. Copyright © 2010 Elsevier Ltd. All rights reserved.

Effect of rice husk ash mass on sustainability pyrolysis zone of fixed bed downdraft gasifier with capacity of 10 kg/hour

NASA Astrophysics Data System (ADS)

Surjosatyo, Adi; Haq, Imaduddin; Dafiqurrohman, Hafif; Gibran, Felly Rihlat

2017-03-01

The formation of pyrolysis sustainability (Sustainable Pyrolysis) is the objective of the gasification process. Pyrolysis zone in the gasification process is the result of the endothermic reaction that get heat from oxidation (combustion) of the fuel with oxygen, where cracking biomass rice husk result of such as charcoal, water vapor, steam tar, and gas - gas (CO, H 2, CH 4, CO 2 and N 2) and must be maintained at a pyrolysis temperature to obtain results plentiful gas (producer gas) or syngas (synthetic gas). Obtaining continuously syngas is indicated by flow rate (discharge) producer gas well and the consistency of the flame on the gas burner, it is highly influenced by the gasification process and the operation of the gasifier and the mass balance (mass balance) between the feeding rate of rice husk with the disposal of ash (ash removal). In experiments conducted is using fixed bed gasifier type downdraft capacity of 10 kg/h. Besides setting the mass of rice husks into the gasifier and disposal arrangements rice husk ash may affect the sustainability of the pyrolysis process, but tar produced during the gasification process causes sticky rice husk ash in the plenum gasifier. Modifications disposal system rice husk ash can facilitate the arrangement of ash disposal then could control the temperature pyrolysis with pyrolysis at temperatures between 500-750 ° C. The experimental study was conducted to determine the effect of mass quantities of rice husk ash issued against sustainability pyrolysis temperature which is obtained at each time disposal of rice husk ash to produce 60-90 grams of ash issued. From some experimental phenomena is expected to be seen pyrolysis and its effect on the flow rate of syngas and the stability of the flame on the gas burner so that this research can find a correlation to obtain performance (performance) gasifier optimal.

Effect of precursor concentration and spray pyrolysis temperature upon hydroxyapatite particle size and density.

PubMed

Cho, Jung Sang; Lee, Jeong-Cheol; Rhee, Sang-Hoon

2016-02-01

In the synthesis of hydroxyapatite powders by spray pyrolysis, control of the particle size was investigated by varying the initial concentration of the precursor solution and the pyrolysis temperature. Calcium phosphate solutions (Ca/P ratio of 1.67) with a range of concentrations from 0.1 to 2.0 mol/L were prepared by dissolving calcium nitrate tetrahydrate and diammonium hydrogen phosphate in deionized water and subsequently adding nitric acid. Hydroxyapatite powders were then synthesized by spray pyrolysis at 900°C and at 1500°C, using these calcium phosphate precursor solutions, under the fixed carrier gas flow rate of 10 L/min. The particle size decreased as the precursor concentration decreased and the spray pyrolysis temperature increased. Sinterability tests conducted at 1100°C for 1 h showed that the smaller and denser the particles were, the higher the relative densities were of sintered hydroxyapatite disks formed from these particles. The practical implication of these results is that highly sinterable small and dense hydroxyapatite particles can be synthesized by means of spray pyrolysis using a low-concentration precursor solution and a high pyrolysis temperature under a fixed carrier gas flow rate. © 2015 Wiley Periodicals, Inc.

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

PubMed

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

2016-05-01

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

Characteristics of maize biochar with different pyrolysis temperatures and its effects on organic carbon, nitrogen and enzymatic activities after addition to fluvo-aquic soil.

PubMed

Wang, Xiubin; Zhou, Wei; Liang, Guoqing; Song, Dali; Zhang, Xiaoya

2015-12-15

In this study, the characteristics of maize biochar produced at different pyrolysis temperatures (300, 450 and 600°C) and its effects on organic carbon, nitrogen and enzymatic activities after addition to fluvo-aquic soil were investigated. As pyrolysis temperature increased, ash content, pH, electrical conductivity, surface area, pore volume and aromatic carbon content of biochar increased while yield, ratios of oxygen:carbon and hydrogen: carbon and alkyl carbon content decreased. During incubation, SOC, total N, and ammonium-N contents increased in all biochar-amended treatments compared with the urea treatment; however, soil nitrate-N content first increased and then decreased with increasing pyrolysis temperature of the applied biochar. Extracellular enzyme activities associated with carbon transformation first increased and then decreased with biochars pyrolyzed at 450 and 600°C. Protease activity markedly increased with increased pyrolysis temperatures, whereas pyrolysis temperature had limited effect on soil urease activity. The results indicated that the responses of extracellular enzymes to biochar were dependent on the pyrolysis temperature, the enzyme itself and incubation time as well. Copyright © 2015. Published by Elsevier B.V.

Direct evidence from in situ FTIR spectroscopy that o-quinonemethide is a key intermediate during the pyrolysis of guaiacol.

PubMed

Cheng, Hao; Wu, Shubin; Huang, Jinbao; Zhang, Xiaohua

2017-04-01

Although o-quinonemethide (6-methylene-2,4-cyclohexadien-1-one) has been proposed as a key intermediate in char formation during the pyrolysis of guaiacol (2-methoxyphenol), direct evidence of this (e.g., spectroscopic data) has not yet been provided. Using in situ FTIR spectroscopy, the pyrolysis of guaiacol was investigated from 30 °C to 630 °C at 40 °C/min. The IR profiles showed direct evidence of o-quinonemethide production at about 350 °C, which vanished rapidly at around 420 °C in the vapor phase, indicating char formation. In addition, at 400 °C, salicyl aldehyde was observed, which decomposed slowly at about 500 °C. In combination with the known products of guaiacol pyrolysis, these results allowed the major reaction pathways of guaiacol pyrolysis to be discerned. Density functional theory calculations were performed, and the results were found to be in good agreement with the experimentally obtained IR profiles. These findings provide guidance on how to suppress secondary reactions of guaiacol during lignin pyrolysis. Graphical abstract On-line analysis of pyrolysis process of guaiacol using in situ FTIR.

Nitrogen dioxide produced by self-sustained pyrolysis of nitrous oxide

NASA Technical Reports Server (NTRS)

Sabol, A. P.

1965-01-01

Apparatus is developed for achieving continuous self-sustaining pyrolysis reaction in the production of nitrogen dioxide from nitrous oxide. The process becomes self-sustaining because of the exothermic reaction and the regenerative heating of the gases in the pyrolysis chamber.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Coal liquefaction with subsequent bottoms pyrolysis

DOEpatents

Walchuk, George P.

1978-01-01

In a coal liquefaction process wherein heavy bottoms produced in a liquefaction zone are upgraded by coking or a similar pyrolysis step, pyrolysis liquids boiling in excess of about 1000.degree. F. are further reacted with molecular hydrogen in a reaction zone external of the liquefaction zone, the resulting effluent is fractionated to produce one or more distillate fractions and a bottoms fraction, a portion of this bottoms fraction is recycled to the reaction zone, and the remaining portion of the bottoms fraction is recycled to the pyrolysis step.

Birth, Death and Transfiguration; The Synthesis of Preceramic Polymers, Their Pyrolysis and Their Conversion to Ceramics (Preprint)

DTIC Science & Technology

1989-05-31

have been able to prepare preceramic polymers whose pyrolysis gives -99% SiC , -99.5% Si 3N 4 , or any mixture of the two by appropriate manipulation of...SYNTHESIS OF PRECERAMIC POLYMERS , THEIR PYROLYSIS AND THEIR CONVERSION TO CERAMICS by Dietmar Seyferth ELCTE D MAY 1 9 989 EEl To be published MAY U...CLASSIFICATION OF THIS PAGE All other editions are obsolete. BIRTH, DEATH AND TRANSFIGURATION: THE SYNTHESIS OF PRECERAMIC POLYMERS , THEIR PYROLYSIS

Co-pyrolysis of polypropylene waste with Brazilian heavy oil.

PubMed

Assumpção, Luiz C F N; Carbonell, Montserrat M; Marques, Mônica R C

2011-01-01

To evaluate the chemical recycling of plastic residues, co-pyrolysis of polypropylene (PP) waste with Brazilian crude oil was evaluated varying the temperature (400°C to 500°C) and the amount of PP fed to the reactor. The co-pyrolysis of plastic waste in an inert atmosphere provided around 80% of oil pyrolytic, and of these, half represent the fraction of diesel oil. This study can be used as a reference in chemical recycling of plastics, specially associated with plastics co-pyrolysis.

Pyrolysis with cyclone burner

DOEpatents

Green, Norman W.; Duraiswamy, Kandaswamy; Lumpkin, Robert E.

1978-07-25

In a continuous process for recovery of values contained in a solid carbonaceous material, the carbonaceous material is comminuted and then subjected to flash pyrolysis in the presence of a particulate heat source over an overflow weir to form a pyrolysis product stream containing a carbon containing solid residue and volatilized hydrocarbons. After the carbon containing solid residue is separated from the pyrolysis product stream, values are obtained by condensing volatilized hydrocarbons. The particulate source of heat is formed by oxidizing carbon in the solid residue and separating out the fines.

Pyrolysis with staged recovery

DOEpatents

Green, Norman W.; Duraiswamy, Kandaswamy; Lumpkin, Robert E.; Winter, Bruce L.

1979-03-20

In a continuous process for recovery of values contained in a solid carbonaceous material, the carbonaceous material is comminuted and then subjected to flash pyrolysis in the presence of a particulate heat source fed over an overflow weir to form a pyrolysis product stream containing a carbon containing solid residue and volatilized hydrocarbons. After the carbon containing solid residue is separated from the pyrolysis product stream, values are obtained by condensing volatilized hydrocarbons. The particulate source of heat is formed by oxidizing carbon in the solid residue.

Kinetics of scrap tyre pyrolysis under vacuum conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, Gartzen; Aguado, Roberto; Olazar, Martin

2009-10-15

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene-butadiene rubber) according to three successive steps. The latter method identifies themore » kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12 K in the reaction starting temperature. The kinetic constant at 503 K for devolatilization of volatile additives at 0.25 atm is 1.7 times higher than that at 1 atm, and that corresponding to styrene-butadiene rubber at 723 K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability. The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.« less

Kinetics of scrap tyre pyrolysis under vacuum conditions.

PubMed

Lopez, Gartzen; Aguado, Roberto; Olazar, Martín; Arabiourrutia, Miriam; Bilbao, Javier

2009-10-01

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene-butadiene rubber) according to three successive steps. The latter method identifies the kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12K in the reaction starting temperature. The kinetic constant at 503K for devolatilization of volatile additives at 0.25atm is 1.7 times higher than that at 1atm, and that corresponding to styrene-butadiene rubber at 723K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability. The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.

Study on the combined sewage sludge pyrolysis and gasification process: mass and energy balance.

PubMed

Wang, Zhonghui; Chen, Dezhen; Song, Xueding; Zhao, Lei

2012-12-01

A combined pyrolysis and gasification process for sewage sludge was studied in this paper for the purpose of its safe disposal with energy self-balance. Three sewage sludge samples with different dry basis lower heat values (LHV(db)) were used to evaluate the constraints on this combined process. Those samples were pre-dried and then pyrolysed within the temperature range of 400-550 degrees C. Afterwards, the char obtained from pyrolysis was gasified to produce fuel gas. The experimental results showed that the char yield ranged between 37.28 and 53.75 wt% of the dry sludge and it changed with ash content, pyrolysis temperature and LHV(db) of the sewage sludge. The gas from char gasification had a LHV around 5.31-5.65 MJ/Nm3, suggesting it can be utilized to supply energy in the sewage sludge drying and pyrolysis process. It was also found that energy balance in the combined process was affected by the LHV(db) of sewage sludge, moisture content and pyrolysis temperature. Higher LHV(db), lower moisture content and higher pyrolysis temperature benefit energy self-balance. For sewage sludge with a moisture content of 80 wt%, LHV(db) of sewage sludge should be higher than 18 MJ/kg and the pyrolysis temperature should be higher than 450 degrees C to maintain energy self-sufficiency when volatile from the pyrolysis process is the only energy supplier; when the LHV(db) was in the range of 14.65-18 MJ/kg, energy self-balance could be maintained in this combined process with fuel gas from char gasification as a supplementary fuel; auxiliary fuel was always needed if the LHV(db) was lower than 14.65 MJ/kg.

Pyrolysis and co-pyrolysis of Laminaria japonica and polypropylene over mesoporous Al-SBA-15 catalyst.

PubMed

Lee, Hyung Won; Choi, Suek Joo; Park, Sung Hoon; Jeon, Jong-Ki; Jung, Sang-Chul; Kim, Sang Chai; Park, Young-Kwon

2014-01-01

The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N2 adsorption-desorption isotherms, and NH3 temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H2O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro-d-galactitol and 1,5-anhydro-d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H2O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis.

Pyrolysis and co-pyrolysis of Laminaria japonica and polypropylene over mesoporous Al-SBA-15 catalyst

NASA Astrophysics Data System (ADS)

Lee, Hyung Won; Choi, Suek Joo; Park, Sung Hoon; Jeon, Jong-Ki; Jung, Sang-Chul; Kim, Sang Chai; Park, Young-Kwon

2014-08-01

The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N2 adsorption-desorption isotherms, and NH3 temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H2O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro- d-galactitol and 1,5-anhydro- d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H2O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis.

Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading

DOE PAGES

Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.; ...

2017-11-24

Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less

Characterization of herb residue and high ash-containing paper sludge blends from fixed bed pyrolysis.

PubMed

Li, Tiantao; Guo, Feiqiang; Li, Xiaolei; Liu, Yuan; Peng, Kuangye; Jiang, Xiaochen; Guo, Chenglong

2018-04-10

High ash-containing paper sludge which is rich in various metal oxides is employed in herb residue pyrolysis to enhance the yield of fuel gas and reduce tar yield in a drop tube fixed bed reactor. Effects of heat treatment temperature and blending ratio of paper sludge on the yields and composition of pyrolysis products (gas, tar and char) were investigated. Results indicate that paper sludge shows a significantly catalytic effect during the pyrolysis processes of herb residue, accelerating the pyrolysis reactions. The catalytic effect resulted in an increase in gas yield but a decrease in tar yield. The catalytic effect degree is affected by the paper sludge proportions, and the strongest catalytic effect of paper sludge is noted at its blending ratio of 50%. At temperature lower than 900 °C, the catalytic effect of paper sludge in the pyrolysis of herb residue promotes the formation of H 2 and CO 2 , inhibits the formation of CH 4 , but shows slight influence on the formations of CO, while the formation of the four gas components was all promoted at 900 °C. SEM results of residue char show that ash particles from paper sludge adhere to the surface of the herb residue char after pyrolysis, which may promote the pyrolysis process of herb residue for more gas releasing. FT-IR results indicate that most functional groups disappear after pyrolysis. The addition of paper sludge promotes deoxidisation and aromatization reactions of hetero atoms tars, forming heavier polycyclic aromatic hydrocarbons and leading to tar yield decrease. Copyright © 2018 Elsevier Ltd. All rights reserved.

Pyrolysis and co-pyrolysis of Laminaria japonica and polypropylene over mesoporous Al-SBA-15 catalyst

PubMed Central

2014-01-01

The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N2 adsorption-desorption isotherms, and NH3 temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H2O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro-d-galactitol and 1,5-anhydro-d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H2O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis. PMID:25136282

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elliott, Douglas C.; Meier, Dietrich; Oasmaa, Anja

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 themore » 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.« less

Improving biomass pyrolysis economics by integrating vapor and liquid phase upgrading

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iisa, Kristiina; Robichaud, David J.; Watson, Michael J.

Partial deoxygenation of bio-oil by catalytic fast pyrolysis with subsequent coupling and hydrotreating can lead to improved economics and will aid commercial deployment of pyrolytic conversion of biomass technologies. Biomass pyrolysis efficiently depolymerizes and deconstructs solid plant matter into carbonaceous molecules that, upon catalytic upgrading, can be used for fuels and chemicals. Upgrading strategies include catalytic deoxygenation of the vapors before they are condensed (in situ and ex situ catalytic fast pyrolysis), or hydrotreating following condensation of the bio-oil. In general, deoxygenation carbon efficiencies, one of the most important cost drivers, are typically higher for hydrotreating when compared to catalyticmore » fast pyrolysis alone. However, using catalytic fast pyrolysis as the primary conversion step can benefit the entire process chain by: (1) reducing the reactivity of the bio-oil, thereby mitigating issues with aging and transport and eliminating need for multi-stage hydroprocessing configurations; (2) producing a bio-oil that can be fractionated through distillation, which could lead to more efficient use of hydrogen during hydrotreating and facilitate integration in existing petroleum refineries; and (3) allowing for the separation of the aqueous phase. In this perspective, we investigate in detail a combination of these approaches, where some oxygen is removed during catalytic fast pyrolysis and the remainder removed by downstream hydrotreating, accompanied by carbon–carbon coupling reactions in either the vapor or liquid phase to maximize carbon efficiency toward value-driven products (e.g. fuels or chemicals). The economic impact of partial deoxygenation by catalytic fast pyrolysis will be explored in the context of an integrated two-stage process. In conclusion, improving the overall pyrolysis-based biorefinery economics by inclusion of production of high-value co-products will be examined.« less

Comparative study on pyrolysis of lignocellulosic and algal biomass using pyrolysis-gas chromatography/mass spectrometry.

PubMed

Li, Kai; Zhang, Liqiang; Zhu, Liang; Zhu, Xifeng

2017-06-01

The cornstalk and chlorella were selected as the representative of lignocelulosic and algal biomass, and the pyrolysis experiments of them were carried out using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The physicochemical properties of samples and the pyrolytic product distribution were presented. And then the compositional differences between the two kinds of pyrolytic products were studied, the relevant pyrolysis mechanisms were analyzed systematically. Pyrolytic vapor from lignocellulosic biomass contained more phenolic and carbonyl compounds while that from algal biomass contained more long-chain fatty acids, nitrogen-containing compounds and fewer carbonyl compounds. Maillard reaction is conducive to the conversion of carbonyl compounds to nitrogenous heterocyclic compounds with better thermal stability. Copyright © 2017 Elsevier Ltd. All rights reserved.

Site-Specific Pyrolysis Induced Cleavage at Aspartic Acid Residue in Peptides and Proteins

PubMed Central

Zhang, Shaofeng; Basile, Franco

2011-01-01

A simple and site-specific non-enzymatic method based on pyrolysis has been developed to cleave peptides and proteins. Pyrolytic cleavage was found to be specific and rapid as it induced a cleavage at the C-terminal side of aspartic acid in the temperature range of 220–250 °C in 10 seconds. Electrospray Ionization (ESI) mass spectrometry (MS) and tandem-MS (MS/MS) were used to characterize and identify pyrolysis cleavage products, confirming that sequence information is conserved after the pyrolysis process in both peptides and protein tested. This suggests that pyrolysis-induced cleavage at aspartyl residues can be used as a rapid protein digestion procedure for the generation of sequence specific protein biomarkers. PMID:17388620

Charcoal from the pyrolysis of rapeseed plant straw-stalk

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karaosmanoglu, F.; Tetik, E.

1999-07-01

Charcoal is an important product of pyrolysis of biomass sources. Charcoal can be used for domestic, agricultural, metallurgical, and chemical purposes. In this study different characteristics of charcoal, one of the rape seed plant straw-stalk pyrolysis product, was researched and presented as candidates.

Firefighting and Emergency Response Study of Advanced Composites Aircraft; Objective 1: Composite Material Damage in Minor Aircraft Fires

DTIC Science & Technology

2013-05-18

26 4.3. 1-D Heat Transfer Model with Pyrolysis and Thermal Damage...Improvements and Added Features ........................................................................31 4.3.4. Pyrolysis Model Calibration... Pyrolysis Model ................................................32 Figure 25. Updated Heat Transfer Algorithm Flow Chart

Simulating Biomass Fast Pyrolysis at the Single Particle Scale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ciesielski, Peter; Wiggins, Gavin; Daw, C Stuart

2017-07-01

Simulating fast pyrolysis at the scale of single particles allows for the investigation of the impacts of feedstock-specific parameters such as particle size, shape, and species of origin. For this reason particle-scale modeling has emerged as an important tool for understanding how variations in feedstock properties affect the outcomes of pyrolysis processes. The origins of feedstock properties are largely dictated by the composition and hierarchical structure of biomass, from the microstructural porosity to the external morphology of milled particles. These properties may be accounted for in simulations of fast pyrolysis by several different computational approaches depending on the level ofmore » structural and chemical complexity included in the model. The predictive utility of particle-scale simulations of fast pyrolysis can still be enhanced substantially by advancements in several areas. Most notably, considerable progress would be facilitated by the development of pyrolysis kinetic schemes that are decoupled from transport phenomena, predict product evolution from whole-biomass with increased chemical speciation, and are still tractable with present-day computational resources.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

Volatile Analysis by Pyrolysis of Regolith for Planetary Resource Exploration

NASA Technical Reports Server (NTRS)

Glavin, Daniel P.; Malespin, Charles; ten Kate, Inge L.; Getty, Stephanie A.; Holmes, Vincent E.; Mumm, Erik; Franz, Heather B.; Noreiga, Marvin; Dobson, Nick; Southard, Adrian E.;

Microwave pyrolysis of oily sludge with activated carbon.

PubMed

Chen, Yi-Rong

2016-12-01

The aim of this study is to explore catalytic microwave pyrolysis of crude oil storage tank sludge for fuels using granular activated carbon (GAC) as a catalyst. The effect of GAC loading on the yield of pyrolysis products was also investigated. Heating rate of oily sludge and yield of microwave pyrolysis products such as oil and fuel gas was found to depend on the ratio of GAC to oily sludge. The optimal GAC loading was found to be 10%, while much smaller and larger feed sizes adversely influenced production. During oily sludge pyrolysis, a maximum oil yield of 77.5% was achieved. Pyrolytic oils with high concentrations of diesel oil and gasoline (about 70 wt% in the pyrolytic oil) were obtained. The leaching of heavy metals, such as Cr, As and Pb, was also suppressed in the solid residue after pyrolysis. This technique provides advantages such as harmless treatment of oily sludge and substantial reduction in the consumption of energy, time and cost.

Study on co-pyrolysis characteristics of rice straw and Shenfu bituminous coal blends in a fixed bed reactor.

PubMed

Li, Shuaidan; Chen, Xueli; Liu, Aibin; Wang, Li; Yu, Guangsuo

2014-03-01

Co-pyrolysis behaviors of rice straw and Shenfu bituminous coal were studied in a fixed bed reactor under nitrogen atmosphere. The pyrolysis temperatures were 700°C, 800°C and 900°C, respectively. Six different biomass ratios were used. Gas, tar components were analyzed by a gas chromatograph and a gas chromatography-mass spectrometry respectively. Under co-pyrolysis conditions, the gas volume yields are higher than the calculated values. Co-pyrolysis tar contains more phenolics, less oxygenate compounds than calculated values. The addition of biomass changes the atmosphere during the pyrolysis process and promotes tar decomposition. The SEM results show that the differences between the blended char and their parents char are not significant. The results of char yields and ultimate analysis also show that no significant interactions exist between the two kinds of particles. The changes of gas yield and components are caused by the secondary reactions and tar decomposition. Copyright © 2014 Elsevier Ltd. All rights reserved.

Pyrolysis characteristics and pathways of protein, lipid and carbohydrate isolated from microalgae Nannochloropsis sp.

PubMed

Wang, Xin; Sheng, Lili; Yang, Xiaoyi

2017-04-01

Microalgal components were isolated gradually to get lipid-rich, protein-rich and carbohydrate-rich components. The aim of this work was to study pyrolysis mechanism of microalgae by real isolated real algae components. Thermogrametric analysis (DTG) curve of microalgae was fitted by single pyrolysis curves of protein, lipid and carbohydrate except special zones, which likely affected by cell disruption and hydrolysis mass loss. Experimental microalgae liquefaction without water index N was 0.6776, 0.3861 and 0.2856 for isolated lipid, protein and carbohydrate. Pyrolysis pathways of lipid are decarboxylation, decarbonylation, fragmentation of glycerin moieties and steroid to form hydrocarbons, carboxylic acids and esters. Pyrolysis pathways of protein are decarboxylation, deamination, hydrocarbon residue fragmentation, dimerization and fragmentation of peptide bonds to form amide/amines/nitriles, esters, hydrocarbons and N-heterocyclic compounds, especially diketopiperazines (DKPs). Pyrolysis pathways of carbohydrate are dehydrated reactions and further fragmentation to form ketones and aldehyde, decomposition of lignin to form phenols, and fragmentation of lipopolysaccharides. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2016-01-01

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

Effects of hydrothermal treatment on the pyrolysis behavior of Chinese fan palm.

PubMed

Yao, Zhongliang; Ma, Xiaoqian

2018-01-01

The effect of hydrothermal treatment (HTT) on Chinese fan palm pyrolysis was investigated. It indicated that HTT could effectively remove a large portion of alkali/alkaline earth metals and disrupt the chemical structure to a certain extent. HTT delayed the initial decomposition temperature but accelerated the pyrolysis process completely. HTT also increased the relative contents of both sugars and hydrocarbons in pyrolysis. At 210°C, HTT had the most significant promotion effect on the sugars formation with the relative content of 30.58%. While, The relative content of phenols, acids, furans, aldehydes, esters and CO 2 decreased more or less after HTT. With increasing pyrolysis temperature, the relative content of most groups of chemicals except hydrocarbons decreased. Response contours were analyzed to find the optimal reaction conditions for generating acids, phenols, sugars and hydrocarbons, respectively. The results indicated both pyrolysis temperature and HTT temperature had distinct influence on relative contents of products. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

DOE PAGES

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

2012-01-01

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

Recycling of organic materials and solder from waste printed circuit boards by vacuum pyrolysis-centrifugation coupling technology.

PubMed

Zhou, Yihui; Wu, WenBiao; Qiu, Keqiang

2011-12-01

Here, we focused on the recycling of waste printed circuit boards (WPCBs) using vacuum pyrolysis-centrifugation coupling technology (VPCT) aiming to obtain valuable feedstock and resolve environmental pollution. The two types of WPCBs were pyrolysed at 600°C for 30 min under vacuum condition. During the pyrolysis process, the solder of WPCBs was separated and recovered when the temperature range was 400-600°C, and the rotating drum was rotated at 1000 rpm for 10 min. The type-A of WPCBs pyrolysed to form an average of 67.91 wt.% residue, 27.84 wt.% oil, and 4.25 wt.% gas; and pyrolysis of the type-B of WPCBs led to an average mass balance of 72.22 wt.% residue, 21.57 wt.% oil, and 6.21 wt.% gas. The GC-MS and FT-IR analyses showed that the two pyrolysis oils consisted mainly of phenols and substituted phenols. The pyrolysis oil can be used for fuel or chemical feedstock for further processing. The recovered solder can be recycled directly and it can also be a good resource of lead and tin for refining. The pyrolysis residues contained various metals, glass fibers and other inorganic materials, which could be recovered after further treatment. The pyrolysis gases consisted mainly of CO, CO(2), CH(4), and H(2), which could be collected and recycled. Copyright © 2011 Elsevier Ltd. All rights reserved.

Reliable Characterization for Pyrolysis Bio-Oils Leads to Enhanced

Science.gov Websites

Upgrading Methods | NREL Reliable Characterization for Pyrolysis Bio-Oils Leads to Enhanced Upgrading Methods Science and Technology Highlights Highlights in Research & Development Reliable Characterization for Pyrolysis Bio-Oils Leads to Enhanced Upgrading Methods Key Research Results Achievement As co

Publications - GMC 13 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 13 Publication Details Title: Total organic carbon, rock-eval pyrolysis and vitrinite information. Bibliographic Reference Phillips Petroleum Company, 1983, Total organic carbon, rock-eval K) Keywords Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of Page

Pyrolysis of humic and fulvic acids

USGS Publications Warehouse

Wershaw, R. L.; Bohner, G.E.

1969-01-01

Pyrolysis of humic and fulvic acids isolated from a North Carolina soil yields a variety of aromatic, heterocyclic and straight chain organ compounds. The pyrolysis products identified by gas chromatography and mass spectrometry indicate that humic and fulvic acids have aromatic and polysaccharide structures in their molecules. ?? 1969.

The Construction of a Simple Pyrolysis Gas Chromatograph.

ERIC Educational Resources Information Center

Hedrick, Jack L.

1982-01-01

Describes a simple and inexpensive pyrolysis gas chromatography (PGC) system constructed from items available in undergraduate institutions. The system is limited, accepting only liquid samples and pyrolyzing "on the fly" rather than statically and not allowing for reductive pyrolysis. Applications, experiments, and typical results are included.…

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

USDA-ARS?s Scientific Manuscript database

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

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

USDA-ARS?s Scientific Manuscript database

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

Robert M. Baldwin | NREL

Science.gov Websites

, upgrading of bio-oil, and advanced biofuels. His interests include: Catalytic fast pyrolysis and bio-oil co Oil," U.S. Patent No. 4,576,708 (1986) Featured Publications "Improving Biomass Pyrolysis of Pyrolysis Oil in Existing Refineries, Part 2," Hydrocarbon Processing (2017) "

Applications and limitations to use of rice hull biochar in container substrates

USDA-ARS?s Scientific Manuscript database

Biochar is the charred organic matter that remains after pyrolysis of biomass or manure. Biochars from different feedstock yield different properties as a result of their differing particle sizes at the time of pyrolysis, inherent ash content of the feedstock, pyrolysis conditions, and storage cond...

Publications - GMC 125 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 125 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite Reference Cunningham, K., and Shell Oil Company, 1989, Total organic carbon, rock-eval pyrolysis, and Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of Page Department of Natural Resources, Division

Publications - GMC 122 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 122 Publication Details Title: Total organic carbon, rock-eval pyrolysis, vitrinite for more information. Bibliographic Reference Exxon, and Geo-Strat, Inc., 1989, Total organic carbon Information gmc122.pdf (1.4 M) Keywords Kerogen; Pyrolysis; Rock-Eval Pyrolysis; Total Organic Carbon

Publications - GMC 62 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 62 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite . Bibliographic Reference Unknown, 1985, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of Page Department of Natural Resources, Division

Publications - GMC 59 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS GMC 59 Publication Details Title: Total organic carbon, rock-eval pyrolysis, and vitrinite . Bibliographic Reference Unknown, 1985, Total organic carbon, rock-eval pyrolysis, and vitrinite reflectance -Eval Pyrolysis; Total Organic Carbon; Vitrinite Reflectance Top of Page Department of Natural Resources

Catalytic pyrolysis-GC/MS of lignin from several sources

USDA-ARS?s Scientific Manuscript database

Lignin from four different sources extracted by various methods were pyrolyzed at 650 degree C using analytical pyrolysis methods, py-GC/MS. Pyrolysis was carried out in the absence and presence of two heterogeneous catalysts , an acidic zeolite (HZSM-5) catalyst and a mixed metal oxide catalyst (Co...

Fuel and fuel blending components from biomass derived pyrolysis oil

DOEpatents

McCall, Michael J.; Brandvold, Timothy A.; Elliott, Douglas C.

2012-12-11

A process for the conversion of biomass derived pyrolysis oil to liquid fuel components is presented. The process includes the production of diesel, aviation, and naphtha boiling point range fuels or fuel blending components by two-stage deoxygenation of the pyrolysis oil and separation of the products.

Co-pyrolysis of swine manure with agricultural plastic waste: Laboratory-scale study

USDA-ARS?s Scientific Manuscript database

Manure-derived biochar is the solid product resulting from pyrolysis of animal manures. It has considerable potential both to improve soil quality with high levels of nutrients and to reduce contaminants in water and soil. However, the combustible gas produced from manure pyrolysis generally does no...

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pomeroy, Marc D

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.

The Preparation of Silicon-Containing Ceramics by Organosilicon Polymer Pyrolysis

DTIC Science & Technology

1988-06-25

polymer , of composition [(CH3SiHNH)a(CH3SiNb]m, gives a black solid, a mixture of SiC , Si3N4, and some free carbon, on pyrolysis ...nitride (eq. 1) [7] is a possibility. 5 Si3N 4(s) + C (s) , 3 SiC (s) +2 N2(g) (1) The study of the pyrolysis products of preceramic polymers is not...approximately one, pyrolysis of the product polymer gave a black ceramic solid in 84% yield which analysis showed to have a formal composition (1 SiC +

Characterization of exopolymers of aquatic bacteria by pyrolysis-mass spectrometry

NASA Technical Reports Server (NTRS)

Ford, T.; Sacco, E.; Black, J.; Kelley, T.; Goodacre, R.; Berkeley, R. C.; Mitchell, R.

1991-01-01

Exopolymers from a diverse collection of marine and freshwater bacteria were characterized by pyrolysis-mass spectrometry (Py-MS). Py-MS provides spectra of pyrolysis fragments that are characteristic of the original material. Analysis of the spectra by multivariate statistical techniques (principal component and canonical variate analysis) separated these exopolymers into distinct groups. Py-MS clearly distinguished characteristic fragments, which may be derived from components responsible for functional differences between polymers. The importance of these distinctions and the relevance of pyrolysis information to exopolysaccharide function in aquatic bacteria is discussed.

Carbon nanoscrolls by pyrolysis of a polymer

NASA Astrophysics Data System (ADS)

Yadav, Prasad; Warule, Sambhaji; Jog, Jyoti; Ogale, Satishchandra

2012-12-01

3D network of carbon nanoscrolls was synthesized starting from pyrolysis of poly(acrylic acid-co-maleic acid) sodium salt. It is a catalyst-free process where pyrolysis of polymer leads to formation of carbon form and sodium carbonate. Upon water soaking of pyrolysis product, the carbon form undergoes self-assembly to form carbon nanoscrolls. The interlayer distance between the walls of carbon nanoscroll was found to be 0.34 nm and the carbon nanoscrolls exhibited a surface area of 188 m2/g as measured by the BET method.

The pyrolysis of toluene and ethyl benzene

NASA Technical Reports Server (NTRS)

Sokolovskaya, V. G.; Samgin, V. F.; Kalinenko, R. A.; Nametkin, N. S.

1987-01-01

The pyrolysis of toluene at 850 to 950 C gave mainly H2, CH4, and benzene; PhEt at 650 to 750 C gave mainly H2, CH4, styrene, benzene, and toluene. The rate constants for PhEt pyrolysis were 1000 times higher than those for toluene pyrolysis; the chain initiation rate constants differed by the same factor. The activation energy differences were 46 kJ/mole for the total reaction and 54 kJ/mole for chain initiation. The chain length was evaluated for the PhEt case (10 + or - 2).

Pyrolysis of carbonaceous materials with solvent quench recovery

DOEpatents

Green, Norman W.; Duraiswamy, Kandaswamy; Lumpkin, Robert E.; Knell, Everett W.; Mirza, Zia I.; Winter, Bruce L.

1978-04-18

In a continuous process for recovery of values contained in a solid carbonaceous material, the carbonaceous material is comminuted and then subjected to flash pyrolysis in the presence of a particulate heat source to form a pyrolysis product stream containing a carbon containing solid residue and volatilized hydrocarbons. After the carbon containing solid residue is separated from the pyrolysis product stream, values are obtained by condensing volatilized hydrocarbons. The particulate source of heat is formed by oxidizing carbon in the solid residue. Apparatus useful for practicing this process are disclosed.

Catalytic biomass pyrolysis process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dayton, David C.; Gupta, Raghubir P.; Turk, Brian S.

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.

Internally Heated Screw Pyrolysis Reactor (IHSPR) heat transfer performance study

NASA Astrophysics Data System (ADS)

Teo, S. H.; Gan, H. L.; Alias, A.; Gan, L. M.

2018-04-01

1.5 billion end-of-life tyres (ELT) were discarded globally each year and pyrolysis is considered the best solution to convert the ELT into valuable high energy-density products. Among all pyrolysis technologies, screw reactor is favourable. However, conventional screw reactor risks plugging issue due to its lacklustre heat transfer performance. An internally heated screw pyrolysis reactor (IHSPR) was developed by local renewable energy industry, which serves as the research subject for heat transfer performance study of this particular paper. Zero-load heating test (ZLHT) was first carried out to obtain the operational parameters of the reactor, followed by the one dimensional steady-state heat transfer analysis carried out using SolidWorks Flow Simulation 2016. Experiments with feed rate manipulations and pyrolysis products analyses were conducted last to conclude the study.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Pyrolysis characteristics and kinetics of acid tar waste from crude benzol refining: A thermogravimetry-mass spectrometry analysis.

PubMed

Chihobo, Chido H; Chowdhury, Arindrajit; Kuipa, Pardon K; Simbi, David J

2016-12-01

Pyrolysis is an attractive thermochemical conversion technology that may be utilised as a safe disposal option for acid tar waste. The kinetics of acid tar pyrolysis were investigated using thermogravimetry coupled with mass spectrometry under a nitrogen atmosphere at different heating rates of 10, 15 and 20 K min -1 The thermogravimetric analysis shows three major reaction peaks centred around 178 °C, 258 °C, and 336 °C corresponding to the successive degradation of water soluble lower molecular mass sulphonic acids, sulphonated high molecular mass hydrocarbons, and high molecular mass hydrocarbons. The kinetic parameters were evaluated using the iso-conversional Kissinger-Akahira-Sunose method. A variation in the activation energy with conversion revealed that the pyrolysis of the acid tar waste progresses through complex multi-step kinetics. Mass spectrometry results revealed a predominance of gases such as hydrogen, methane and carbon monoxide, implying that the pyrolysis of acid tar waste is potentially an energy source. Thus the pyrolysis of acid tar waste may present a viable option for its environmental treatment. There are however, some limitations imposed by the co-evolution of corrosive gaseous components for which appropriate considerations must be provided in both pyrolysis reactor design and selection of construction materials. © The Author(s) 2016.

Production and characterization of chars from cherry pulp via pyrolysis.

PubMed

Pehlivan, E; Özbay, N; Yargıç, A S; Şahin, R Z

2017-12-01

Pyrolysis is an eco-friendly process to achieve valuable products like bio-oil, char and gases. In the last decades, biochar production from pyrolysis of a wide variety of industrial and agricultural wastes become popular, which can be utilized as adsorbent instead of the expensive activated carbons. In this study, cherry pulp was pyrolyzed in a fixed bed tubular reactor at five different temperatures (400, 500,550, 600 and 700 °C) and three different heating rates (10, 100 and 200 °C/min) to obtain biochar. Proximate, ultimate, nitrogen adsorption/desorption isotherms, scanning electron microscopy, thermogravimetric analysis, x-ray fluorescence, x-ray diffraction, and Fourier transform infrared spectroscopy were performed on cherry pulp and its chars to examine the chemical alterations after the pyrolysis process. Biochar yields were decreased with increasing pyrolysis temperature and heating rate, based on experimental results. Porous biochars are carbon rich and includes high potassium content. The aromaticity of biochars increased and O/C mass ratio reduced with an increase in the pyrolysis temperature as a result of the development of compact aromatic structure in char. Pyrolysis provides a promising conversion procedure for the production of high energy density char which has promising applications in existing coal-fired boilers without any upgrading. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

An economic analysis of mobile pyrolysis for northern New Mexico forests.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brady, Patrick D.; Brown, Alexander L.; Mowry, Curtis Dale

2011-12-01

In the interest of providing an economically sensible use for the copious small-diameter wood in Northern New Mexico, an economic study is performed focused on mobile pyrolysis. Mobile pyrolysis was selected for the study because transportation costs limit the viability of a dedicated pyrolysis plant, and the relative simplicity of pyrolysis compared to other technology solutions lends itself to mobile reactor design. A bench-scale pyrolysis system was used to study the wood pyrolysis process and to obtain performance data that was otherwise unavailable under conditions theorized to be optimal given the regional problem. Pyrolysis can convert wood to three mainmore » products: fixed gases, liquid pyrolysis oil and char. The fixed gases are useful as low-quality fuel, and may have sufficient chemical energy to power a mobile system, eliminating the need for an external power source. The majority of the energy content of the pyrolysis gas is associated with carbon monoxide, followed by light hydrocarbons. The liquids are well characterized in the historical literature, and have slightly lower heating values comparable to the feedstock. They consist of water and a mix of hundreds of hydrocarbons, and are acidic. They are also unstable, increasing in viscosity with time stored. Up to 60% of the biomass in bench-scale testing was converted to liquids. Lower ({approx}550 C) furnace temperatures are preferred because of the decreased propensity for deposits and the high liquid yields. A mobile pyrolysis system would be designed with low maintenance requirements, should be able to access wilderness areas, and should not require more than one or two people to operate the system. The techno-economic analysis assesses fixed and variable costs. It suggests that the economy of scale is an important factor, as higher throughput directly leads to improved system economic viability. Labor and capital equipment are the driving factors in the viability of the system. The break-even selling price for the baseline assumption is about $11/GJ, however it may be possible to reduce this value by 20-30% depending on other factors evaluated in the non-baseline scenarios. Assuming a value for the char co-product improves the analysis. Significantly lower break-even costs are possible in an international setting, as labor is the dominant production cost.« less

Reinforcement of the bio-gas conversion from pyrolysis of wheat straw by hot caustic pre-extraction.

PubMed

Zhang, Lilong; Chen, Keli; He, Liang; Peng, Lincai

2018-01-01

Pyrolysis has attracted growing interest as a versatile means to convert biomass into valuable products. Wheat straw has been considered to be a promising biomass resource due to its low price and easy availability. However, most of the products obtained from wheat straw pyrolysis are usually of low quality. Hot soda extraction has the advantage of selective dissolution of lignin whilst retaining the carbohydrates. This can selectively convert biomass into high-quality desired products and suppress the formation of undesirable products. The aim of this study was to investigate the pyrolysis properties of wheat straw under different hot caustic pretreatment conditions. Compared with the untreated straw, a greater amount of gas was released and fewer residues were retained in the extracted wheat straw, which was caused by an increase in porosity. When the NaOH loading was 14%, the average pore size of the extracted straw increased by 12% and the cumulative pore volume increased by 157% compared with the untreated straw. The extracted straw obtained from the 14% NaOH extraction was clearly selective for pyrolysis products. On one hand, many lignin pyrolysis products disappeared, and only four main lignin-unit-pyrolysis products were retained. On the other hand, polysaccharide pyrolysis products were enriched. Both propanone and furfural have outstanding peak intensities that could account for approximately 30% of the total pyrolysis products. However, with the excessive addition of NaOH (i.e. > 22% w/w) during pretreatment, the conversion of bio-gas products decreased. Thermogravimetric and low-temperature nitrogen-adsorption analysis showed that the pore structure had been seriously destroyed, leading to the closing of the release paths of the bio-gas and thus increasing the re-polymerisation of small bio-gas molecules. After suitable extraction (14% NaOH loading extraction), a considerable amount (25%) of the soluble components dissolved out of the straw. This resulted in an increase in both pore size and volume. This condition appeared to be optimally selective for the release of value-added pyrolysis products such as furfural, ketones and lignin monomer units. However, excessive addition of alkali (22%) for extraction could change the original interior structure, resulting in a decrease in both pore size and volume. This interior structure modification limited the release of pyrolysis products, and greater carbonisation occurred.

Pyrolysis characteristics and kinetics of lignin derived from enzymatic hydrolysis residue of bamboo pretreated with white-rot fungus.

PubMed

Yan, Keliang; Liu, Fang; Chen, Qing; Ke, Ming; Huang, Xin; Hu, Weiyao; Zhou, Bo; Zhang, Xiaoyu; Yu, Hongbo

2016-01-01

The lignocellulose biorefinery based on the sugar platform usually focuses on polysaccharide bioconversion, while lignin is only burned for energy recovery. Pyrolysis can provide a novel route for the efficient utilization of residual lignin obtained from the enzymatic hydrolysis of lignocellulose. The pyrolysis characteristics of residual lignin are usually significantly affected by the pretreatment process because of structural alteration of lignin during pretreatment. In recent years, biological pretreatment using white-rot fungi has attracted extensive attention, but there are only few reports on thermal conversion of lignin derived from enzymatic hydrolysis residue (EHRL) of the bio-pretreated lignocellulose. Therefore, the study investigated the pyrolysis characteristics and kinetics of EHRL obtained from bamboo pretreated with Echinodontium taxodii in order to evaluate the potential of thermal conversion processes of EHRL. Fourier transform infrared spectroscopy spectra showed that EHRL of bamboo treated with E. taxodii had the typical lignin structure, but aromatic skeletal carbon and side chain of lignin were partially altered by the fungus. Thermogravimetric analysis indicated that EHRL pyrolysis at different heating rates could be divided into two depolymerization stages and covered a wide temperature range from 500 to 900 K. The thermal decomposition reaction can be well described by two third-order reactions. The kinetics study indicated that the EHRL of bamboo treated with white-rot fungus had lower apparent activation energies, lower peak temperatures of pyrolysis reaction, and higher char residue than the EHRL of raw bamboo. Pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) was applied to characterize the fast pyrolysis products of EHRL at 600 ℃. The ratios of guaiacyl-type to syringyl-type derivatives yield (G/S) and guaiacyl-type to p-hydroxy-phenylpropane-type derivatives yield (G/H) for the treated sample were increased by 33.18 and 25.30 % in comparison with the raw bamboo, respectively. The structural alterations of lignin during pretreatment can decrease the thermal stability of EHRL from the bio-treated bamboo and concentrate the guaiacyl-type derivatives in the fast pyrolysis products. Thus, the pyrolysis can be a promising route for effective utilization of the enzymatic hydrolysis residue from bio-pretreated lignocellulose.

Recycling of electronic waste: Printed wiring boards

NASA Astrophysics Data System (ADS)

Luyima, Alex

Pyrolysis and leaching are the dominant techniques applied in the recycling of waste printed wiring boards (PWBs). Waste PWB pyrolysis is a highly polluting technology and produces brominated pyrolysis oils in addition to hydrogen bromide (HBr) gas. Moreover, leaching as a treatment process of waste PWBs is not well investigated. In this work, the pyrolysis of waste PWBs has been studied with the aim of reducing the amount of brominated oils and HBr gas evolved. The effects of powder inorganic chemicals (CaO, CaCO3, Fe 2O3, Al2O3, Y-Zeolite, and ZSM-5) additions on the pyrolysis of waste PWBs has been studied through experiments using a thermogravimetric-differential thermal analyzer connected to a mass spectrometer (TG-DTA-MS) and in a tube furnace at 900 °C. It has been shown that the kinetic models by Friedman, Flynn-Wall-Ozawa, and Kissinger are applicable to waste PWB pyrolysis at temperatures below 400 °C. Moreover, CaO, CaCO3, Fe2O3, Y-Zeolite, and ZSM-5 show a potential to reduce the amount of HBr gas evolved during pyrolysis in TG-DTA-MS. However, in the tube furnace pyrolysis experiments, CaO and CaCO3 were found to be the most effective chemical additions, with more than 90% reduction in total bromine (HBr and other brominated gases) evolved. It has also been demonstrated that the sequential leaching of waste PWBs with hydrochloric acid, nitric acid and aqua regia is capable of selective recovery of base and precious metals contained in waste PWBs.

Life cycle assessment of pyrolysis, gasification and incineration waste-to-energy technologies: Theoretical analysis and case study of commercial plants.

PubMed

Dong, Jun; Tang, Yuanjun; Nzihou, Ange; Chi, Yong; Weiss-Hortala, Elsa; Ni, Mingjiang

2018-06-01

Municipal solid waste (MSW) pyrolysis and gasification are in development, stimulated by a more sustainable waste-to-energy (WtE) option. Since comprehensive comparisons of the existing WtE technologies are fairly rare, this study aims to conduct a life cycle assessment (LCA) using two sets of data: theoretical analysis, and case studies of large-scale commercial plants. Seven systems involving thermal conversion (pyrolysis, gasification, incineration) and energy utilization (steam cycle, gas turbine/combined cycle, internal combustion engine) are modeled. Theoretical analysis results show that pyrolysis and gasification, in particular coupled with a gas turbine/combined cycle, have the potential to lessen the environmental loadings. The benefits derive from an improved energy efficiency leading to less fossil-based energy consumption, and the reduced process emissions by syngas combustion. Comparison among the four operating plants (incineration, pyrolysis, gasification, gasification-melting) confirms a preferable performance of the gasification plant attributed to syngas cleaning. The modern incineration is superior over pyrolysis and gasification-melting at present, due to the effectiveness of modern flue gas cleaning, use of combined heat and power (CHP) cycle, and ash recycling. The sensitivity analysis highlights a crucial role of the plant efficiency and pyrolysis char land utilization. The study indicates that the heterogeneity of MSW and syngas purification technologies are the most relevant impediments for the current pyrolysis/gasification-based WtE. Potential development should incorporate into all process aspects to boost the energy efficiency, improve incoming waste quality, and achieve efficient residues management. Copyright © 2018 Elsevier B.V. All rights reserved.

Compound-specific stable carbon isotopic signature of carbohydrate pyrolysis products from C3 and C4 plants.

PubMed

González-Pérez, José A; Jiménez-Morillo, Nicasio T; de la Rosa, José M; Almendros, Gonzalo; González-Vila, Francisco J

2016-02-01

Pyrolysis-compound specific isotopic analysis (Py-CSIA: Py-GC-(FID)-C-IRMS) is a relatively novel technique that allows on-line quantification of stable isotope proportions in chromatographically separated products released by pyrolysis. Validation of the Py-CSIA technique is compulsory for molecular traceability in basic and applied research. In this work, commercial sucrose from C4 (sugarcane) and C3 (sugarbeet) photosystem plants and admixtures were studied using analytical pyrolysis (Py-GC/MS), bulk δ(13)C IRMS and δ(13)C Py-CSIA. Major pyrolysis compounds were furfural (F), furfural-5-hydroxymethyl (HMF) and levoglucosan (LV). Bulk and main pyrolysis compound δ(13)C (‰) values were dependent on plant origin: C3 (F, -24.65 ± 0.89; HMF, -22.07 ± 0.41‰; LV, -21.74 ± 0.17‰) and C4 (F, -14.35 ± 0.89‰; HMF, -11.22 ± 0.54‰; LV, -11.44 ± 1.26‰). Significant regressions were obtained for δ(13)C of bulk and pyrolysis compounds in C3 and C4 admixtures. Furfural (F) was found (13)C depleted with respect to bulk and HMF and LV, indicating the incorporation of the light carbon atom in position 6 of carbohydrates in the furan ring after pyrolysis. This is the first detailed report on the δ(13)C signature of major pyrolytically generated carbohydrate-derived molecules. The information provided by Py-CSIA is valuable for identifying source marker compounds of use in food science/fraud detection or in environmental research. © 2015 Society of Chemical Industry.

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

NASA Astrophysics Data System (ADS)

Supramono, D.; Lusiani, S.

2016-11-01

Over the past few decades, interest in developing biomass-derived fuel has been increasing rapidly due to the decrease in fossil fuel reserves. Bio-oil produced by biomass pyrolysis however contains high oxygen compounds resulting in low calorific-value fuel and therefore requiring upgrading. In co-pyrolysis of the feed blend of plastics of High Density Polyethylene (HDPE) and biomass of com cob particles, at some compositions free radicals from plastic decomposition containing more hydrogen radicals are able to bond oxygen radicals originating from biomass to reduce oxygenate compounds in the bio-oil thus increasing bio-oil quality. This phenomenon is usually called synergetic effect. In addition to that, the pattern of heating of the feed blend in the pyrolysis reactor is predicted to affect biooil quality and yield. In a batch reactor, co-pyrolysis of corncobs and HDPE requires low heating rate to reach a peak temperature at temperature rise period followed by heating for some time at peak temperature called holding time at constant temperature period. No research has been carried out to investigate how long holding time is set in co-pyrolysis of plastic and biomass to obtain high yield of bio-oil. Holding time may affect either crosslinking of free radicals in gas phase, which increases char product, or secondary pyrolysis in the gas phase, which increases non-condensable gas in the gas phase of pyrolysis reactor, both of which reduce bio-oil yield. Therefore, holding time of co-pyrolysis affects the mass rate of bio-oil formation as the pyrolysis proceeds and quality of the bio-oil. In the present work, effects of holding time on the yield and quality of bio-oil have been investigated using horizontal fixed bed of the feed blends at heating rate of 5°C, peak temperature of 500°C and N2 flow rate of 700 ml/minute. Holding time was varied from 0 to 70 minutes with 10 minutes interval. To investigate the effects of holding time, the composition of HDPE in the feed blend was varied 0, 50 and 100%, while the synergetic effect was investigated by varying the composition of HDPE in the feed blend 0, 25, 50, 75, and 100%. The results show that synergetic effect for non-oxygenate compound production started to work at 63% HDPE in the feed blend and beyond. It was observed that extension of holding time exceeding 0 minutes allowed increase ofbio-oil production rate followed reduction of the rate. Pyrolysis ofboth the corncob feed and the feed blend containing 50% HDPE equally reached maximum bio-oil production rate at holding time of 50 minutes, while that of HDPE feed at 30 minutes. The result pertaining to holding time indicates that biomass in the feed blend governs crosslinking - secondary pyrolysis in the co-pyrolysis.

Magnetic carbon nanostructures: microwave energy-assisted pyrolysis vs. conventional pyrolysis.

PubMed

Zhu, Jiahua; Pallavkar, Sameer; Chen, Minjiao; Yerra, Narendranath; Luo, Zhiping; Colorado, Henry A; Lin, Hongfei; Haldolaarachchige, Neel; Khasanov, Airat; Ho, Thomas C; Young, David P; Wei, Suying; Guo, Zhanhu

2013-01-11

Magnetic carbon nanostructures from microwave assisted- and conventional-pyrolysis processes are compared. Unlike graphitized carbon shells from conventional heating, different carbon shell morphologies including nanotubes, nanoflakes and amorphous carbon were observed. Crystalline iron and cementite were observed in the magnetic core, different from a single cementite phase from the conventional process.

ASPEN+ and economic modeling of equine waste utilization for localized hot water heating via fast pyrolysis

USDA-ARS?s Scientific Manuscript database

ASPEN Plus based simulation models have been developed to design a pyrolysis process for the on-site production and utilization of pyrolysis oil from equine waste at the Equine Rehabilitation Center at Morrisville State College (MSC). The results indicate that utilization of all available Equine Reh...

High-temperature pyrolysis of blended animal manures for producing renewable energy and value-added biochar

USDA-ARS?s Scientific Manuscript database

In this study, we used a commercial pilot-scale pyrolysis reactor system to produce combustible gas and biochar at 620 degrees Celsium from three sources (chicken litter, swine solids, mixture of swine solids with rye grass). Pyrolysis of swine solids produced gas with the greatest higher heating va...

Physicochemical and adsorptive properties of fast-pyrolysis bio-chars and their steam activated counterparts

USDA-ARS?s Scientific Manuscript database

Fast pyrolysis is rapid heating in the absence of oxygen resulting in decomposition of organic material. When applied to biomass, it produces bio-oil, bio-char and gas. The Agricultural Research Service (ARS) of the USDA has studied fluidized-bed fast pyrolysis of several bimoass including perenni...

Fuels and chemicals from equine-waste-derived tail gas reactive pyrolysis oil: technoeconomic analysis, environmental and exergetic life cycle assessment

USDA-ARS?s Scientific Manuscript database

Horse manure, whose improper disposal imposes considerable environmental costs, constitutes an apt feedstock for conversion to renewable fuels and chemicals when tail gas reactive pyrolysis (TGRP) is employed. TGRP is a modification of fast pyrolysis that recycles its non-condensable gases and produ...

Chemical yields from low-temperature pyrolysis of CCA-treated wood

Treesearch

Qirong Fu; Dimitris Argyropolous; Lucian Lucia; David Tilotta; Stan Lebow

2009-01-01

Low-temperature pyrolysis offers a feasible option for wood-waste management and the recovery of a variety of useful chemicals. The effect of chromated copper arsenate (CCA) wood preservative on the yield and composition of various pyrolysis products was investigated in the present research. A novel quantitative 31P nuclear magnetic resonance (...

Pyrolysis kinetic and product analysis of different microalgal biomass by distributed activation energy model and pyrolysis-gas chromatography-mass spectrometry.

PubMed

Yang, Xuewei; Zhang, Rui; Fu, Juan; Geng, Shu; Cheng, Jay Jiayang; Sun, Yuan

2014-07-01

To assess the energy potential of different microalgae, Chlorella sorokiniana and Monoraphidium were selected for studying the pyrolytic behavior at different heating rates with the analytical method of thermogravimetric analysis (TG), distributed activation energy model (DAEM) and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). Results presented that Monoraphidium 3s35 showed superiority for pyrolysis at low heating rate. Calculated by DAEM, during the conversion rate range from 0.1 to 0.7, the activation energies of C. sorokiniana 21 were much lower than that of Monoraphidium 3s35. Both C. sorokiniana 21 and Monoraphidium 3s35 can produce certain amount (up to 20.50%) of alkane compounds, with 9-Octadecyne (C18H34) as the primary compound. Short-chain alkanes (C7-C13) with unsaturated carbon can be released in the pyrolysis at 500°C for both microalgal biomass. It was also observed that the pyrolysis of C. sorokiniana 21 released more alcohol compounds, while Monoraphidium 3s35 produced more saccharides. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization of carbon silica hybrid fillers obtained by pyrolysis of waste green tires by the STEM–EDX method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Al-Hartomy, Omar A.; Department of Physics, Faculty of Science, University of Tabuk, Tabuk 71491; Al-Ghamdi, Ahmed A.

2015-03-15

Dual phase carbon–silica hybrid fillers obtained by pyrolysis-cum-water vapor of waste green tires have been characterized by energy dispersive X-ray spectroscopy in a scanning transmission electron microscope, silicate analysis, weight analysis, atomic absorption spectroscopy and by inductively coupled plasma–optical emission spectroscopy. The results achieved have shown that the location and distribution of the phases in the carbon silica hybrid fillers as well as their most essential characteristics are influenced by the pyrolysis conditions. The carbon phase of the filler thus obtained is located predominantly in the space among silica aggregates which have already been existing while it has been formedmore » by elastomer destruction in the course of pyrolysis. The presence of ZnS also has been found in the hybrid fillers investigated. - Highlights: • Dual phase fillers obtained by pyrolysis of waste green tires have been characterized. • The STEM–EDX method was used for characterization. • The phase distributions in the fillers are influenced by the pyrolysis conditions.« less

Pyrolysis of polyethylene mixed with paper and wood: Interaction effects on tar, char and gas yields.

PubMed

Grieco, E M; Baldi, G

2012-05-01

In the present study the interactions between the main constituents of the refuse derived fuel (plastics, paper, and wood) during pyrolysis were studied. Binary mixtures of polyethylene-paper and polyethylene/sawdust have been transformed into pellets and pyrolyzed. Various mixtures with different composition were analyzed and pyrolysis products (tar, gas, and char) were collected. The mixtures of wood/PE and paper/PE have a different behavior. The wood/PE mixtures showed a much reduced interaction of the various compounds because the yields of pyrolysis products of the mixture can be predicted as linear combination of those of the pure components. On the contrary, a strong char yield increase was found at a low heating rate for paper/PE mixtures. In order to explain the results, the ability of wood and paper char to adsorb and convert the products of PE pyrolysis into was studied. Adsorption and desorption tests were performed on the char obtained by paper and wood by using n-hexadecane as a model compound for the heavy products of PE pyrolysis. Copyright © 2011 Elsevier Ltd. All rights reserved.

An approach for upgrading biomass and pyrolysis product quality using a combination of aqueous phase bio-oil washing and torrefaction pretreatment.

PubMed

Chen, Dengyu; Cen, Kehui; Jing, Xichun; Gao, Jinghui; Li, Chen; Ma, Zhongqing

2017-06-01

Bio-oil undergoes phase separation because of poor stability. Practical application of aqueous phase bio-oil is challenging. In this study, a novel approach that combines aqueous phase bio-oil washing and torrefaction pretreatment was used to upgrade the biomass and pyrolysis product quality. The effects of individual and combined pretreatments on cotton stalk pyrolysis were studied using TG-FTIR and a fixed bed reactor. The results showed that the aqueous phase bio-oil washing pretreatment removed metals and resolved the two pyrolysis peaks in the DTG curve. Importantly, it increased the bio-oil yield and improved the pyrolysis product quality. For example, the water and acid content of bio-oil decreased significantly along with an increase in phenol formation, and the heating value of non-condensable gases improved, and these were more pronounced when combined with torrefaction pretreatment. Therefore, the combined pretreatment is a promising method, which would contribute to the development of polygeneration pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of Inert and Oxidizing Atmospheres on the Physical and Optical Properties of Luminescent Carbon Dots Prepared through Pyrolysis of a Model Molecule.

PubMed

Machado, Cláudia Emanuele; Tartuci, Letícia Gazola; de Fátima Gorgulho, Honória; de Oliveira, Luiz Fernando Cappa; Bettini, Jefferson; Pereira dos Santos, Daniela; Ferrari, Jefferson Luis; Schiavon, Marco Antônio

2016-03-18

This work used L-tartaric acid as a model molecule to evaluate how the use of inert and oxidizing atmospheres during pyrolysis affected the physical and optical properties of the resulting carbon dots (CDs). Pyrolysis revealed to be a simple procedure that afforded CDs in a single step, dismissed the addition of organic solvents, and involved only one extraction stage that employed water. By X-ray diffraction a dependency between the structure of the CDs and the atmosphere (oxidizing or inert) used during the pyrolysis was found. Potentiometric titration demonstrated that the CDs were largely soluble in water; it also aided characterization of the various groups that contained sp(3) -hybridized carbon atoms on the surface of the dots. Raman spectroscopy suggested that different amounts of sp(2)- and sp(3)-hybridized carbon atoms emerged on the CDs depending on the pyrolysis atmosphere. In conclusion, the pyrolysis atmosphere influenced the physical properties, such as the composition and the final structure. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

DOEpatents

Nicholas, Christpher P; Boldingh, Edwin P

2013-12-17

A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and show to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hyrdocarbons into hydrocarbons removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

DOEpatents

Nicholas, Christopher P; Boldingh, Edwin P

2014-10-07

A new family of coherently grown composites of TUN and IMF zeotypes has been synthesized and shown to be effective catalysts for catalytic pyrolysis of biomass. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.n+R.sub.rQ.sub.qAl.sub.1-xE.sub.xSi.sub.yO.s- ub.z where M represents zinc or a metal or metals from Group 1, Group 2, Group 3 or the lanthanide series of the periodic table, R is an A,.OMEGA.-dihalosubstituted paraffin such as 1,4-dibromobutane, Q is a neutral amine containing 5 or fewer carbon atoms such as 1-methylpyrrolidine and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-39 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

Development of bio-fuel from palm frond via fast pyrolysis

NASA Astrophysics Data System (ADS)

Solikhah, M. D.; Raksodewanto, A. A.; Kismanto, A.; Karuana, F.; Heryana, Y.; Riza; Pratiwi, F. T.

2017-05-01

In order to fulfill the fuel demand in the future, Indonesia has to find a sustainable alternative for its energy. Energy source in the form of biomass is a promising alternative since its availability is abundance in this tropical country. Biomass can be converted into liquid fuel via fast pyrolysis by contacting the solid biomass into hot medium in the absence of oxygen. Hot sand is the common heat carrier for fast pyrolysis purposes but it is very abrasive and required high pyrolysis temperature (450-600 °C). This paper will discuss on the equipment design and experiment of fast pyrolysis of palm frond using high boiling point thermal oil as heat carrier. Experiments show that by using thermal oil as heat carrier, bio-oil can be produced at lower pyrolysis temperature of 350 °C, compared to the one using hot sand as heating carrier. The yield of bio-oil production is 36.4 % of biomass feeding. The water content of bio-oil is 52.77 % mass while heating value is 10.25 MJ/kg.

Co-pyrolysis of lignocellulosic biomass and microalgae: Products characteristics and interaction effect.

PubMed

Chen, Wei; Chen, Yingquan; Yang, Haiping; Xia, Mingwei; Li, Kaixu; Chen, Xu; Chen, Hanping

2017-12-01

Co-pyrolysis of biomass has a potential to change the quality of pyrolytic bio-oil. In this work, co-pyrolysis of bamboo, a typical lignocellulosic biomass, and Nannochloropsis sp. (NS), a microalgae, was carried out in a fixed bed reactor at a range of mixing ratio of NS and bamboo, to find out whether the quality of pyrolytic bio-oil was improved. A significant improvement on bio-oil after co-pyrolysis of bamboo and NS was observed that bio-oil yield increased up to 66.63wt% (at 1:1) and the content of long-chain fatty acids in bio-oil also dramatically increased (the maximum up to 50.92% (13.57wt%) at 1:1) whereas acetic acid, O-containing species, and N-containing compounds decreased greatly. Nitrogen transformation mechanism during co-pyrolysis also was explored. Results showed that nitrogen in microalgae preferred to transform into solid char and gas phase during co-pyrolysis, while more pyrrolic-N and quaternary-N generated with diminishing protein-N and pyridinic-N in char. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microwave-assisted co-pyrolysis of pretreated lignin and soapstock for upgrading liquid oil: Effect of pretreatment parameters on pyrolysis behavior.

PubMed

Duan, Dengle; Ruan, Roger; Lei, Hanwu; Liu, Yuhuan; Wang, Yunpu; Zhang, Yayun; Zhao, Yunfeng; Dai, Leilei; Wu, Qiuhao; Zhang, Shumei

2018-06-01

The co-pyrolysis of pretreated lignin and soapstock was carried out to upgrade vapors under microwave irradiation. Results showed that the yield of 29.92-42.21 wt% of upgraded liquid oil was achieved under varied pretreatment conditions. Char yield decreased from 32.44 wt% for untreated control to 24.35 wt% for the 150 °C pretreated samples. The increased temperature, irradiation time and acid concentration were conducive to decrease the relative contents of phenols and oxygenates in liquid oils. The main components of the liquid oil were gasoline fraction (mono-aromatics and C5-C12 aliphatics), which ranged from 57.38 to 71.98% under various pretreatment conditions. Meanwhile, the diesel fraction (C12+ aliphatics) ranged from 13.16 to 22.62% from co-pyrolysis of pretreated lignin and soapstock, comparing with 10.18% of C12+ aliphatics from co-pyrolysis of non-pretreated lignin and soapstock. A possible mechanism was proposed for co-pyrolysis of pretreated lignin and soapstock for upgraded liquid oils. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

PubMed

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

2015-10-01

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

Effect of operating parameters on bio-fuel production from waste furniture sawdust.

PubMed

Uzun, Basak Burcu; Kanmaz, Gülin

2013-04-01

Fast pyrolysis is an effective technology for conversion of biomass into energy and value-added chemicals instead of burning them directly. In this study, fast pyrolysis of waste furniture sawdust (pine sawdust) was investigated under various reaction conditions (reaction time, pyrolysis temperature, heating rate, residence time and particle size) in a tubular reactor. The optimum reaction conditions for bio-oil production was found as reaction time of 5 min, pyrolysis temperature of 500 °C, heating rate of 300 °C min(-1) under nitrogen flow rate of 400 cm(3) min(-1). At these conditions, maximum bio-oil yield was obtained as 42.09%. Pyrolysis oils were characterized by using various elemental analyses, fourier - transformation infrared (FT-IR) spectrometry and gas chromatography-mass spectrometry (GC-MS). The results of the GC-MS showed that cracking of large molecular phenolics was followed by partial conversion into phenol and alkylated phenols (45%) during the pyrolysis. According to the experimental and characterization results; the liquid product could be used as feedstock for the chemical industry or petroleum crude for refinery.

Variation in cell wall composition among forage maize (Zea mays L.) inbred lines and its impact on digestibility: analysis of neutral detergent fiber composition by pyrolysis-gas chromatography-mass spectrometry.

PubMed

Fontaine, Anne-Sophie; Bout, Siobhán; Barrière, Yves; Vermerris, Wilfred

2003-12-31

Cell wall digestibility is an important determinant of forage quality, but the relationship between cell wall composition and digestibility is poorly understood. We analyzed the neutral detergent fiber (NDF) fraction of nine maize inbred lines and one brown midrib3 mutant with pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). Among 29 pyrolysis fragments that were quantified, two carbohydrate-derived and six lignin-derived fragments showed statistically significant genetic variation. The pyrolysis products 4-vinyl phenol and 2,6-dimethoxy-4-vinyl phenol were negatively correlated with digestibility, whereas furfural and 3-(4-hydroxyphenyl)-3-oxopropanal showed a positive correlation with digestibility. Linear discriminant analysis of the pyrolysis data resulted in the resolution of groups of inbred lines with different digestibility properties based on their chemical composition. These analyses reveal that digestibility is governed by complex interactions between different cell wall compounds, but that several pyrolysis fragments can be used as markers to distinguish between maize lines with different digestibility.

Characteristics and kinetics study of simultaneous pyrolysis of microalgae Chlorella vulgaris, wood and polypropylene through TGA.

PubMed

Azizi, Kolsoom; Keshavarz Moraveji, Mostafa; Abedini Najafabadi, Hamed

2017-11-01

Thermal decomposition behavior and kinetics of microalgae Chlorella vulgaris, wood and polypropylene were investigated using thermogravimetric analysis (TGA). Experiments were carried out at heating rates of 10, 20 and 40°C/min from ambient temperature to 600°C. The results show that pyrolysis process of C. vulgaris and wood can be divided into three stages while pyrolysis of polypropylene occurs almost totally in one step. It is shown that wood can delay the pyrolysis of microalgae while microalgae can accelerate the pyrolysis of wood. The existence of polymer during the pyrolysis of microalgae or wood will lead to two divided groups of peaks in DTG curve of mixtures. The results showed that interaction is inhibitive rather than synergistic during the decomposition process of materials. Kinetics of process is studied by the Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The average E values obtained from FWO and KAS methods were 131.228 and 142.678kJ/mol, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetics evaluation and thermal decomposition characteristics of co-pyrolysis of municipal sewage sludge and hazelnut shell.

PubMed

Zhao, Bing; Xu, Xinyang; Li, Haibo; Chen, Xi; Zeng, Fanqiang

2018-01-01

Hazelnut shell, as novel biomass, has lower ash content and abundant hydrocarbon, which can be utilized resourcefully with municipal sewage sludge (MSS) by co-pyrolyisis to decrease total content of pollution. The co-pyrolysis of MSS and hazelnut shell blend was analyzed by a method of multi-heating rates and different blend ratios with TG-DTG-MS under N 2 atmosphere. The apparent activation energy of co-pyrolysis was calculated by three iso-conversional methods. Satava-Sestak method was used to determine mechanism function G(α) of co-pyrolysis, and Lorentzian function was used to simulate multi-peaks curves. The results showed there were four thermal decomposition stages, and the biomass were cracked and evolved at different temperature ranges. The apparent activation energy increased from 123.99 to 608.15kJ/mol. The reaction mechanism of co-pyrolysis is random nucleation and nuclei growth. The apparent activation energy and mechanism function afford a theoretical groundwork for co-pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evaluation of agricultural residues pyrolysis under non-isothermal conditions: Thermal behaviors, kinetics, and thermodynamics.

PubMed

Chen, Jianbiao; Wang, Yanhong; Lang, Xuemei; Ren, Xiu'e; Fan, Shuanshi

2017-10-01

The thermal conversion characteristics, kinetics, and thermodynamics of agricultural residues, rape straw (RS) and wheat bran (WB), were investigated under non-isothermal conditions. TGA experiments showed that the pyrolysis characteristics of RS were quite different from those of WB. As reflected by the comprehensive devolatilization index, when the heating rate increased from 10 to 30Kmin -1 , the pyrolysis performance of RS and WB were improved 5.27 and 5.96 times, respectively. The kinetic triplets of the main pyrolysis process of agricultural residues were calculated by the Starink method and the integral master-plots method. Kinetic analysis results indicated that the most potential kinetic models for the pyrolysis of RS and WB were D 2 and F 2.7 , respectively. The thermodynamic parameters (ΔH, ΔG, and ΔS) were determined by the activated complex theory. The positive ΔH, positive ΔG, and negative ΔS at characteristic temperatures validated that the pyrolysis of agricultural residues was endothermic and non-spontaneous. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2015-01-01

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

Cumulative effects of bamboo sawdust addition on pyrolysis of sewage sludge: Biochar properties and environmental risk from metals.

PubMed

Jin, Junwei; Wang, Minyan; Cao, Yucheng; Wu, Shengchun; Liang, Peng; Li, Yanan; Zhang, Jianyun; Zhang, Jin; Wong, Ming Hung; Shan, Shengdao; Christie, Peter

2017-03-01

A novel type of biochar was produced by mixing bamboo sawdust with sewage sludge (1:1, w/w) via a co-pyrolysis process at 400-600°C. Changes in physico-chemical properties and the intrinsic speciation of metals were investigated before and after pyrolysis. Co-pyrolysis resulted in a lower biochar yield but a higher C content in the end product compared with use of sludge alone as the raw material. FT-IR analysis indicates that phosphine derivatives containing PH bonds were formed in the co-pyrolyzed biochars. In addition, co-pyrolysis of sludge with bamboo sawdust transformed the potentially toxic metals in the sludge into more stable fractions, leading to a considerable decrease in their direct toxicity and bioavailability in the co-pyrolyzed biochar. In conclusion, the co-pyrolysis technology provides a feasible method for the safe disposal of metal-contaminated sewage sludge in an attempt to minimize the environmental risk from potentially toxic metals after land application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hydrogen-Rich Syngas Production from Gasification and Pyrolysis of Solar Dried Sewage Sludge: Experimental and Modeling Investigations

PubMed Central

Ghrib, Amina; Friaa, Athar; Ouerghi, Aymen; Naoui, Slim; Belayouni, Habib

2017-01-01

Solar dried sewage sludge (SS) conversion by pyrolysis and gasification processes has been performed, separately, using two laboratory-scale reactors, a fixed-bed pyrolyzer and a downdraft gasifier, to produce mainly hydrogen-rich syngas. Prior to SS conversion, solar drying has been conducted in order to reduce moisture content (up to 10%). SS characterization reveals that these biosolids could be appropriate materials for gaseous products production. The released gases from SS pyrolysis and gasification present relatively high heating values (up to 9.96 MJ/kg for pyrolysis and 8.02  9.96 MJ/kg for gasification) due to their high contents of H2 (up to 11 and 7 wt%, resp.) and CH4 (up to 17 and 5 wt%, resp.). The yields of combustible gases (H2 and CH4) show further increase with pyrolysis. Stoichiometric models of both pyrolysis and gasification reactions were determined based on the global biomass formula, CαHβOγNδSε, in order to assist in the products yields optimization. PMID:28856162

Review of NMR characterization of pyrolysis oils

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Islam, M.R., E-mail: mrislam1985@yahoo.com; Joardder, M.U.H.; Hasan, S.M.

2011-09-15

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 formore » the production of crude pyrolysis oil that could be used as boiler fuel oil and for the production of upgraded liquid-products.« less

Comparative assessment of municipal sewage sludge incineration, gasification and pyrolysis for a sustainable sludge-to-energy management in Greece.

PubMed

Samolada, M C; Zabaniotou, A A

2014-02-01

For a sustainable municipal sewage sludge management, not only the available technology, but also other parameters, such as policy regulations and socio-economic issues should be taken in account. In this study, the current status of both European and Greek Legislation on waste management, with a special insight in municipal sewage sludge, is presented. A SWOT analysis was further developed for comparison of pyrolysis with incineration and gasification and results are presented. Pyrolysis seems to be the optimal thermochemical treatment option compared to incineration and gasification. Sewage sludge pyrolysis is favorable for energy savings, material recovery and high added materials production, providing a 'zero waste' solution. Finally, identification of challenges and barriers for sewage sludge pyrolysis deployment in Greece was investigated. Copyright © 2013 Elsevier Ltd. All rights reserved.

Review of NMR characterization of pyrolysis oils

DOE PAGES

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

2016-08-24

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

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

NASA Astrophysics Data System (ADS)

Rinaldi, Nino; Simanungkalit, Sabar P.; Kiky Corneliasari, S.

2017-01-01

Fast pyrolysis process of palm fronds has been conducted in the fluidized bed reactor to yield bio-oil product (pyrolysis oil). The process employed sea sand as the heat transfer medium. The objective of this study is to design of the fluidized bed rector, to conduct fast pyrolysis process to product bio-oil from palm fronds, and to characterize the feed and bio-oil product. The fast pyrolysis process was conducted continuously with the feeding rate around 500 g/hr. It was found that the biomass conversion is about 35.5% to yield bio-oil, however this conversion is still minor. It is suggested due to the heating system inside the reactor was not enough to decompose the palm fronds as a feedstock. Moreover, the acids compounds ware mostly observed on the bio-oil product.

Chemical pyrolysis of E-waste plastics: Char characterization.

PubMed

Shen, Yafei; Chen, Xingming; Ge, Xinlei; Chen, Mindong

2018-05-15

This work studied the disposal of the non-metallic fraction from waste printed circuit board (NMF-WPCB) via the chemical pretreatments followed by pyrolysis. As a main heavy metal, the metallic Cu could be significantly removed by 92.4% using the HCl leaching process. Subsequently, the organic-Br in the brominated flame retardants (BFRs) plastics could be converted into HBr by pyrolysis. The alkali pretreatment was benefit for the Br fixation in the solid char. The Br fixation efficiency could reach up to 53.6% by the NaOH pretreatment followed by the pyrolysis process. The formed HBr could react with NaOH/KOH to generate the stabilized NaBr/KBr. Therefore, the integrated chemical pretreatment could be used for the eco-friendly disposal of the NMF-WPCB via pyrolysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Pyrolysis process for the treatment of food waste.

PubMed

Grycová, Barbora; Koutník, Ivan; Pryszcz, Adrian

2016-10-01

Different waste materials were pyrolysed in the laboratory pyrolysis unit to the final temperature of 800°C with a 10min delay at the final temperature. After the pyrolysis process a mass balance of the resulting products, off-line analysis of the pyrolysis gas and evaluation of solid and liquid products were carried out. The gas from the pyrolysis experiments was captured discontinuously into Tedlar gas sampling bags and the selected components were analyzed by gas chromatography (methane, ethene, ethane, propane, propene, hydrogen, carbon monoxide and carbon dioxide). The highest concentration of measured hydrogen (WaCe 61%vol.; WaPC 66%vol.) was analyzed at the temperature from 750 to 800°C. The heating values of the solid and liquid residues indicate the possibility of its further use for energy recovery. Copyright © 2016 Elsevier Ltd. All rights reserved.

Steam Pyrolysis of Polyimides: Effects of Steam on Raw Material Recovery.

PubMed

Kumagai, Shogo; Hosaka, Tomoyuki; Kameda, Tomohito; Yoshioka, Toshiaki

2015-11-17

Aromatic polyimides (PIs) have excellent thermal stability, which makes them difficult to recycle, and an effective way to recycle PIs has not yet been established. In this work, steam pyrolysis of the aromatic PI Kapton was performed to investigate the recovery of useful raw materials. Steam pyrolysis significantly enhanced the gasification of Kapton at 900 °C, resulting in 1963.1 mL g(-1) of a H2 and CO rich gas. Simultaneously, highly porous activated carbon with a high BET surface area was recovered. Steam pyrolysis increased the presence of polar functional groups on the carbon surface. Thus, it was concluded that steam pyrolysis shows great promise as a recycling technique for the recovery of useful synthetic gases and activated carbon from PIs without the need for catalysts and organic solvents.

TG-FTIR analysis on pyrolysis and combustion of marine sediment

NASA Astrophysics Data System (ADS)

Oudghiri, Fatiha; Allali, Nabil; Quiroga, José María; Rodríguez-Barroso, María Rocío

2016-09-01

In this paper, the pyrolysis and combustion of sediment have been compared using thermogravimetric analysis (TG) coupled with Fourier transform infrared spectrometry (TG-FTIR) analysis. The TG results showed that both the pyrolysis and combustion of sediment presented four weight loss stages, each. The evolving gaseous products during pyrolysis were H2O, CO2 and hydrocarbons, while combustion yielded considerable amounts of CO2, in addition to H2O, CO, Cdbnd C, Cdbnd O and NH3. Comparing the pyrolysis and combustion TG-FTIR curves, it is possible to evaluate the effect of oxygen presence in the temperature range of 200-600 °C, which increases the volatilisation rate of organic matter in sediment. For the better detection of organic and inorganic matter in sediment by TG-FTIR analysis it is recommended to work in combustion mode of sediment.

Method of increasing anhydrosugars, pyroligneous fractions and esterified bio-oil

DOEpatents

Steele, Philip H; Yu, Fei; Li, Qi; Mitchell, Brian

2014-12-30

The device and method are provided to increase anhydrosugars yield during pyrolysis of biomass. This increase is achieved by injection of a liquid or gas into the vapor stream of any pyrolysis reactor prior to the reactor condensers. A second feature of our technology is the utilization of sonication, microwave excitation, or shear mixing of the biomass to increase the acid catalyst rate for demineralization or removal of hemicellulose prior to pyrolysis. The increased reactivity of these treatments reduces reaction time as well as the required amount of catalyst to less than half of that otherwise required. A fractional condensation system employed by our pyrolysis reactor is another feature of our technology. This system condenses bio-oil pyrolysis vapors to various desired fractions by differential temperature manipulation of individual condensers comprising a condenser chain.

Pyrolysis of waste tyres: A review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, Paul T., E-mail: p.t.williams@leeds.ac.uk

2013-08-15

Graphical abstract: - Highlights: • Pyrolysis of waste tyres produces oil, gas and char, and recovered steel. • Batch, screw kiln, rotary kiln, vacuum and fluidised-bed are main reactor types. • Product yields are influenced by reactor type, temperature and heating rate. • Pyrolysis oils are complex and can be used as chemical feedstock or fuel. • Research into higher value products from the tyre pyrolysis process is reviewed. - Abstract: 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 inmore » 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{sub 2}, C{sub 1}–C{sub 4} hydrocarbons, CO{sub 2}, CO and H{sub 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.« less

Pyrolysis of automotive shredder residue in a bench scale rotary kiln.

PubMed

Notarnicola, Michele; Cornacchia, Giacinto; De Gisi, Sabino; Di Canio, Francesco; Freda, Cesare; Garzone, Pietro; Martino, Maria; Valerio, Vito; Villone, Antonio

2017-07-01

Automotive shredder residue (ASR) can create difficulties when managing, with its production increasing. It is made of different type of plastics, foams, elastomers, wood, glasses and textiles. For this reason, it is complicated to dispose of in a cost effective way, while also respecting the stringent environmental restrictions. Among thermal treatments, pyrolysis seems to offer an environmentally attractive method for the treatment of ASR; it also allows for the recovery of valuable secondary materials/fuels such as pyrolysis oils, chars, and gas. While, there is a great deal of significant research on ASR pyrolysis, the literature on higher scale pyrolysis experiments is limited. To improve current literature, the aim of the study was to investigate the pyrolysis of ASR in a bench scale rotary kiln. The Italian ASR was separated by dry-sieving into two particle size fractions: d<30mm and d>30mm. Both the streams were grounded, pelletized and then pyrolyzed in a continuous bench scale rotary kiln at 450, 550 and 650°C. The mass flow rate of the ASR pellets was 200-350g/h and each test ran for about 4-5h. The produced char, pyrolysis oil and syngas were quantified to determine product distribution. They were thoroughly analyzed with regard to their chemical and physical properties. The results show how higher temperatures increase the pyrolysis gas yield (44wt% at 650°C) as well as its heating value. The low heating value (LHV) of syngas ranges between 18 and 26MJ/Nm 3 dry. The highest pyrolysis oil yield (33wt.%) was observed at 550°C and its LHV ranges between 12.5 and 14.5MJ/kg. Furthermore, only two out of the six produced chars respect the LHV limit set by the Italian environmental regulations for landfilling. The obtained results in terms of product distribution and their chemical-physical analyses provide useful information for plant scale-up. Copyright © 2017 Elsevier Ltd. All rights reserved.

Oil production by entrained pyrolysis of biomass and processing of oil and char

DOEpatents

Knight, James A.; Gorton, Charles W.

1990-01-02

Entrained pyrolysis of lignocellulosic material proceeds from a controlled pyrolysis-initiating temperature to completion of an oxygen free environment at atmospheric pressure and controlled residence time to provide a high yield recovery of pyrolysis oil together with char and non-condensable, combustible gases. The residence time is a function of gas flow rate and the initiating temperature is likewise a function of the gas flow rate, varying therewith. A controlled initiating temperature range of about 400.degree. C. to 550.degree. C. with corresponding gas flow rates to maximize oil yield is disclosed.

Method for preventing plugging in the pyrolysis of agglomerative coals

DOEpatents

Green, Norman W.

1979-01-23

To prevent plugging in a pyrolysis operation where an agglomerative coal in a nondeleteriously reactive carrier gas is injected as a turbulent jet from an opening into an elongate pyrolysis reactor, the coal is comminuted to a size where the particles under operating conditions will detackify prior to contact with internal reactor surfaces while a secondary flow of fluid is introduced along the peripheral inner surface of the reactor to prevent backflow of the coal particles. The pyrolysis operation is depicted by two equations which enable preselection of conditions which insure prevention of reactor plugging.

Flash Pyrolysis and Fractional Pyrolysis of Oleaginous Biomass in a Fluidized-bed Reactor

NASA Astrophysics Data System (ADS)

Urban, Brook

Thermochemical conversion methods such as pyrolysis have the potential for converting diverse biomass feedstocks into liquid fuels. In particular, bio-oil yields can be maximized by implementing flash pyrolysis to facilitate rapid heat transfer to the solids along with short vapor residence times to minimize secondary degradation of bio-oils. This study first focused on the design and construction of a fluidized-bed flash pyrolysis reactor with a high-efficiency bio-oil recovery unit. Subsequently, the reactor was used to perform flash pyrolysis of soybean pellets to assess the thermochemical conversion of oleaginous biomass feedstocks. The fluidized bed reactor design included a novel feed input mechanism through suction created by flow of carrier gas through a venturi which prevented plugging problems that occur with a more conventional screw feeders. In addition, the uniquely designed batch pyrolysis unit comprised of two tubes of dissimilar diameters. The bottom section consisted of a 1" tube and was connected to a larger 3" tube placed vertically above. At the carrier gas flow rates used in these studies, the feed particles remained fluidized in the smaller diameter tube, but a reduction in carrier gas velocity in the larger diameter "disengagement chamber" prevented the escape of particles into the condensers. The outlet of the reactor was connected to two Allihn condensers followed by an innovative packed-bed dry ice condenser. Due to the high carrier gas flow rates in fluidized bed reactors, bio-oil vapors form dilute aerosols upon cooling which that are difficult to coalesce and recover by traditional heat exchange condensers. The dry ice condenser provided high surface area for inertial impaction of these aerosols and also allowed easy recovery of bio-oils after natural evaporation of the dry ice at the end of the experiments. Single step pyrolysis was performed between 250-610°C with a vapor residence time between 0.3-0.6s. At 550°C or higher, 70% of the initial feed mass was recovered as bio-oil. However, the mass of high calorific lipid-derived components in the collected bio-oils remained nearly constant at reaction temperatures above 415°C; between 80-90% of the feedstock lipids were recovered in the bio-oil fraction. In addition, multi-step fractional flash pyrolysis experiments were performed to assess the possibility of producing higher quality bio-oils since a large fraction of protein and carbohydrates degrade at lower temperatures (320-400°C). A low temperature pyrolysis step was first performed and was followed by pyrolysis of the residues at higher temperature. This fractional pyrolysis approach which produced higher quality bio-oil with low water- and nitrogen- content from the higher temperature steps.

Analytical pyrolysis mass spectrometry: new vistas opened by temperature-resolved in-source PYMS

NASA Astrophysics Data System (ADS)

Boon, Jaap J.

1992-09-01

Analytical pyrolysis mass spectrometry (PYMS) is introduced and its applications to the analysis of synthetic polymers, biopolymers, biomacromolecular systems and geomacromolecules are critically reviewed. Analytical pyrolysis inside the ionisation chamber of a mass spectrometer, i.e. in-source PYMS, gives a complete inventory of the pyrolysis products evolved from a solid sample. The temperature-resolved nature of the experiment gives a good insight into the temperature dependence of the volatilisation and pyrolytic dissociation processes. Chemical ionisation techniques appear to be especially suitable for the analysis of oligomeric fragments released in early stages of the pyrolysis of polymer systems. Large oligomeric fragments were observed for linear polymers such as cellulose (pentadecamer), polyhydroxyoctanoic acid (tridecamer) and polyhydroxybutyric acid (heneicosamer). New in-source PYMS data are presented on artists' paints, the plant polysaccharides cellulose and xyloglucan, several microbial polyhydroxyalkanoates, wood and enzyme-digested wood, biodegraded roots and a fossil cuticle of Miocene age. On-line and off-line pyrolysis chromatography mass spectrometric approaches are also discussed. New data presented on high temperature gas chromatography--mass spectrometry of deuterio-reduced permethylated pyrolysates of cellulose lead to a better understanding of polysaccharide dissociation mechanisms. Pyrolysis as an on-line sample pretreatment method for organic macromolecules in combination with MS techniques is a very challenging field of mass spectrometry. Pyrolytic dissociation and desorption is not at all a chaotic process but proceeds according to very specific mechanisms.

Catalytic fast pyrolysis of biomass impregnated with potassium phosphate in a hydrogen atmosphere for the production of phenol and activated carbon

NASA Astrophysics Data System (ADS)

Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

2018-02-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550 oC in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1605 m2/g.

[Bio-oil production from biomass pyrolysis in molten salt].

PubMed

Ji, Dengxiang; Cai, Tengyue; Ai, Ning; Yu, Fengwen; Jiang, Hongtao; Ji, Jianbing

2011-03-01

In order to investigate the effects of pyrolysis conditions on bio-oil production from biomass in molten salt, experiments of biomass pyrolysis were carried out in a self-designed reactor in which the molten salt ZnCl2-KCl (with mole ratio 7/6) was selected as heat carrier, catalyst and dispersion agent. The effects of metal salt added into ZnCl2-KCl and biomass material on biomass pyrolysis were discussed, and the main compositions of bio-oil were determined by GC-MS. Metal salt added into molten salt could affect pyrolysis production yields remarkably. Lanthanon salt could enhance bio-oil yield and decrease water content in bio-oil, when mole fraction of 5.0% LaCl3 was added, bio-oil yield could reach up to 32.0%, and water content of bio-oil could reduce to 61.5%. The bio-oil and char yields were higher when rice straw was pyrolysed, while gas yield was higher when rice husk was used. Metal salts showed great selectivity on compositions of bio-oil. LiCl and FeCl2 promoted biomass to pyrolyse into smaller molecular weight compounds. CrCl3, CaCl2 and LaCl3 could restrain second pyrolysis of bio-oil. The research provided a scientific reference for production of bio-oil from biomass pyrolysis in molten salt.

Pyrolysis behavior of different type of materials contained in the rejects of packaging waste sorting plants.

PubMed

Adrados, A; De Marco, I; Lopez-Urionabarrenechea, A; Caballero, B M; Laresgoiti, M F

2013-01-01

In this paper rejected streams coming from a waste packaging material recovery facility have been characterized and separated into families of products of similar nature in order to determine the influence of different types of ingredients in the products obtained in the pyrolysis process. The pyrolysis experiments have been carried out in a non-stirred batch 3.5 dm(3) reactor, swept with 1 L min(-1) N(2), at 500°C for 30 min. Pyrolysis liquids are composed of an organic phase and an aqueous phase. The aqueous phase is greater as higher is the cellulosic material content in the sample. The organic phase contains valuable chemicals as styrene, ethylbenzene and toluene, and has high heating value (HHV) (33-40 MJ kg(-1)). Therefore they could be used as alternative fuels for heat and power generation and as a source of valuable chemicals. Pyrolysis gases are mainly composed of hydrocarbons but contain high amounts of CO and CO(2); their HHV is in the range of 18-46 MJ kg(-1). The amount of COCO(2) increases, and consequently HHV decreases as higher is the cellulosic content of the waste. Pyrolysis solids are mainly composed of inorganics and char formed in the process. The cellulosic materials lower the quality of the pyrolysis liquids and gases, and increase the production of char. Copyright © 2012 Elsevier Ltd. All rights reserved.

Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon

PubMed Central

Lu, Qiang; Zhang, Zhen-xi; Wang, Xin; Guo, Hao-qiang; Cui, Min-shu; Yang, Yong-ping

2018-01-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K3PO4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K3PO4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K3PO4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO2 activation method, the specific surface area was as high as 1,605 m2/g. PMID:29515994

Preparation of brightness stabilization agent for lignin containing pulp from biomass pyrolysis oils

DOEpatents

Agblevor, Foster A.; Besler-Guran, Serpil

2001-01-01

A process for producing a brightness stabilization mixture of water-soluble organic compounds from biomass pyrolysis oils comprising: a) size-reducing biomass material and pyrolyzing the size-reduced biomass material in a fluidized bed reactor; b) separating a char/ash component while maintaining char-pot temperatures to avoid condensation of pyrolysis vapors; c) condensing pyrolysis gases and vapors, and recovering pyrolysis oils by mixing the oils with acetone to obtain an oil-acetone mixture; d) evaporating acetone and recovering pyrolysis oils; e) extracting the pyrolysis oils with water to obtain a water extract; f) slurrying the water extract with carbon while stirring, and filtering the slurry to obtain a colorless filtrate; g) cooling the solution and stabilizing the solution against thermally-induced gelling and solidification by extraction with ethyl acetate to form an aqueous phase lower layer and an organic phase upper layer; h) discarding the upper organic layer and extracting the aqueous layer with ethyl acetate, and discarding the ethyl acetate fraction to obtain a brown-colored solution not susceptible to gelling or solidification upon heating; i) heating the solution to distill off water and other light components and concentrating a bottoms fraction comprising hydroxyacetaldehyde and other non-volatile components having high boiling points; and j) decolorizing the stabilized brown solution with activated carbon to obtain a colorless solution.

Thermogravimetric kinetic study of agricultural residue biomass pyrolysis based on combined kinetics.

PubMed

Wang, Xun; Hu, Mian; Hu, Wanyong; Chen, Zhihua; Liu, Shiming; Hu, Zhiquan; Xiao, Bo

2016-11-01

Pyrolytic kinetic of an agricultural residue (AR) feedstock, a mixture of plants (cotton, wheat, rich, corn) stems, was investigated based on combined kinetics. The most suitable mechanism for AR one-step pyrolysis was f(α)=(1-α)(1.1816)α(-1.8428) with kinetic parameters of: apparent activation energy 221.7kJ/mol, pre-exponential factor 4.17E16s(-1). Pyrolysis of AR feedstock could not be described by one-step reaction attributes to heterogeneous features of pyrolysis processes. Combined kinetics three-parallel-reaction (CK-TPR) model fitted the pyrolysis experimental data very well. Reaction mechanisms for pseudo hemicelluloses, cellulose, lignin in CK-TPR model was f(α)=(1-α)(1.6244)α(-0.3371)[-ln(1-α)](-0.0515), f(α)=(1-α)(1.0597)α(-0.6909)[-ln(1-α)](0.9026) and f(α)=(1-α)(2.9577)α(-4.7719), respectively. Apparent activation energy of three pseudo components followed the order of Elignin(197.3kJ/mol)>Ecellulose(176.3kJ/mol)>Ehemicelluloses (151.1kJ/mol). Mechanism of hemicelluloses pyrolysis could be further expressed as f(α)=(1-α)(1.4). The pyrolytic mechanism of cellulose met the Nucleation well. However, mechanism of lignin pyrolysis was complex, which possibly was the combined effects of Nucleation, Diffusion, Geometrical contraction, and Power law. Copyright © 2016 Elsevier Ltd. All rights reserved.

Staged thermal fractionation for segregation of lignin and cellulose pyrolysis products: An experimental study of residence time and temperature effects

DOE PAGES

Waters, Christopher L.; Janupala, Rajiv R.; Mallinson, Richard G.; ...

2017-05-25

Thermal conversion technologies may be the most efficient means of production of transportation fuels from lignocellulosic biomass. In order to increase the viability and improve the carbon emissions profile of pyrolysis biofuels, improvements must be made to the required catalytic upgrading to increase both hydrogen utilization efficiency and final liquid carbon yields. However, no current single catalytic valorization strategy can be optimized to convert the complex mixture of compounds produced upon fast pyrolysis of biomass. Staged thermal fractionation, which entails a series of sequentially increasing temperature steps to decompose biomass, has been proposed as a simple means to create vapormore » product streams of enhanced purity as compared to fast pyrolysis. In this work, we use analytical pyrolysis to investigate the effects of time and temperature on a thermal step designed to segregate the lignin and cellulose pyrolysis products of a biomass which has been pre-torrefied to remove hemicellulose. At process conditions of 380 °C and 180 s isothermal hold time, a stream containing less than 20% phenolics (carbon basis) was produced, and upon subsequent fast pyrolysis of the residual solid a stream of 81.5% levoglucosan (carbon basis) was produced. The thermal segregation comes at the expense of vapor product carbon yield, but the improvement in catalytic performance may offset these losses.« less

The Search for Hesperian Organic Matter on Mars: Pyrolysis Studies of Sediments Rich in Sulfur and Iron.

PubMed

Lewis, James M T; Najorka, Jens; Watson, Jonathan S; Sephton, Mark A

2018-04-01

Jarosite on Mars is of significant geological and astrobiological interest, as it forms in acidic aqueous conditions that are potentially habitable for acidophilic organisms. Jarosite can provide environmental context and may host organic matter. The most common extraction technique used to search for organic compounds on the surface of Mars is pyrolysis. However, thermal decomposition of jarosite releases oxygen into pyrolysis ovens, which degrades organic signals. Jarosite has a close association with the iron oxyhydroxide goethite in many depositional/diagenetic environments. Hematite can form by dehydration of goethite or directly from jarosite under certain aqueous conditions. Goethite and hematite are significantly more amenable than jarosite for pyrolysis experiments employed to search for organic matter. Analysis of the mineralogy and organic chemistry of samples from a natural acidic stream revealed a diverse response for organic compounds during pyrolysis of goethite-rich layers but a poor response for jarosite-rich or mixed jarosite-goethite samples. Goethite units that are associated with jarosite, but do not contain jarosite themselves, should be targeted for organic detection pyrolysis experiments on Mars. These findings are extremely timely, as exploration targets for Mars Science Laboratory include Vera Rubin Ridge (formerly known as "Hematite Ridge"), which may have formed from goethite precursors. Key Words: Mars-Pyrolysis-Jarosite-Goethite-Hematite-Biosignatures. Astrobiology 18, 454-464.

Influence of pyrolysis temperature on properties and environmental safety of heavy metals in biochars derived from municipal sewage sludge.

PubMed

Jin, Junwei; Li, Yanan; Zhang, Jianyun; Wu, Shengchun; Cao, Yucheng; Liang, Peng; Zhang, Jin; Wong, Ming Hung; Wang, Minyan; Shan, Shengdao; Christie, Peter

2016-12-15

Dried raw sludge was pyrolyzed at temperatures ranging from 400 to 600°C at the increase of 50°C intervals to investigate the influence of pyrolysis temperature on properties and environmental safety of heavy metals in biochar derived from municipal sewage sludge. The sludge biochar yield decreased significantly with increasing pyrolysis temperature but the pH, ash content and specific surface area increased. Conversion of sludge to biochar markedly decreased the H/C and N/C ratios. FT-IR analysis confirmed a dramatic depletion of H and N and a higher degree of aromatic condensation in process of biochar formation at higher temperatures. The total concentrations of Cu, Zn, Pb, Cr, Mn, and Ni increased with conversion of sludge to biochar and increasing pyrolysis temperature. However, using BCR sequential extraction and analysis, it was found that most of the heavy metals existed in the oxizable and residual forms after pyrolysis, especially at 600°C, resulting in a significant reduction in their bioavailability, leading to a very low environmental risk of the biochar. The present study indicates pyrolysis is a promising sludge treatment method for heavy metals immobilization in biochar, and highlights the potential to minimize the harmful effects of biochar by controlling pyrolysis temperature. Copyright © 2016 Elsevier B.V. All rights reserved.

Investigation on the removal of H2S from microwave pyrolysis of sewage sludge by an integrated two-stage system.

PubMed

Zhang, Jun; Tian, Yu; Yin, Linlin; Zuo, Wei; Gong, Zhenlong; Zhang, Jie

2017-08-01

In this study, an integrated two-stage system, including the in-situ catalytic microwave pyrolysis (ICMP) and subsequent catalytic wet oxidation (CWO) processes, was proposed to remove H 2 S released from microwave-induced pyrolysis of sewage sludge. The emission profile and H 2 S removal from the pyrolysis of raw sewage sludge (SS) and sewage sludge spiked with conditioner CaO (SS-CaO) were investigated. The results showed that CaO played a positive role on sulfur fixation during the pyrolysis process. It was found that SS-CaO (10 wt.%) contributed to about 35% of H 2 S removal at the first stage (ICMP process). Additionally, the CWO process was demonstrated to have promising potential for posttreatment of remaining H 2 S gas. At the Fe 3+ concentration of 30 g/L, the maximum H 2 S removal efficiency of 94.8% was obtained for a single Fe 3+ /Cu 2+ solution. Finally, at the pyrolysis temperature of 800 °C, 99.7% of H 2 S was eliminated by the integrated two-stage system meeting the discharge standard of China. Therefore, the integrated two-stage system of ICMP + CWO may provide a promising strategy to remove H 2 S dramatically for the biomass pyrolysis industry.

Catalytic Fast Pyrolysis of Biomass Impregnated with Potassium Phosphate in a Hydrogen Atmosphere for the Production of Phenol and Activated Carbon.

PubMed

Lu, Qiang; Zhang, Zhen-Xi; Wang, Xin; Guo, Hao-Qiang; Cui, Min-Shu; Yang, Yong-Ping

2018-01-01

A new technique was proposed to co-produce phenol and activated carbon (AC) from catalytic fast pyrolysis of biomass impregnated with K 3 PO 4 in a hydrogen atmosphere, followed by activation of the pyrolytic solid residues. Lab-scale catalytic fast pyrolysis experiments were performed to quantitatively determine the pyrolytic product distribution, as well as to investigate the effects of several factors on the phenol production, including pyrolysis atmosphere, catalyst type, biomass type, catalytic pyrolysis temperature, and catalyst impregnation content. In addition, the pyrolytic solid residues were activated to prepare ACs with high specific surface areas. The results indicated that phenol could be obtained due to the synergistic effects of K 3 PO 4 and hydrogen atmosphere, with the yield and selectivity reaching 5.3 wt% and 17.8% from catalytic fast pyrolysis of poplar wood with 8 wt% K 3 PO 4 at 550°C in a hydrogen atmosphere. This technique was adaptable to different woody materials for phenol production. Moreover, gas product generated from the pyrolysis process was feasible to be recycled to provide the hydrogen atmosphere, instead of extra hydrogen supply. In addition, the pyrolytic solid residue was suitable for AC preparation, using CO 2 activation method, the specific surface area was as high as 1,605 m 2 /g.

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hui; Energy Research Institute, University of Leeds, Leeds LS2 9JT; Wu, Chunfei, E-mail: c.wu@leeds.ac.uk

2015-02-15

Highlights: • PAH from pyrolysis of 9 MSW fractions was investigated. • Pyrolysis of plastics released more PAH than that of biomass. • Naphthalene was the most abundant PAH in the tar. • The mechanism of PAH release from biomass and plastics was proposed. - Abstract: The formation of 2–4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. Themore » results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock.« less

Staged thermal fractionation for segregation of lignin and cellulose pyrolysis products: An experimental study of residence time and temperature effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Waters, Christopher L.; Janupala, Rajiv R.; Mallinson, Richard G.

Thermal conversion technologies may be the most efficient means of production of transportation fuels from lignocellulosic biomass. In order to increase the viability and improve the carbon emissions profile of pyrolysis biofuels, improvements must be made to the required catalytic upgrading to increase both hydrogen utilization efficiency and final liquid carbon yields. However, no current single catalytic valorization strategy can be optimized to convert the complex mixture of compounds produced upon fast pyrolysis of biomass. Staged thermal fractionation, which entails a series of sequentially increasing temperature steps to decompose biomass, has been proposed as a simple means to create vapormore » product streams of enhanced purity as compared to fast pyrolysis. In this work, we use analytical pyrolysis to investigate the effects of time and temperature on a thermal step designed to segregate the lignin and cellulose pyrolysis products of a biomass which has been pre-torrefied to remove hemicellulose. At process conditions of 380 °C and 180 s isothermal hold time, a stream containing less than 20% phenolics (carbon basis) was produced, and upon subsequent fast pyrolysis of the residual solid a stream of 81.5% levoglucosan (carbon basis) was produced. The thermal segregation comes at the expense of vapor product carbon yield, but the improvement in catalytic performance may offset these losses.« less

High-temperature pyrolysis of blended animal manures for producing renewable energy and value-added biochar

USDA-ARS?s Scientific Manuscript database

In this study, we used a commercial pilot-scale, skid-mounted pyrolysis reactor system to produce combustible gas and biochar at 620ºC from three sources (chicken litter, swine solids, mixture of swine solids with rye grass). Pyrolysis of swine solids produced gas with the greatest higher heating va...

Guayule (parthenium argentatum) pyrolysis biorefining: production of hydrocarbon compatible bio-oils from guayule bagasse via tail-gas reactive pyrolysis

USDA-ARS?s Scientific Manuscript database

Guayule (Parthenium argentatum) is a woody desert shrub grown in the southwestern United States as a source of natural rubber, organic resins, and high energy biofuel feedstock from crop residues. We used guayule bagasse, the residual biomass after latex extraction as feedstock in a pyrolysis proces...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiong, Qingang; Robichaud, David J.

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

An exergy based assessment of the production and conversion of switchgrass, equine waste and forest residue to bio-oil using fast pyrolysis

USDA-ARS?s Scientific Manuscript database

The resource efficiency of biofuel production via biomass pyrolysis is evaluated using exergy as an assessment metric. Three feedstocks, important to various sectors of US agriculture, switchgrass, forest residue and equine waste are considered for conversion to bio-oil (pyrolysis oil) via fast pyro...

Thermal Stability of Fluorinated Polydienes Synthesized by Addition of Difluorocarbene

DTIC Science & Technology

2012-01-01

polydienes proceeds through a two-stage decomposition involving chain scission, crosslinking, dehydrogenation, and dehalogenation . The pyrolysis leads...polydienes proceeds through a two-stage decomposition involving chain scission, crosslinking, dehydrogenation, and dehalogenation . The pyrolysis leads to... dehalogenation . The pyrolysis leads to graphite-like residues, whereas their polydiene precursors decompose completely under the same conditions. The

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

USDA-ARS?s Scientific Manuscript database

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

Role of potassium exchange in catalytic pyrolysis of biomass over ZSM-5: Formation of alkyl phenols and furans

USDA-ARS?s Scientific Manuscript database

Catalytic fast pyrolysis of biomass with ZSM-5 type zeolites is a commonly considered in situ upgrading technique for the production of partially deoxygenated bio-oils. The acidity and structure of ZSM-5 catalysts favor the production of aromatic hydrocarbons from oxygenates present in the pyrolysis...

Toxicity of pyrolysis gases from polyether sulfone

NASA Technical Reports Server (NTRS)

Hilado, C. J.; Olcomendy, E. M.

1979-01-01

A sample of polyether sulfone was evaluated for toxicity of pyrolysis gases, using the toxicity screening test method developed at the University of San Francisco. Animal response times were relatively short at pyrolysis temperatures of 600 to 800 C, with death occurring within 6 min. The principal toxicant appeared to be a compound other than carbon monoxide.

Impregnation of bio-oil from small diameter pine into wood for moisture resistance

Treesearch

Thomas J. Robinson; Brian K. Via; Oladiran Fasina; Sushil Adhikari; Emily Carter

2011-01-01

Wood pyrolysis oil consists of hundreds of complex compounds, many of which are phenolic-based and exhibit hydrophobic properties. Southern yellow pine was impregnated with a pyrolysis oil-based penetrant using both a high pressure and vacuum impregnation systems, with no significant differences in retention levels. Penetrant concentrations ranging from 5-50% pyrolysis...

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

USDA-ARS?s Scientific Manuscript database

Tail-gas reactive pyrolysis (TGRP) of biomass produces bio-oil that is lower in oxygen (~15 wt% total) and significantly more hydrocarbon-rich than traditional bio-oils or even catalytic fast pyrolysis. TGRP bio-oils lend themselves toward mild and inexpensive upgrading procedures. We isolated oxyge...

Simplifying pyrolysis; using gasification to produce corn stover and wheat straw biochar for sorptive and horitcultural media

USDA-ARS?s Scientific Manuscript database

Biochar is a renewable, useful material that can be utilized in many different applications. Biochar is commonly produced via pyrolysis methods using a retort-style oven with inert gas. Gasification is another method that can utilize pyrolysis to produce biochar, but with the advantage of not requir...

Effluent Gas Flux Characterization During Pyrolysis of Chicken Manure

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

NASA Astrophysics Data System (ADS)

Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney

2016-07-01

Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H513CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H513CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

The hierarchical porous structure bio-char assessments produced by co-pyrolysis of municipal sewage sludge and hazelnut shell and Cu(II) adsorption kinetics.

PubMed

Zhao, Bing; Xu, Xinyang; Zeng, Fanqiang; Li, Haibo; Chen, Xi

2018-05-04

The co-pyrolysis technology was applied to municipal sewage sludge (MSS) and hazelnut shell with alkaline activating agent K 2 CO 3 under N 2 atmosphere. The innovative bio-char produced by co-pyrolysis had significant physical and chemical characteristics. The specific surface area reached 1990.23 m 2 /g, and the iodine absorption number was 1068.22 mg/g after co-pyrolysis at 850 °C. Although hazelnut shell was a kind of solid waste, it also had abundant cellulose resource, which could contribute to porous structure of bio-char during co-pyrolysis with MSS and decrease total heavy metals contents of raw material to increase security of bio-chars. Meanwhile, the residual fractions of heavy metals in bio-char were above 92.95% after co-pyrolysis at 900 °C except Cd to prevent heavy metals digestion, and the bio-char presented significant immobilization behavior from co-pyrolysis technology. Moreover, the yield and the iodine absorption number of bio-chars under different process variables were analyzed, and it was confirmed that appropriate process variables could contribute the yield and the iodine absorption number of bio-char and prevent to etch pore structure excessively to collapse. The changes of surface functional groups and crystallographic structure before and after co-pyrolysis were analyzed by FTIR and XRD, respectively. The hierarchical porous structure of bio-char was presented by SEM and N 2 adsorption-desorption isotherm. The Cu(II) adsorption capacity of the bio-char was 42.28 mg/g after 24 h, and surface functional groups acted as active binding sites for Cu(II) adsorption. Langmuir model and pseudo-second-order model can describe process of Cu(II) adsorption well.

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

PubMed

Hammer, Nicole L; Boateng, Akwasi A; Mullen, Charles A; Wheeler, M Clayton

2013-10-15

Aspen Plus(®) based simulation models have been developed to design a pyrolysis process for on-site production and utilization of pyrolysis oil from equine waste at the Equine Rehabilitation Center at Morrisville State College (MSC). The results indicate that utilization of all the available waste from the site's 41 horses requires a 6 oven dry metric ton per day (ODMTPD) pyrolysis system but it will require a 15 ODMTPD system for waste generated by an additional 150 horses at the expanded area including the College and its vicinity. For this a dual fluidized bed combustion reduction integrated pyrolysis system (CRIPS) developed at USDA's Agricultural Research Service (ARS) was identified as the technology of choice for pyrolysis oil production. The Aspen Plus(®) model was further used to consider the combustion of the produced pyrolysis oil (bio-oil) in the existing boilers that generate hot water for space heating at the Equine Center. The model results show the potential for both the equine facility and the College to displace diesel fuel (fossil) with renewable pyrolysis oil and alleviate a costly waste disposal problem. We predict that all the heat required to operate the pyrolyzer could be supplied by non-condensable gas and about 40% of the biochar co-produced with bio-oil. Techno-economic Analysis shows neither design is economical at current market conditions; however the 15 ODMTPD CRIPS design would break even when diesel prices reach $11.40/gal. This can be further improved to $7.50/gal if the design capacity is maintained at 6 ODMTPD but operated at 4950 h per annum. Published by Elsevier Ltd.

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg

2016-07-05

Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 us. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures upmore » to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 13CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 13CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less

Pyrolysis of wastewater sludge and composted organic fines from municipal solid waste: laboratory reactor characterisation and product distribution.

PubMed

Agar, David A; Kwapinska, Marzena; Leahy, James J

2018-02-26

Sludge from municipal wastewater treatment plants and organic fines from mechanical sorting of municipal solid waste (MSW) are two common widespread waste streams that are becoming increasingly difficult to utilise. Changing perceptions of risk in food production has limited the appeal of sludge use on agricultural land, and outlets via landfilling are diminishing rapidly. These factors have led to interest in thermal conversion technologies whose aim is to recover energy and nutrients from waste while reducing health and environmental risks associated with material re-use. Pyrolysis yields three output products: solid char, liquid oils and gas. Their relative distribution depends on process parameters which can be somewhat optimised depending on the end use of product. The potential of pyrolysis for the conversion of wastewater sludge (SS) and organic fines of MSW (OF) to a combustion gas and a carbon-rich char has been investigated. Pyrolysis of SS and OF was done using a laboratory fixed-bed reactor. Herein, the physical characterisation of the reactor is described, and results on pyrolysis yields are presented. Feedstock and chars have been characterised using standard laboratory methods, and the composition of pyrolysis gases was analysed using micro gas chromatography. Product distribution (char/liquid/gas) from the pyrolysis of sewage sludge and composted MSW fines at 700°C for 10 min were 45/26/29 and 53/14/33%, respectively. The combustible fractions of pyrolysis gases range from 36 to 54% for SS feedstock and 62 to 72% from OF. The corresponding lower heating value range of sampled gases were 11.8-19.1 and 18.2-21.0 MJ m -3 , respectively.

Catalytic fast pyrolysis of lignocellulosic biomass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Changjun; Wang, Huamin; Karim, Ayman M.

2014-11-21

Increasing energy demand, especially in the transportation sector, and soaring CO2 emissions necessitate the exploitation of renewable sources of energy. Despite the large variety of new energy Q3 carriers, liquid hydrocarbon still appears to be the most attractive and feasible form of transportation fuel taking into account the energy density, stability and existing infrastructure. Biomass is an abundant, renewable source of energy; however, utilizing it in a cost-effective way is still a substantial challenge. Lignocellulose is composed of three major biopolymers, namely cellulose, hemicellulose and lignin. Fast pyrolysis of biomass is recognized as an efficient and feasible process to selectivelymore » convert lignocellulose into a liquid fuel—bio-oil. However bio-oil from fast pyrolysis contains a large amount of oxygen, distributed in hundreds of oxygenates. These oxygenates are the cause of many negative properties, such as low heating values, high corrosiveness, high viscosity, and instability; they also greatly Q4 limit the application of bio-oil particularly as transportation fuel. Hydrocarbons derived from biomass are most attractive because of their high energy density and compatibility with the existing infrastructure. Thus, converting lignocellulose into transportation fuels via catalytic fast pyrolysis has attracted much attention. Many studies related to catalytic fast pyrolysis of biomass have been published. The main challenge of this process is the development of active and stable catalysts that can deal with a large variety of decomposition intermediates from lignocellulose. This review starts with the current understanding of the chemistry in fast pyrolysis of lignocellulose and focuses on the development of catalysts in catalytic fast pyrolysis. Recent progress in the experimental studies on catalytic fast pyrolysis of biomass is also summarized with the emphasis on bio-oil yields and quality.« less

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

PubMed

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

2016-02-01

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

Co-pyrolysis of swine manure with agricultural plastic waste: laboratory-scale study.

PubMed

Ro, Kyoung S; Hunt, Patrick G; Jackson, Michael A; Compton, David L; Yates, Scott R; Cantrell, Keri; Chang, SeChin

2014-08-01

Manure-derived biochar is the solid product resulting from pyrolysis of animal manures. It has considerable potential both to improve soil quality with high levels of nutrients and to reduce contaminants in water and soil. However, the combustible gas produced from manure pyrolysis generally does not provide enough energy to sustain the pyrolysis process. Supplementing this process may be achieved with spent agricultural plastic films; these feedstocks have large amounts of available energy. Plastic films are often used in soil fumigation. They are usually disposed in landfills, which is wasteful, expensive, and environmentally unsustainable. The objective of this work was to investigate both the energetics of co-pyrolyzing swine solids with spent plastic mulch films (SPM) and the characteristics of its gas, liquid, and solid byproducts. The heating value of the product gas from co-pyrolysis was found to be much higher than that of natural gas; furthermore, the gas had no detectable toxic fumigants. Energetically, sustaining pyrolysis of the swine solids through the energy of the product gas could be achieved by co-pyrolyzing dewatered swine solids (25%m/m) with just 10% SPM. If more than 10% SPM is used, the co-pyrolysis would generate surplus energy which could be used for power generation. Biochars produced from co-pyrolyzing SPM and swine solid were similar to swine solid alone based on the surface area and the (1)H NMR spectra. The results of this study demonstrated the potential of using pyrolysis technology to manage two prominent agricultural waste streams (SPM and swine solids) while producing value-added biochar and a power source that could be used for local farm operations. Published by Elsevier Ltd.

Thermogravimetric study on pyrolysis kinetics of Chlorella pyrenoidosa and bloom-forming cyanobacteria.

PubMed

Hu, Mian; Chen, Zhihua; Guo, Dabin; Liu, Cuixia; Xiao, Bo; Hu, Zhiquan; Liu, Shiming

2015-02-01

The pyrolysis process of two microalgae, Chlorella pyrenoidosa (CP) and bloom-forming cyanobacteria (CB) was examined by thermo-gravimetry to investigate their thermal decomposition behavior under non-isothermal conditions. It has found that the pyrolysis of both microalgae consists of three stages and stage II is the major mass reduction stage with mass loss of 70.69% for CP and 64.43% for CB, respectively. The pyrolysis kinetics of both microalgae was further studied using single-step global model (SSGM) and distributed activation energy model (DAEM). The mean apparent activation energy of CP and CB in SSGM was calculated as 143.71 and 173.46 kJ/mol, respectively. However, SSGM was not suitable for modeling pyrolysis kinetic of both microalgae due to the mechanism change during conversion. The DAEM with 200 first-order reactions showed an excellent fit between simulated data and experimental results. Copyright © 2014 Elsevier Ltd. All rights reserved.

Whole Microorganisms Studied by Pyrolysis-Gas Chromatography-Mass Spectrometry: Significance for Extraterrestrial Life Detection Experiments 1

PubMed Central

Simmonds, Peter G.

1970-01-01

Pyrolysis-gas chromatography-mass spectrometric studies of two microorganisms, Micrococcus luteus and Bacillus subtilis var. niger, indicate that the majority of thermal fragments originate from the principal classes of bio-organic matter found in living systems such as protein and carbohydrate. Furthermore, there is a close qualitative similarity between the type of pyrolysis products found in microorganisms and the pyrolysates of other biological materials. Conversely, there is very little correlation between microbial pyrolysates and comparable pyrolysis studies of meteoritic and fossil organic matter. These observations will aid in the interpretation of a soil organic analysis experiment to be performed on the surface of Mars in 1975. The science payload of this landed mission will include a combined pyrolysis-gas chromatography-mass spectrometry instrument as well as several “direct biology experiments” which are designed to search for extraterrestrial life. PMID:16349890

Pyrolysis and catalytic pyrolysis as a recycling method of waste CDs originating from polycarbonate and HIPS.

PubMed

Antonakou, E V; Kalogiannis, K G; Stephanidis, S D; Triantafyllidis, K S; Lappas, A A; Achilias, D S

2014-12-01

Pyrolysis appears to be a promising recycling process since it could convert the disposed polymers to hydrocarbon based fuels or various useful chemicals. In the current study, two model polymers found in WEEEs, namely polycarbonate (PC) and high impact polystyrene (HIPS) and their counterparts found in waste commercial Compact Discs (CDs) were pyrolysed in a bench scale reactor. Both, thermal pyrolysis and pyrolysis in the presence of two catalytic materials (basic MgO and acidic ZSM-5 zeolite) was performed for all four types of polymers. Results have shown significant recovery of the monomers and valuable chemicals (phenols in the case of PC and aromatic hydrocarbons in the case of HIPS), while catalysts seem to decrease the selectivity towards the monomers and enhance the selectivity towards other desirable compounds. Copyright © 2014 Elsevier Ltd. All rights reserved.

Quantitation of sugar content in pyrolysis liquids after acid hydrolysis using high-performance liquid chromatography without neutralization.

PubMed

Johnston, Patrick A; Brown, Robert C

2014-08-13

A rapid method for the quantitation of total sugars in pyrolysis liquids using high-performance liquid chromatography (HPLC) was developed. The method avoids the tedious and time-consuming sample preparation required by current analytical methods. It is possible to directly analyze hydrolyzed pyrolysis liquids, bypassing the neutralization step usually required in determination of total sugars. A comparison with traditional methods was used to determine the validity of the results. The calibration curve coefficient of determination on all standard compounds was >0.999 using a refractive index detector. The relative standard deviation for the new method was 1.13%. The spiked sugar recoveries on the pyrolysis liquid samples were between 104 and 105%. The research demonstrates that it is possible to obtain excellent accuracy and efficiency using HPLC to quantitate glucose after acid hydrolysis of polymeric and oligomeric sugars found in fast pyrolysis bio-oils without neutralization.

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

NASA Astrophysics Data System (ADS)

Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

2017-06-01

Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.

Co-pyrolysis behavior of fermentation residues with woody sawdust by thermogravimetric analysis and a vacuum reactor.

PubMed

Zheng, Yan; Zhang, Yimin; Xu, Jingna; Li, Xiayang; Charles Xu, Chunbao

2017-12-01

This study aimed at cost-effective utilization of fermentation residues (FR) from biogas project for bio-energy via co-pyrolysis of FR and woody sawdust (WS). In this study, a vacuum reactor was used to study the pyrolysis behaviors of individual and blend samples of FR and WS. Obvious synergistic effects were observed, resulting in a lower char yield but a higher gas yield. The presence of woody sawdust promoted the devolatilization of FR, and improved the syngas (H 2 and CO) content in the gaseous products. Compared to those of the char from pyrolysis of individual feedstock, co-pyrolysis of FR and WS in the vacuum reactor promoted the cracking reactions of large aromatic rings, enlarged the surface area and reduced the oxygenated groups of the resulted char. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

Pattiya, Adisak; Suttibak, Suntorn

2012-07-01

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

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

PubMed

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

2010-01-01

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

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

DOE PAGES

Thompson, Logan C.; Ciesielski, Peter N.; Jarvis, Mark W.; ...

2017-07-12

Here, biomass particles can experience variable thermal conditions during fast pyrolysis due to differences in their size and morphology, and from local temperature variations within a reactor. These differences lead to increased heterogeneity of the chemical products obtained in the pyrolysis vapors and bio-oil. Here we present a simple, high-throughput method to investigate the thermal history experienced by large ensembles of particles during fast pyrolysis by imaging and quantitative image analysis. We present a correlation between the surface luminance (darkness) of the biochar particle and the highest temperature that it experienced during pyrolysis. Next, we apply this correlation to large,more » heterogeneous ensembles of char particles produced in a laminar entrained flow reactor (LEFR). The results are used to interpret the actual temperature distributions delivered by the reactor over a range of operating conditions.« less

Characterization and inventory of PBDD/F emissions from deca-BDE, polyethylene (PE) and metal blends during the pyrolysis process.

PubMed

Mei, Jun; Wang, Xiuji; Xiao, Xiao; Cai, Ying; Tang, Yuhui; Chen, Pei

2017-04-01

The thermal treatment of waste electrical and electronic equipment (WEEE) is regarded as the largest potential contributor to the environmental release of polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs). Herein, the pyrolysis of decabromodiphenyl ether (deca-BDE), polyethylene (PE) and metal blends was conducted to investigate the emission characteristics of PBDD/Fs at different thermal treatment conditions. The total yield of polybrominated dibenzo-p-dioxins (PBDDs) was less than that of polybrominated dibenzofurans (PBDFs) during the pyrolysis of the PE matrix and metal blends. 2,3,7,8-TBDF and 1,2,3,7,8-PBDF were the dominant congeners emitted from the pyrolysis. Temperature, presence of oxygen and type of added metal were the critical influencing factors for the PBDD/F formation rates and speciation in the pyrolysis process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Acidity of biomass fast pyrolysis bio-oils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oasmaa, Anja; Elliott, Douglas C.; Korhonen, Jaana

2010-12-17

The use of the TAN method for measuring the acidity of biomass fast pyrolysis bio-oil was evaluated. Suggestions for carrying out the analysis have been made. The TAN method by ASTM D664 or D3339 can be used for measuring the acidity of fast pyrolysis bio-oils and their hydrotreating products. The main difference between the methods is that ASTM D664 is specified for higher TAN values than ASTM D3339. Special focus should be placed on the interpretation of the TAN curves because they differ significantly from those of mineral oils. The curve for bio-oils is so gentle that the automatic detectionmore » may not observe the end point properly and derivatization should be used. The acidity of fast pyrolysis bio-oils is mainly derived (60-70%) from volatile acids. Other groups of compounds in fast pyrolysis bio-oils that influence acidity include phenolics, fatty and resin acids, and hydroxy acids.« less

Requirements for transportation of fast pyrolysis bio-oil in Finland

NASA Astrophysics Data System (ADS)

Karhunen, Antti; Laihanen, Mika; Ranta, Tapio

2016-11-01

The purpose of this paper is to discuss the requirements and challenges of pyrolysis oil's transportation in Finland. Pyrolysis oil is a new type of renewable liquid fuel that can be utilised in applications such as heat and electricity production. It has never been transported on a large scale in Finland. Possible options are transport by road, rail and waterway. The most significant requirements in its transportation are created by acidity and high density of pyrolysis oil, which impose requirements for the materials and transport equipment. The study described here shows that constant domestic transportation of pyrolysis oil is most reasonably operated with tank trucks. Rail-based transport may have potential for domestic fixed routes, and transport by water could be utilised in exporting. All transportation methods have limitations and advantages relative to each other. Ultimately, the production site and end-user's locations will determine the most suitable transport method.

Chapter 8: Pyrolysis Mechanisms of Lignin Model Compounds Using a Heated Micro-Reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robichaud, David J.; Nimlos, Mark R.; Ellison, G. Barney

2015-10-03

Lignin is an important component of biomass, and the decomposition of its thermal deconstruction products is important in pyrolysis and gasification. In this chapter, we investigate the unimolecular pyrolysis chemistry through the use of singly and doubly substituted benzene molecules that are model compounds representative of lignin and its primary pyrolysis products. These model compounds are decomposed in a heated micro-reactor, and the products, including radicals and unstable intermediates, are measured using photoionization mass spectrometry and matrix isolation infrared spectroscopy. We show that the unimolecular chemistry can yield insight into the initial decomposition of these species. At pyrolysis and gasificationmore » severities, singly substituted benzenes typically undergo bond scission and elimination reactions to form radicals. Some require radical-driven chain reactions. For doubly substituted benzenes, proximity effects of the substituents can change the reaction pathways.« less

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

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

USDA-ARS?s Scientific Manuscript database

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

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

USDA-ARS?s Scientific Manuscript database

Biochar (BC) is a product of thermochemical conversion of biomass via pyrolysis, together with gas (syngas), liquid (bio-oil), and heat. Fast pyrolysis is a promising process for bio-oil generation, which leaves 10-30% of the original biomass as char. When applied to soils, BC may increase soil C s...

Fluidized bed catalytic pyrolysis of eucalyptus over hzsm-5: effect of acid density and gallium modification on catalyst deactivation

USDA-ARS?s Scientific Manuscript database

Catalytic fast pyrolysis of eucalyptus wood was performed on a continuous laboratory scale fluidized bed fast pyrolysis system. Catalytic activity was monitored from use of fresh catalyst up to a cumulative biomass to catalyst ratio (B/C) of 4/1 over extruded pellets of three different ZSM-5 catalys...

Damage Caused to Polyurethane Foams by Aging, Simulated Sunlight Exposure, Heat and Fire

DTIC Science & Technology

1984-07-01

vented configuration ............ .................. 11 4 Sample of the tan-colored solid formed upon pyrolysis of blue foam ..... .............. .. 21...54 26 Infrared absorption spectrum of the solid, tan-colored pyrolysis product formed from blue polyurethane foam ..... .............. .. 55 27...Infrared absorption spectrum of the liquid, brown-colored pyrolysis product formed from blue polyurethane foam ..... .............. .. 56 28 Fuel vent

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

USDA-ARS?s Scientific Manuscript database

Fast pyrolysis of lignocellulosic biomass produces organic liquids (bio-oil), bio-char, water, and non-condensable gases. The non-condensable gas component typically contains syngas (H2, CO and CO2) as well as small hydrocarbons (CH4, C2H6, and C3H8). Tail Gas Reactive Pyrolysis (TGRP), a patent p...

Behavior of chlorine during coal pyrolysis

USGS Publications Warehouse

Shao, D.; Hutchinson, E.J.; Cao, H.; Pan, W.-P.; Chou, C.-L.

1994-01-01

The behavior of chlorine in Illinois coals during pyrolysis was evaluated by combined thermo-gravimetry-Fourier transform infrared spectroscopy-ion chromatography (TG-FTIR-IC) techniques. It was found that more than 90% of chlorine in Illinois coals (IBC-103, 105, 106, and 109) was liberated as HCl gas during pyrolysis from 300 to 600??C, with the rate reaching a maximum at 440 ??C. Similarity of the HCl and NH3 release profiles during pyrolysis of IBC-109 supports the hypothesis that the chlorine in coal may be associated with nitrogen and the chlorine is probably bonded to the basic nitrogen sites on the inner walls of coal micropores. ?? 1994 American Chemical Society.

Molecular Structure and Reactivity in the Pyrolysis of Aldehydes

NASA Astrophysics Data System (ADS)

Sias, Eric; Cole, Sarah; Sowards, John; Warner, Brian; Wright, Emily; McCunn, Laura R.

2016-06-01

The effect of alkyl chain structure on pyrolysis mechanisms has been investigated in a series of aldehydes. Isovaleraldehyde, CH_3CH(CH_3)CH_2CHO, and pivaldehyde, (CH_3)_3CCHO, were subject to thermal decomposition in a resistively heated SiC tubular reactor at 800-1200 °C. Matrix-isolation FTIR spectroscopy was used to identify pyrolysis products. Carbon monoxide and isobutene were major products from each of the aldehydes, which is consistent with what is known from previous studies of unbranched alkyl-chain aldehydes. Other products observed include vinyl alcohol, propene, acetylene, and ethylene, revealing complexities to be considered in the pyrolysis of large, branched-chain aldehydes.

Solar coal gasification reactor with pyrolysis gas recycle

DOEpatents

Aiman, William R.; Gregg, David W.

1983-01-01

Coal (or other carbonaceous matter, such as biomass) is converted into a duct gas that is substantially free from hydrocarbons. The coal is fed into a solar reactor (10), and solar energy (20) is directed into the reactor onto coal char, creating a gasification front (16) and a pyrolysis front (12). A gasification zone (32) is produced well above the coal level within the reactor. A pyrolysis zone (34) is produced immediately above the coal level. Steam (18), injected into the reactor adjacent to the gasification zone (32), reacts with char to generate product gases. Solar energy supplies the energy for the endothermic steam-char reaction. The hot product gases (38) flow from the gasification zone (32) to the pyrolysis zone (34) to generate hot char. Gases (38) are withdrawn from the pyrolysis zone (34) and reinjected into the region of the reactor adjacent the gasification zone (32). This eliminates hydrocarbons in the gas by steam reformation on the hot char. The product gas (14) is withdrawn from a region of the reactor between the gasification zone (32) and the pyrolysis zone (34). The product gas will be free of tar and other hydrocarbons, and thus be suitable for use in many processes.

Performance of compact fast pyrolysis reactor with Auger-type modules for the continuous liquid biofuel production

NASA Astrophysics Data System (ADS)

Nishimura, Shun; Ebitani, Kohki

2018-01-01

Development of a compact fast pyrolysis reactor constructed using Auger-type technology to afford liquid biofuel with high yield has been an interesting concept in support of local production for local consumption. To establish a widely useable module package, details of the performance of the developing compact module reactor were investigated. This study surveyed the properties of as-produced pyrolysis oil as a function of operation time, and clarified the recent performance of the developing compact fast pyrolysis reactor. Results show that after condensation in the scrubber collector, e.g. approx. 10 h for a 25 kg/h feedstock rate, static performance of pyrolysis oil with approximately 20 MJ/kg (4.8 kcal/g) calorific values were constantly obtained after an additional 14 h. The feeding speed of cedar chips strongly influenced the time for oil condensation process: i.e. 1.6 times higher feeding speed decreased the condensation period by half (approx. 5 h in the case of 40 kg/h). Increasing the reactor throughput capacity is an important goal for the next stage in the development of a compact fast pyrolysis reactor with Auger-type modules.

Study on the NO removal efficiency of the lignite pyrolysis coke catalyst by selective catalytic oxidation method

PubMed Central

Wen, Xin; Ma, Zhenhua; Zhang, Lei; Sha, Xiangling; He, Huibin; Zeng, Tianyou; Wang, Yusu; Chen, Jihao

2017-01-01

Selective catalytic oxidation (SCO) method is commonly used in wet denitration technology; NO after the catalytic oxidation can be removed with SO2 together by wet method. Among the SCO denitration catalysts, pyrolysis coke is favored by the advantages of low cost and high catalytic activity. In this paper, SCO method combined with pyrolysis coke catalyst was used to remove NO from flue gas. The effects of different SCO operating conditions and different pyrolysis coke catalyst made under different process conditions were studied. Besides, the specific surface area of the catalyst and functional groups were analyzed with surface area analyzer and Beohm titration. The results are: (1) The optimum operating conditions of SCO is as follows: the reaction temperature is 150°C and the oxygen content is 6%. (2) The optimum pyrolysis coke catalyst preparation processes are as follows: the pyrolysis final temperature is 750°C, and the heating rate is 44°C / min. (3) The characterization analysis can be obtained: In the denitration reaction, the basic functional groups and the phenolic hydroxyl groups of the catalyst play a major role while the specific surface area not. PMID:28793346

Clay-sewage sludge co-pyrolysis. A TG-MS and Py-GC study on potential advantages afforded by the presence of clay in the pyrolysis of wastewater sewage sludge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ischia, Marco, E-mail: marco.ischia@ing.unitn.it; Maschio, Roberto Dal; Grigiante, Maurizio

2011-01-15

Wastewater sewage sludge was co-pyrolyzed with a well characterized clay sample, in order to evaluate possible advantages in the thermal disposal process of solid waste. Characterization of the co-pyrolysis process was carried out both by thermogravimetric-mass spectrometric (TG-MS) analysis, and by reactor tests, using a lab-scale batch reactor equipped with a gas chromatograph for analysis of the evolved gas phase (Py-GC). Due to the presence of clay, two main effects were observed in the instrumental characterization of the process. Firstly, the clay surface catalyzed the pyrolysis reaction of the sludge, and secondly, the release of water from the clay, atmore » temperatures of approx. 450-500 deg. C, enhanced gasification of part of carbon residue of the organic component of sludge following pyrolysis. Moreover, the solid residue remaining after pyrolysis process, composed of the inorganic component of sludge blended with clay, is characterized by good features for possible disposal by vitrification, yielding a vitreous matrix that immobilizes the hazardous heavy metals present in the sludge.« less

Effects of Nonequilibrium Chemistry and Darcy-Forchheimer Pyrolysis Flow for Charring Ablator

NASA Technical Reports Server (NTRS)

Chen, Yih-Kanq; Milos, Frank S.

2013-01-01

The fully implicit ablation and thermal response code simulates pyrolysis and ablation of thermal protection materials and systems. The governing equations, which include energy conservation, a three-component decomposition model, and a surface energy balance, are solved with a moving grid.This work describes new modeling capabilities that are added to a special version of code. These capabilities include a time-dependent pyrolysis gas flow momentum equation with Darcy-Forchheimer terms and pyrolysis gas species conservation equations with finite rate homogeneous chemical reactions. The total energy conservation equation is also enhanced for consistency with these new additions. Two groups of parametric studies of the phenolic impregnated carbon ablator are performed. In the first group, an Orion flight environment for a proposed lunar-return trajectory is considered. In the second group, various test conditions for arcjet models are examined. The central focus of these parametric studies is to understand the effect of pyrolysis gas momentum transfer on material in-depth thermal responses with finite-rate, equilibrium, or frozen homogeneous gas chemistry. Results indicate that the presence of chemical nonequilibrium pyrolysis gas flow does not significantly alter the in-depth thermal response performance predicted using the chemical equilibrium gas model.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yimin; Goldberg, Marshall

2015-02-01

This guide -- the JEDI Fast Pyrolysis Biorefinery Model User Reference Guide -- was developed to assist users in operating and understanding the JEDI Fast Pyrolysis Biorefinery Model. The guide provides information on the model's underlying methodology, as well as the parameters and data sources used to develop the cost data utilized in the model. This guide also provides basic instruction on model add-in features and a discussion of how the results should be interpreted. Based on project-specific inputs from the user, the JEDI Fast Pyrolysis Biorefinery Model estimates local (e.g., county- or state-level) job creation, earnings, and output frommore » total economic activity for a given fast pyrolysis biorefinery. These estimates include the direct, indirect and induced economic impacts to the local economy associated with the construction and operation phases of biorefinery projects.Local revenue and supply chain impacts as well as induced impacts are estimated using economic multipliers derived from the IMPLAN software program. By determining the local economic impacts and job creation for a proposed biorefinery, the JEDI Fast Pyrolysis Biorefinery Model can be used to field questions about the added value biorefineries might bring to a local community.« less

Synthesis of Bio-aromatics from Black Liquors Using Catalytic Pyrolysis

PubMed Central

2018-01-01

Bio-aromatics (benzene, toluene, xylenes, BTX) were prepared by the catalytic pyrolysis of six different black liquors using both in situ and ex situ approaches. A wide range of catalysts was screened and conditions were optimized in microscale reactors. Up to 7 wt % of BTX, based on the organic fraction of the black liquors, was obtained for both the in situ and ex situ pyrolysis (T = 500–600 °C) using a Ga-modified H-ZSM-5 catalyst. The in situ catalytic pyrolysis of black liquors from hardwood paper mills afforded slightly higher yields of aromatics/BTX than softwood black liquors, a trend that could be confirmed by the results obtained in the ex situ catalytic pyrolysis. An almost full deoxygenation of the lignin and carbohydrate fraction was achieved and both organic fractions were converted to a broad range of (substituted) aromatics. The zeolite catalyst used was remarkably stable and even after 100 experiments in batch mode with intermittent oxidative catalyst regeneration, the yields and selectivity toward BTX remained similar. The ex situ pyrolysis of black liquor has potential for large-scale implementation in a paper mill without disturbing the paper production process. PMID:29607268

Characterization of typical heavy metals in pyrolysis MSWI fly ash.

PubMed

Xu, Tengtun; Wang, Li'ao; Zeng, Yunmin; Zhao, Xue; Wang, Lei; Zhan, Xinyuan; Li, Tong; Yang, Lu

2018-06-07

Thermal treatment methods are used extensively in the process of municipal solid waste incineration fly ash. However, the characterization of heavy metals during this process should be understood more clearly in order to control secondary pollution. In this paper, the content, speciation and leaching toxicity of mercury (Hg), plumbum (Pb), cadmium (Cd) and zinc (Zn) in fly ash treated under different temperatures and time were firstly analysed as pre-tests. Later, pilot-scale pyrolysis equipment was used to explore the concentration and speciation changes in the heavy metals of fly ash. Finally, the phase constitution and microstructure changes in fly ash were compared before and after pyrolysis using X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. The results showed that (a) The appropriate processing temperature was between 400°C and 450°C, and the processing time should be 1 h. (b) The stability of heavy metals in fly ash increased after pyrolysis. (c) XRD and SEM results indicated that phase constitution changed a little, but the microstructure varied to a porous structure similar to that of a coral reef after pyrolysis. These results suggest that pyrolysis could be an effective method in controlling heavy metal pollution in fly ash.

A geochemical study of macerals from a Miocene lignite and an Eocene bituminous coal, Indonesia

USGS Publications Warehouse

Stankiewicz, B.A.; Kruge, M.A.; Mastalerz, Maria

1996-01-01

Optical and chemical studies of maceral concentrates from a Miocene lignite and an Eocene high-volatile bituminous C coal from southeastern Kalimantan, Indonesia were undertaken using pyro-Lysis, optical, electron microprobe and FTIR techniques Pyrolysis products of vitrinite from bituminous coal were dominated by straight-chain aliphatics and phenols. The huminite of the Miocene lignite produced mostly phenolic compounds upon pyrolysis. Differences in the pyrolysis products between the huminite and vitrinite samples reflect both maturation related and paleobotanical differences. An undefined aliphatic source and/or bacterial biomass were the likely contributors of n-alkyl moieties to the vitrinite. The resinite fraction in the lignite yielded dammar-derived pyrolysis products, as well as aliphatics and phenols as the products of admixed huminite and other liptinites. The optically defined resinite-rich fraction of the bituminous coal from Kalimantan produced abundant n-aliphatic moieties upon pyrolysis, but only two major resin markers (cadalene and 1,6-dimethylnaphthalene). This phenomenon is likely due to the fact that Eocene resins were not dammar-related. Data from the electron microprobe and Fourier transform infrared spectrometry strongly support the results obtained by Py GC MS and microscopy.

Processing of uranium oxide and silicon carbide based fuel using polymer infiltration and pyrolysis

NASA Astrophysics Data System (ADS)

Singh, Abhishek K.; Zunjarrao, Suraj C.; Singh, Raman P.

2008-09-01

Ceramic composite pellets consisting of uranium oxide, UO 2, contained within a silicon carbide matrix, were fabricated using a novel processing technique based on polymer infiltration and pyrolysis (PIP). In this process, particles of depleted uranium oxide, in the form of U 3O 8, were dispersed in liquid allylhydridopolycarbosilane (AHPCS), and subjected to pyrolysis up to 900 °C under a continuous flow of ultra high purity argon. The pyrolysis of AHPCS, at these temperatures, produced near-stoichiometric amorphous silicon carbide ( a-SiC). Multiple polymer infiltration and pyrolysis (PIP) cycles were performed to minimize open porosity and densify the silicon carbide matrix. Analytical characterization was conducted to investigate chemical interaction between U 3O 8 and SiC. It was observed that U 3O 8 reacted with AHPCS during the very first pyrolysis cycle, and was converted to UO 2. As a result, final composition of the material consisted of UO 2 particles contained in an a-SiC matrix. The physical and mechanical properties were also quantified. It is shown that this processing scheme promotes uniform distribution of uranium fuel source along with a high ceramic yield of the parent matrix.

Pyrolysis Treatment of Chromite Ore Processing Residue by Biomass: Cellulose Pyrolysis and Cr(VI) Reduction Behavior.

PubMed

Zhang, Da-Lei; Zhang, Mei-Yi; Zhang, Chu-Hui; Sun, Ying-Jie; Sun, Xiao; Yuan, Xian-Zheng

2016-03-15

The pyrolysis treatment with biomass is a promising technology for the remediation of chromite-ore-processing residue (COPR). However, the mechanism of this process is still unclear. In this study, the behavior of pyrolysis reduction of Cr(VI) by cellulose, the main component of biomass, was elucidated. The results showed that the volatile fraction (VF) of cellulose, ie. gas and tar, was responsible for Cr(VI) reduction. All organic compounds, as well as CO and H2 in VF, potentially reduced Cr(VI). X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine-structure (EXAFS) spectroscopy confirmed the reduction of Cr(VI) to Cr(III) and the formation of amorphous Cr2O3. The remnant Cr(VI) content in COPR can be reduced below the detection limit (2 mg/kg) by the reduction of COPR particle and extension of reaction time between VF and COPR. This study provided a deep insight on the co-pyrolysis of cellulose with Cr(VI) in COPR and an ideal approach by which to characterize and optimize the pyrolysis treatment for COPR by other organics.

Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

USGS Publications Warehouse

Lewan, M.D.; Kotarba, M.J.; Curtis, John B.; Wieclaw, D.; Kosakowski, P.

2006-01-01

The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S2 generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S2 generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S2 generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen. ?? 2006 Elsevier Inc. All rights reserved.

Effects of complexation between organic matter (OM) and clay mineral on OM pyrolysis

NASA Astrophysics Data System (ADS)

Bu, Hongling; Yuan, Peng; Liu, Hongmei; Liu, Dong; Liu, Jinzhong; He, Hongping; Zhou, Junming; Song, Hongzhe; Li, Zhaohui

2017-09-01

The stability and persistence of organic matter (OM) in source rocks are of great significance for hydrocarbon generation and the global carbon cycle. Clay-OM associations commonly occur in sedimentation and diagenesis processes and can influence the pyrolytic behaviors of OM. In this study, clay-OM complexes, i.e., interlayer clay-OM complexes and clay-OM mixture, were prepared and exposed to high-pressure pyrolysis conditions in confined gold capsule reactors to assess variations in OM pyrolysis products in the presence of clay minerals. Three model organic compounds, octadecanoic acid (OA), octadecy trimethyl ammonium bromide (OTAB), and octadecylamine (ODA), were employed and montmorillonite (Mt) was selected as the representative clay mineral. The solid acidity of Mt plays a key role in affecting the amount and composition of the pyrolysis gases generated by the clay-OM complexes. The Brønsted acid sites significantly promote the cracking of hydrocarbons through a carbocation mechanism and the isomerization of normal hydrocarbons. The Lewis acid sites are primarily involved in the decarboxylation reaction during pyrolysis and are responsible for CO2 generation. Mt exhibits either a catalysis effect or pyrolysis-inhibiting during pyrolysis of a given OM depending on the nature of the model organic compound and the nature of the clay-OM complexation. The amounts of C1-5 hydrocarbons and CO2 that are released from the Mt-OA and Mt-ODA complexes were higher than those of the parent OA and ODA, respectively, indicating a catalysis effect of Mt. In contrast, the amount of C1-5 hydrocarbons produced from the pyrolysis of Mt-OTAB complexes was lower than that of OTAB, which we attribute to an inhibiting effect of Mt. This pyrolysis-inhibiting effect works through the Hoffmann elimination that is promoted by the catalysis of the Brønsted acid sites of Mt, therefore releasing smaller amounts of gas hydrocarbons than the nucleophilic reaction that is induced by the halide ions in OTAB. In particular, the interlayer space of Mt acts as an 'amplifier' that magnifies the above-mentioned catalysis or pyrolysis-inhibiting effect, due to the greater number of Brønsted acid sites with high acidity in the interlayer space. These findings are potentially important for understanding the storage and transfer mechanisms of natural OM in sedimentation and diagenesis processes.

Renewable hydrocarbons for jet fuels from biomass and plastics via microwave-induced pyrolysis and hydrogenation processes

NASA Astrophysics Data System (ADS)

Zhang, Xuesong

This dissertation aims to enhance the production of aromatic hydrocarbons in the catalytic microwave-induced pyrolysis, and maximize the production of renewable cycloalkanes for jet fuels in the hydrogenation process. In the process, ZSM-5 catalyst as the highly efficient catalyst was employed for catalyzing the pyrolytic volatiles from thermal decomposition of cellulose (a model compound of lignocellulosic biomass). A central composite experiment design (CCD) was used to optimize the product yields as a function of independent factors (e.g. catalytic temperature and catalyst to feed mass ratio). The low-density polyethylene (a mode compound of waste plastics) was then carried out in the catalytic microwave-induced pyrolysis in the presence of ZSM-5 catalyst. Thereafter, the catalytic microwave-induced co-pyrolysis of cellulose with low-density polyethylene (LDPE) was conducted over ZSM-5 catalyst. The results showed that the production of aromatic hydrocarbons was significantly enhanced and the coke formation was also considerably reduced comparing with the catalytic microwave pyrolysis of cellulose or LDPE alone. Moreover, practical lignocellulosic biomass (Douglas fir sawdust pellets) was converted into aromatics-enriched bio-oil by catalytic microwave pyrolysis. The bio-oil was subsequently hydrogenated by using the Raney Ni catalyst. A liquid-liquid extraction step was implemented to recover the liquid organics and remove the water content. Over 20% carbon yield of liquid product regarding lignocellulosic biomass was obtained. Up to 90% selectivity in the liquid product belongs to jet fuel range cycloalkanes. As the integrated processes was developed, catalytic microwave pyrolysis of cellulose with LDPE was conducted to improve aromatic production. After the liquid-liquid extraction by the optimal solvent (n-heptane), over 40% carbon yield of hydrogenated organics based on cellulose and LDPE were achieved in the hydrogenation process. As such, real lignocellulosic biomass with LDPE were transformed into aromatics via co-feed catalytic microwave pyrolysis. It was also found that close to 40% carbon yield of hydrogenated organics were garnered. Based on these outcomes, the reaction kinetics regarding non-catalytic co-pyrolysis and catalytic co-pyrolysis of biomass with plastics were also presented. In addition, the techno-economic analysis of the catalytically integrated processes from lignocellulosic biomass to renewable cycloalkanes for jet fuels was evaluated in the dissertation as well.

Morphological characteristics of waste polyethylene/polypropylene plastics during pyrolysis and representative morphological signal characterizing pyrolysis stages.

PubMed

Wang, H; Chen, D; Yuan, G; Ma, X; Dai, X

2013-02-01

In this work, the morphological characteristics of waste polyethylene (PE)/polypropylene (PP) plastics during their pyrolysis process were investigated, and based on their basic image changing patterns representative morphological signals describing the pyrolysis stages were obtained. PE and PP granules and films were used as typical plastics for testing, and influence of impurities was also investigated. During pyrolysis experiments, photographs of the testing samples were taken sequentially with a high-speed infrared camera, and the quantitative parameters that describe the morphological characteristics of these photographs were explored using the "Image Pro Plus (v6.3)" digital image processing software. The experimental results showed that plastics pyrolysis involved four stages: melting, two stages of decomposition which are characterized with bubble formation caused by volatile evaporating, and ash deposition; and each stage was characterized with its own phase changing behaviors and morphological features. Two stages of decomposition are the key step of pyrolysis since they took up half or more of the reaction time; melting step consumed another half of reaction time in experiments when raw materials were heated up from ambient temperatures; and coke-like deposition appeared as a result of decomposition completion. Two morphological signals defined from digital image processing, namely, pixel area of the interested reaction region and bubble ratio (BR) caused by volatile evaporating were found to change regularly with pyrolysis stages. In particular, for all experimental scenarios with plastics films and granules, the BR curves always exhibited a slowly drop as melting started and then a sharp increase followed by a deep decrease corresponding to the first stage of intense decomposition, afterwards a second increase - drop section corresponding to the second stage of decomposition appeared. As ash deposition happened, the BR dropped to zero or very low values. When impurities were involved, the shape of BR curves showed that intense decomposition started earlier but morphological characteristics remained the same. In addition, compared to parameters such as pressure, the BR reflects reaction stages better and its change with pyrolysis process of PE/PP plastics with or without impurities was more intrinsically process correlated; therefore it can be adopted as a signal for pyrolysis process characterization, as well as offering guide to process improvement and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

Validation Results for Core-Scale Oil Shale Pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.more » 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.« less

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

DOE PAGES

Neupane, Sneha; Adhikari, Sushil; Wang, Zhouhong; ...

2015-01-27

Torrefaction has been shown to improve the chemical composition of bio-oils produced from fast pyrolysis by lowering its oxygen content and enhancing the aromatic yield. A Py-GC/MS study was employed to investigate the effect of torrefaction temperatures (225, 250 and 275 °C) and residence times (15, 30 and 45 min) on product distribution from non-catalytic and H +ZSM-5 catalyzed pyrolysis of pinewood. During torrefaction, structural transformations in biomass constitutive polymers: hemicellulose, cellulose and lignin took place, which were evaluated using component analysis, solid state CP/MAS 13C NMR and XRD techniques. Torrefaction caused deacetylation and decomposition of hemicellulose, cleavage of arylmore » ether linkages and demethoxylation of lignin, degradation of cellulose and an overall increase in aromaticity of biomass, all of which affected the product yield from pyrolysis of torrefied biomass. For non-catalytic pyrolysis, selectivity of phenolic compounds increased with an increase in torrefaction severity while that of furan compounds decreased. In the case of catalytic pyrolysis, the sample torrefied at 225 °C-30 min and 250 °C-15 min resulted in a significant increase in aromatic hydrocarbon (HC) and also total carbon yield (approx. 1.6 times higher) as compared to catalytic pyrolysis of non-torrefied pine. Cleavage of aryl ether linkages and demethoxylation in lignin due to torrefaction caused increased yield of phenolic compounds, which in the presence of a catalyst were dehydrated to form aromatic HC.« less

A steady state model of agricultural waste pyrolysis: A mini review.

PubMed

Trninić, M; Jovović, A; Stojiljković, D

2016-09-01

Agricultural waste is one of the main renewable energy resources available, especially in an agricultural country such as Serbia. Pyrolysis has already been considered as an attractive alternative for disposal of agricultural waste, since the technique can convert this special biomass resource into granular charcoal, non-condensable gases and pyrolysis oils, which could furnish profitable energy and chemical products owing to their high calorific value. In this regard, the development of thermochemical processes requires a good understanding of pyrolysis mechanisms. Experimental and some literature data on the pyrolysis characteristics of corn cob and several other agricultural residues under inert atmosphere were structured and analysed in order to obtain conversion behaviour patterns of agricultural residues during pyrolysis within the temperature range from 300 °C to 1000 °C. Based on experimental and literature data analysis, empirical relationships were derived, including relations between the temperature of the process and yields of charcoal, tar and gas (CO2, CO, H2 and CH4). An analytical semi-empirical model was then used as a tool to analyse the general trends of biomass pyrolysis. Although this semi-empirical model needs further refinement before application to all types of biomass, its prediction capability was in good agreement with results obtained by the literature review. The compact representation could be used in other applications, to conveniently extrapolate and interpolate these results to other temperatures and biomass types. © The Author(s) 2016.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pendse, Hemant P.

Maine and its industries identified more efficient utilization of biomass as a critical economic development issue. In Phase I of this implementation project, a research team was assembled, research equipment was implemented and expertise was demonstrated in pyrolysis, hydrodeoxygenation of pyrolysis oils, catalyst synthesis and characterization, and reaction engineering. Phase II built upon the infrastructure to innovate reaction pathways and process engineering, and integrate new approaches for fuels and chemical production within pulp and paper and other industries within the state. This research cluster brought together chemists, engineers, physicists and students from the University of Maine, Bates College, and Bowdoinmore » College. The project developed collaborations with Oak Ridge National Laboratory and Brookhaven National Laboratory. The specific research projects within this proposal were of critical interest to the DoE - in particular the biomass program within EERE and the catalysis/chemical transformations program within BES. Scientific and Technical Merit highlights of this project included: (1) synthesis and physical characterization of novel size-selective catalyst/supports using engineered mesoporous (1-10 nm diameter pores) materials, (2) advances in fundamental knowledge of novel support/ metal catalyst systems tailored for pyrolysis oil upgrading, (3) a microcalorimetric sensing technique, (4) improved methods for pyrolysis oil characterization, (5) production and characterization of woody biomass-derived pyrolysis oils, (6) development of two new patented bio oil pathways: thermal deoxygenation (TDO) and formate assisted pyrolysis (FASP), and (7) technoeconomics of pyrolysis of Maine forest biomass. This research cluster has provided fundamental knowledge to enable and assess pathways to thermally convert biomass to hydrocarbon fuels and chemicals.« less

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

DOE PAGES

Mukarakate, Calvin; Mittal, Ashutosh; Ciesielski, Peter N.; ...

2016-07-19

Here, cellulose is the primary biopolymer responsible for maintaining the structural and mechanical integrity of cell walls and, during the fast pyrolysis of biomass, may be restricting cell wall expansion and inhibiting phase transitions that would otherwise facilitate efficient escape of pyrolysis products. Here, we test whether modifications in two physical properties of cellulose, its crystalline allomorph and degree of crystallinity, alter its performance during fast pyrolysis. We show that both crystal allomorph and relative crystallinity of cellulose impact the slate of primary products produced by fast pyrolysis. For both cellulose-I and cellulose-II, changes in crystallinity dramatically impact the fastmore » pyrolysis product portfolio. In both cases, only the most highly crystalline samples produced vapors dominated by levoglucosan. Cellulose-III, on the other hand, produces largely the same slate of products regardless of its relative crystallinity and produced as much or more levoglucosan at all crystallinity levels compared to cellulose-I or II. In addition to changes in products, the different cellulose allomorphs affected the viscoelastic properties of cellulose during rapid heating. Real-time hot-stage pyrolysis was used to visualize the transition of the solid material through a molten phase and particle shrinkage. SEM analysis of the chars revealed additional differences in viscoelastic properties and molten phase behavior impacted by cellulose crystallinity and allomorph. Regardless of relative crystallinity, the cellulose-III samples displayed the most obvious evidence of having transitioned through a molten phase.« less

Oxidative and inert pyrolysis on-line coupled to gas chromatography with mass spectrometric detection: On the pyrolysis products of tobacco additives.

PubMed

Paschke, Meike; Hutzler, Christoph; Henkler, Frank; Luch, Andreas

2016-11-01

According to European legislation, tobacco additives may not increase the toxicity or the addictive potency of the product, but there is an ongoing debate on how to reliably characterize and measure such properties. Further, too little is known on pyrolysis patterns of tobacco additives to assume that no additional toxicological risks need to be suspected. An on-line pyrolysis technique was used and coupled to gas chromatography-mass spectrometry (GC/MS) to identify the pattern of chemical species formed upon thermal decomposition of 19 different tobacco additives like raw cane sugar, licorice or cocoa. To simulate the combustion of a cigarette it was necessary to perform pyrolysis at inert conditions as well as under oxygen supply. All individual additives were pyrolyzed under inert or oxidative conditions at 350, 700 and 1000°C, respectively, and the formation of different toxicants was monitored. We observed the generation of vinyl acrylate, fumaronitrile, methacrylic anhydride, isobutyric anhydride and 3-buten-2-ol exclusively during pyrolysis of tobacco additives. According to the literature, these toxicants so far remained undetectable in tobacco or tobacco smoke. Further, the formation of 20 selected polycyclic aromatic hydrocarbons (PAHs) with molecular weights of up to 278Da was monitored during pyrolysis of cocoa in a semi-quantitative approach. It was shown that the adding of cocoa to tobacco had no influence on the relative amounts of the PAHs formed. Copyright © 2016 Elsevier GmbH. All rights reserved.

Recycling slaughterhouse waste into fertilizer: how do pyrolysis temperature and biomass additions affect phosphorus availability and chemistry?

PubMed

Zwetsloot, Marie J; Lehmann, Johannes; Solomon, Dawit

2015-01-01

Pyrolysis of slaughterhouse waste could promote more sustainable phosphorus (P) usage through the development of alternative P fertilizers. This study investigated how pyrolysis temperature (220, 350, 550 and 750 °C), rendering before pyrolysis, and wood or corn biomass additions affect P chemistry in bone char, plant availability, and its potential as P fertilizer. Linear combination fitting of synchrotron-based X-ray absorption near edge structure spectra demonstrated that higher pyrolysis temperatures decreased the fit with organic P references, but increased the fit with a hydroxyapatite (HA) reference, used as an indicator of high calcium phosphate (CaP) crystallinity. The fit to the HA reference increased from 0% to 69% in bone with meat residue and from 20% to 95% in rendered bone. Biomass additions to the bone with meat residue reduced the fit to the HA reference by 83% for wood and 95% for corn, and additions to rendered bone by 37% for wood. No detectable aromatic P forms were generated by pyrolysis. High CaP crystallinity was correlated with low water-extractable P, but high formic acid-extractable P indicative of high plant availability. Bone char supplied available P which was only 24% lower than Triple Superphosphate fertilizer and two- to five-fold higher than rock phosphate. Pyrolysis temperature and biomass additions can be used to design P fertilizer characteristics of bone char through changing CaP crystallinity that optimize P availability to plants. © 2014 Society of Chemical Industry.

Biochar characteristics produced from rice husks and their sorption properties for the acetanilide herbicide metolachlor.

PubMed

Wei, Lan; Huang, Yufen; Li, Yanliang; Huang, Lianxi; Mar, Nyo Nyo; Huang, Qing; Liu, Zhongzhen

2017-02-01

Rice husk biochar (RHBC) was prepared for use as adsorbents for the herbicide metolachlor. The characteristics and sorption properties of metolachlor adsorbed by the RHBC prepared at different pyrolysis temperatures were determined by analysis of physico-chemical characteristics, Fourier transform infrared spectroscopy (FTIR), Boehm titration, scanning electron microscopy (SEM), and thermodynamics and kinetics adsorption. With increasing pyrolysis temperature, the RHBC surface area greatly increased (from 2.57 to 53.08 m 2  g -1 ). RHBC produced at the highest temperature (750 °C) had the greatest surface area; SEM also showed the formation of a porous surface on RH-750 biochar. The sorption capacity of RHBC also increased significantly with increasing pyrolysis temperature and was characterized by the Freundlich constant K f for the adsorption capacity increasing from 125.17-269.46 (pyrolysis at 300 °C) to 339.94-765.24 (pyrolysis at 750 °C). The results indicated that the surface area and pore diameter of RHBC produced with high pyrolysis temperature (i.e., 750 °C) had the greatest impact on the adsorption of metolachlor. The FTIR, Boehm titration, and SEM analysis showed that the greatest number of surface groups were on RHBC produced at the lowest temperature (300 °C). The biochars produced at different pyrolysis temperatures had different mechanisms of adsorbing metolachlor, which exhibited a transition from hydrogen bonds dominant at low pyrolytic temperature to pore-filling dominant at higher pyrolytic temperature.

Characteristics of the microwave pyrolysis and microwave CO2-assisted gasification of dewatered sewage sludge.

PubMed

Chun, Young Nam; Jeong, Byeo Ri

2017-07-28

Microwave drying-pyrolysis or drying-gasification characteristics were examined to convert sewage sludge into energy and resources. The gasification was carried out with carbon dioxide as a gasifying agent. The examination results were compared with those of the conventional heating-type electric furnace to compare both product characteristics. Through the pyrolysis or gasification, gas, tar, and char were generated as products. The produced gas was the largest component of each process, followed by the sludge char and the tar. During the pyrolysis process, the main components of the produced gas were hydrogen and carbon monoxide, with a small amount of hydrocarbons such as methane and ethylene. In the gasification process, however, the amount of carbon monoxide was greater than the amount of hydrogen. In microwave gasification, a large amount of heavy tar was produced. The largest amount of benzene in light tar was generated from the pyrolysis or gasification. Ammonia and hydrogen cyanide, which are precursors of NO x , were also generated. In the microwave heating method, the sludge char produced by pyrolysis and gasification had pores in the mesopore range. This could be explained that the gas obtained from the microwave pyrolysis or gasification of the wet sewage sludge can be used as an alternative fuel, but the tar and NO x precursors in the produced gas should be treated. Sludge char can be used as a biomass solid fuel or as a tar removal adsorbent if necessary.

Release of hydrogen sulfide during microwave pyrolysis of sewage sludge: Effect of operating parameters and mechanism.

PubMed

Zhang, Jun; Zuo, Wei; Tian, Yu; Yin, Linlin; Gong, Zhenlong; Zhang, Jie

2017-06-05

The effects of sludge characteristics, pyrolysis temperature, heating rate and catalysts on the release of H 2 S and mechanism of H 2 S formation during sludge pyrolysis were investigated in a microwave heating reactor (MHR). The evolution of sulfur-containing compounds in the pyrolysis chars obtained at temperature range of 400-800°C was characterized by XPS. For a given temperature, the maximum concentration of H 2 S appeared at moisture content of 80%. Compared to the influence of heating rate on the H 2 S yields, pyrolysis temperature and catalyst played a more significant role on the release of H 2 S during microwave pyrolysis process. The H 2 S concentration increased with increasing temperature from 400°C to 800°C while decreased with increasing heating rate. Both the Nickel-based catalyst and Dolomite displayed significant desulfurization effect and Ni-based catalyst exhibited the larger desulfurization capability than that of Dolomite. The organic sulfur compounds accounted for about 60% of the total sulfur in the sludge which was the main reason for the formation of H 2 S. The mechanism analysis indicated that the cleavage reactions of mercaptan and aromatic-S compounds at temperatures below 600°C and the cracking reaction of sulfate above 700°C respectively were responsible for the H 2 S release during sludge pyrolysis. Copyright © 2017 Elsevier B.V. All rights reserved.

Production of zinc and manganese oxide particles by pyrolysis of alkaline and Zn-C battery waste.

PubMed

Ebin, Burçak; Petranikova, Martina; Steenari, Britt-Marie; Ekberg, Christian

2016-05-01

Production of zinc and manganese oxide particles from alkaline and zinc-carbon battery black mass was studied by a pyrolysis process at 850-950°C with various residence times under 1L/minN2(g) flow rate conditions without using any additive. The particular and chemical properties of the battery waste were characterized to investigate the possible reactions and effects on the properties of the reaction products. The thermodynamics of the pyrolysis process were studied using the HSC Chemistry 5.11 software. The carbothermic reduction reaction of battery black mass takes place and makes it possible to produce fine zinc particles by a rapid condensation, after the evaporation of zinc from a pyrolysis batch. The amount of zinc that can be separated from the black mass is increased by both pyrolysis temperature and residence time. Zinc recovery of 97% was achieved at 950°C and 1h residence time using the proposed alkaline battery recycling process. The pyrolysis residue is mainly MnO powder with a low amount of zinc, iron and potassium impurities and has an average particle size of 2.9μm. The obtained zinc particles have an average particle size of about 860nm and consist of hexagonal crystals around 110nm in size. The morphology of the zinc particles changes from a hexagonal shape to s spherical morphology by elevating the pyrolysis temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.

Innovative Processing of Composites for Ultra-High Temperature Applications. Book 3

DTIC Science & Technology

1993-11-01

SiC Samples Prepared with Four Preceramic Polymer Infiltration / Pyrolysis (at 15750C) Cycles Figure 21 Scanning Electron...Micrograph of Large Pores near the Surface of Siliconized SIC Sample with Four Preceramic Polymer Infiltration / Pyrolysis (at 1575*C) Cycles II...In order to achieve dense, bulk composites with maximum SiC /Si ratio, two infiltration / pyrolysis cycles were used. S (4) After siliconization,

Novel Precursor Approached for CMC Derived by Polymer Pyrolysis

DTIC Science & Technology

1994-02-15

to remove signals from probe polymer materials. C. Pyrolysis Methods The conversion of polymeric PMVS to SiC -containing ceramic was studied by... Composite Fabrication Methods Ceramic matrix composites with different matrix compositions were fabricated using the Polymer Impregnation- Pyrolysis (PIP...Pyrolyzed composites were re- infiltrated with the appropriate polymer matrix source under vacuum, and cured in an autoclave under 100 psi overpressure of N2

Behavior of sulfur during coal pyrolysis

USGS Publications Warehouse

Shao, D.; Hutchinson, E.J.; Heidbrink, J.; Pan, W.-P.; Chou, C.-L.

1994-01-01

The behavior of sulfur in Illinois coals during pyrolysis was evaluated by thermogravimetry/ Fourier transform-infrared spectroscopy (TG/FT-IR) techniques. SO2, COS, and H2S were major gaseous sulfur-containing products observed during coal pyrolysis. The release rates of the gaseous sulfur species showed several peaks within the temperature ranges, which were due to the emission of different forms of sulfur in coal. ?? 1994.

Formate-assisted pyrolysis

DOEpatents

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

2015-03-17

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

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

USDA-ARS?s Scientific Manuscript database

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

Study of thermal behavior of vitamin D3 by pyrolysis-GC-MS in combination with boiling point-retention time correlation.

PubMed

Sun, Yu'an; Liu, Baoxia; Wang, Guoqing; Zhang, Rongjie; Xie, Bing

2005-01-01

The thermal behavior of vitamin D3 was studied based on pyrolysis-GC-MS technique. It was pyrolyzed at 600 degrees C, 750 degrees C, 900 degrees C, respectively. The pyrolysis product were separated With an HP-5 column and identified by the NIST mass spectral search program in combination with the correlation of boiling point and retention time (BP-RT). There are totally 50 components, including mono aromatics and polycyclic aromatic hydrocarbons (PAHs), were determined. It is shown that the contents of the PAHs are increasing with the increasing of the pyrolysis temperature. The contents of the determined components vary from 0.04% to 37.08%.

Pyrolysis-mass spectrometry/pattern recognition on a well-characterized suite of humic samples

USGS Publications Warehouse

MacCarthy, P.; DeLuca, S.J.; Voorhees, K.J.; Malcolm, R.L.; Thurman, E.M.

1985-01-01

A suite of well-characterized humic and fulvic acids of freshwater, soil and plant origin was subjected to pyrolysis-mass spectrometry and the resulting data were analyzed by pattern recognition and factor analysis. A factor analysis plot of the data shows that the humic acids and fulvic acids can be segregated into two distinct classes. Carbohydrate and phenolic components are more pronounced in the pyrolysis products of the fulvic acids, and saturated and unsaturated hydrocarbons contribute more to the humic acid pyrolysis products. A second factor analysis plot shows a separation which appears to be based primarily on whether the samples are of aquatic or soil origin. ?? 1985.

An Optically Accessible Pyrolysis Microreactor

NASA Astrophysics Data System (ADS)

Baraban, Joshua H.; David, Donald E.; Ellison, Barney; Daily, John W.

2016-06-01

We report an optically accessible pyrolysis micro-reactor suitable for in situ laser spectroscopic measurements. A radiative heating design allows for completely unobstructed views of the micro-reactor along two axes. The maximum temperature demonstrated here is only 1300 K (as opposed to 1700 K for the usual SiC micro-reactor) because of the melting point of fused silica, but alternative transparent materials will allow for higher temperatures. Laser induced fluorescence measurements on nitric oxide are presented as a proof of principle for spectroscopic characterization of pyrolysis conditions. (This work has been published in J. H. Baraban, D. E. David, G. B. Ellison, and J. W. Daily. An Optically Accessible Pyrolysis Micro-Reactor. Review of Scientific Instruments, 87(1):014101, 2016.)

Recent developments in fast pyrolysis of ligno-cellulosic materials.

PubMed

Kersten, Sascha; Garcia-Perez, Manuel

2013-06-01

Pyrolysis is a thermochemical process to convert ligno-cellulosic materials into bio-char and pyrolysis oil. This oil can be further upgraded or refined for electricity, transportation fuels and chemicals production. At the time of writing, several demonstration factories are considered worldwide aiming at maturing the technology. Research is focusing on understanding the underlying processes at all relevant scales, ranging from the chemistry of cell wall deconstruction to optimization of pyrolysis factories, in order to produce better quality oils for targeted uses. Among the several bio-oil applications that are currently investigated the production and fermentation of pyrolytic sugars explores the promising interface between thermochemistry and biotechnology. Copyright © 2013 Elsevier Ltd. All rights reserved.

Methods and apparatuses for deoxygenating biomass-derived pyrolysis oil

DOEpatents

Baird, Lance Awender; Brandvold, Timothy A.

2015-10-20

Embodiments of methods and apparatuses for deoxygenating a biomass-derived pyrolysis oil are provided. In one example, a method comprises the steps of separating a low-oxygen biomass-derived pyrolysis oil effluent into a low-oxygen-pyoil organic phase stream and an aqueous phase stream. Phenolic compounds are removed from the aqueous phase stream to form a phenolic-rich diluent recycle stream. A biomass-derived pyrolysis oil stream is diluted and heated with the phenolic-rich diluent recycle stream to form a heated diluted pyoil feed stream. The heated diluted pyoil feed stream is contacted with a deoxygenating catalyst in the presence of hydrogen to deoxygenate the heated diluted pyoil feed stream.

Bacterial biomarkers thermally released from dissolved organic matter

USGS Publications Warehouse

Greenwood, P.F.; Leenheer, J.A.; McIntyre, C.; Berwick, L.; Franzmann, P.D.

2006-01-01

Hopane biomarker products were detected using microscale sealed vessel (MSSV) pyrolysis gas chromatography-mass spectrometry (GC-MS) analysis of dissolved organic matter from natural aquatic systems colonised by bacterial populations. MSSV pyrolysis can reduce the polyhydroxylated alkyl side chain of bacteriohopanepolyols, yielding saturated hopane products which are more amenable to GC-MS detection than their functionalised precursors. This example demonstrates how the thermal conditions of MSSV pyrolysis can reduce the biologically-inherited structural functionality of naturally occurring organic matter such that additional structural fragments can be detected using GC methods. This approach complements traditional analytical pyrolysis methods by providing additional speciation information useful for establishing the structures and source inputs of recent or extant organic material. ?? 2006.

Vacuum pyrolysis characteristics and parameter optimization of recycling organic materials from waste tantalum capacitors.

PubMed

Chen, Zhenyang; Niu, Bo; Zhang, Lingen; Xu, Zhenming

2018-01-15

Recycling rare metal tantalum from waste tantalum capacitors (WTCs) is significant to alleviate the shortage of tantalum resource. However, environmental problems will be caused if the organic materials from WTCs are improperly disposed. This study presented a promising vacuum pyrolysis technology to recycle the organic materials from WTCs. The organics removal rate could reach 94.32wt% according to TG results. The optimal parameters were determined as 425°C, 50Pa and 30min on the basis of response surface methodology (RSM). The oil yield and residual rate was 18.09wt% and 74.94wt%, respectively. All pyrolysis products can be recycled through a reasonable route. Besides, to deeply understand the pyrolysis process, the pyrolysis mechanism was also proposed based on the product and free radical theory. This paper provides an efficient process for recycling the organic material from WTCs, which can facilitate the following tantalum recovery. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of solid organic waste processing by oxidative pyrolysis

NASA Astrophysics Data System (ADS)

Kolibaba, O. B.; Sokolsky, A. I.; Gabitov, R. N.

2017-11-01

A thermal analysis of a mixture of municipal solid waste (MSW) of the average morphological composition and its individual components was carried out in order to develop ways to improve the efficiency of its utilization for energy production in thermal reactors. Experimental studies were performed on a synchronous thermal analyzer NETZSCH STA 449 F3 Jupiter combined with a quadrupole mass spectrometer QMC 403. Based on the results of the experiments, the temperature ranges of the pyrolysis process were determined as well as the rate of decrease of the mass of the sample of solid waste during the drying and oxidative pyrolysis processes, the thermal effects accompanying these processes, as well as the composition and volumes of gases produced during oxidative pyrolysis of solid waste and its components in an atmosphere with oxygen content of 1%, 5%, and 10%. On the basis of experimental data the dependences of the yield of gas on the moisture content of MSW were obtained under different pyrolysis conditions under which a gas of various calorific values was produced.

CFD Modeling of a Laser-Induced Ethane Pyrolysis in a Wall-less Reactor

NASA Astrophysics Data System (ADS)

Stadnichenko, Olga; Snytnikov, Valeriy; Yang, Junfeng; Matar, Omar

2014-11-01

Ethylene, as the most important feedstock, is widely used in chemical industry to produce various rubbers, plastics and synthetics. A recent study found the IR-laser irradiation induced ethane pyrolysis yields 25% higher ethylene production rates compared to the conventional steam cracking method. Laser induced pyrolysis is initiated by the generation of radicals upon heating of the ethane, then, followed by ethane/ethylene autocatalytic reaction in which ethane is converted into ethylene and other light hydrocarbons. This procedure is governed by micro-mixing of reactants and the feedstock residence time in reactor. Under mild turbulent conditions, the turbulence enhances the micro-mixing process and allows a high yield of ethylene. On the other hand, the high flow rate only allows a short residence time in the reactor which causes incomplete pyrolysis. This work attempts to investigate the interaction between turbulence and ethane pyrolysis process using large eddy simulation method. The modelling results could be applied to optimize the reactor design and operating conditions. Skolkovo Foundation through the UNIHEAT Project.

Production of activated carbon by using pyrolysis process in an ammonia atmosphere

NASA Astrophysics Data System (ADS)

Indayaningsih, N.; Destyorini, F.; Purawiardi, R. I.; Insiyanda, D. R.; Widodo, H.

2017-04-01

Activated carbon is materials that have wide applications, including supercapacitor materials, absorbent in chemical industry, and absorbent material in the chemical industry. This study has carried out for the manufacturing of activated carbon from inexpensive materials through efficient processes. Carbon material was made from coconut fibers through pyrolysis process at temperature of 650, 700, 750 and 800°C. Aim of this study was to obtain carbon material that has a large surface area. Pyrolysis process is carried out in an inert atmosphere (N2 gas) at a temperature of 450°C for 30 minutes, followed by pyrolysis process in an ammonia atmosphere at 800°C for 2 hours. The pyrolysis results showed that the etching process in ammonia is occurred; as it obtained some greater surface area when compared with the pyrolisis process in an atmosphere by inert gas only. The resulted activated carbon also showed to have good properties in surface area and total pore volume.

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

PubMed Central

Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

2017-01-01

Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes. PMID:28660882

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

George, Anthe; Geier, Manfred; Dedrick, Daniel E.

2014-10-01

The viability of thermochemically-derived biofuels can be greatly enhanced by reducing the process parasitic energy loads. Integrating renewable power into biofuels production is one method by which these efficiency drains can be eliminated. There are a variety of such potentially viable "hybrid-renewable" approaches; one is to integrate concentrated solar power (CSP) to power biomass-to-liquid fuels (BTL) processes. Barriers to CSP integration into BTL processes are predominantly the lack of fundamental kinetic and mass transport data to enable appropriate systems analysis and reactor design. A novel design for the reactor has been created that can allow biomass particles to be suspendedmore » in a flow gas, and be irradiated with a simulated solar flux. Pyrolysis conditions were investigated and a comparison between solar and non-solar biomass pyrolysis was conducted in terms of product distributions and pyrolysis oil quality. A novel method was developed to analyse pyrolysis products, and investigate their stability.« less

Energy Conversion Loop: A Testbed for Nuclear Hybrid Energy Systems Use in Biomass Pyrolysis

NASA Astrophysics Data System (ADS)

Verner, Kelley M.

Nuclear hybrid energy systems are a possible solution for contemporary energy challenges. Nuclear energy produces electricity without greenhouse gas emissions. However, nuclear power production is not as flexible as electrical grids demand and renewables create highly variable electricity. Nuclear hybrid energy systems are able to address both of these problems. Wasted heat can be used in processes such as desalination, hydrogen production, or biofuel production. This research explores the possible uses of nuclear process heat in bio-oil production via biomass pyrolysis. The energy conversion loop is a testbed designed and built to mimic the heat from a nuclear reactor. Small scale biomass pyrolysis experiments were performed and compared to results from the energy conversion loop tests to determine future pyrolysis experimentation with the energy conversion loop. Further improvements must be made to the energy conversion loop before more complex experiments may be performed. The current conditions produced by the energy conversion loop are not conducive for current biomass pyrolysis experimentation.tion.

A study on experimental characteristic of microwave-assisted pyrolysis of microalgae.

PubMed

Hu, Zhifeng; Ma, Xiaoqian; Chen, Chunxiang

2012-03-01

The microwave-assisted pyrolysis of Chlorella vulgaris was carried out under different microwave power levels, catalysts and contents of activated carbon and solid residue. The products, pyrolysis temperature and temperature rising rate were analyzed in order to obtain the optimal conditions. The results indicated that the higher the microwave power level was, the higher the maximum temperature rising rate and pyrolysis temperature were. The maximum bio-oil yield (35.83 wt.%) and gas yield (52.37%) were achieved under the microwave power of 1500 W and 2250 W, respectively. And 2250 W was the optimal power to obtain bio-fuel product. High microwave power level and catalyst can enhance the production of gas. Catalysts can promote the pyrolysis of C. vulgaris, and activated carbon was the best among the tested catalysts followed by the solid residue. The optimal content of activated carbon is 5% with the maximum bio-fuel yield of 87.47%. Copyright © 2011 Elsevier Ltd. All rights reserved.

Ex-situ catalytic pyrolysis of wastewater sewage sludge - A micro-pyrolysis study.

PubMed

Wang, Kaige; Zheng, Yan; Zhu, Xifeng; Brewer, Catherine E; Brown, Robert C

2017-05-01

Concerns over increasing amounts of sewage sludge and unsustainability of current disposal methods have led to development of alternative routes for sludge management. The large amount of organics in sewage sludge makes it potential feedstock for energy or fuel production via thermochemical pathways. In this study, ex-situ catalytic pyrolysis using HZSM-5 catalyst was explored for the production of olefinic and aromatic hydrocarbons and nutrient-rich char from sewage sludge. The optimal pyrolysis and catalysis temperatures were found to be 500°C and 600°C, respectively. Carbon yields of hydrocarbons from sewage sludge were higher than for lignocellulose; yield differences were attributed to the high extractives content in the sludge. Full recovery of most inorganic elements were found in the char, which suggests that catalyst deactivation maybe alleviated through ex-situ catalytic pyrolysis. Most of the nitrogen was retained in the char while 31.80% was released as ammonia, which suggests a potential for nitrogen recycling. Copyright © 2017 Elsevier Ltd. All rights reserved.

Bioavailability of Metsulfuron and Sulfentrazone Herbicides in Soil as Affected by Amendment with Two Contrasting Willow Biochars.

PubMed

Szmigielski, Anna M; Hangs, Ryan D; Schoenau, Jeff J

2018-02-01

This study investigated the effect of two willow (Salix spp.) biochars, produced using either fast- or slow-pyrolysis, on the bioavailability of metsulfuron and sulfentrazone herbicides in soil. Five rates (0%, 1%, 2%, 3%, and 4%; w/w) of each biochar were used, along with varying rates of metsulfuron (0-3.2 µg ai kg -1 ) and sulfentrazone (0-200 µg ai kg -1 ), followed by a sugar beet bioassay. The fast-pyrolysis biochar had minimal effect, while the slow-pyrolysis biochar decreased the bioavailability of both herbicides. Despite using the same feedstock, the two biochars had different physical and chemical properties, of which specific surface area was most contrasting (3.0 and 175 m 2  g -1 for fast- and slow-pyrolysis biochar, respectively). Increased anionic herbicide adsorption associated with greater surface area of the slow-pyrolysis biochar is considered to be the primary mechanism responsible for reducing herbicide bioavailability with this biochar.

Valorization of Rhizoclonium sp. algae via pyrolysis and catalytic pyrolysis.

PubMed

Casoni, Andrés I; Zunino, Josefina; Piccolo, María C; Volpe, María A

2016-09-01

The valorization of Rhizoclonium sp. algae through pyrolysis for obtaining bio-oils is studied in this work. The reaction is carried out at 400°C, at high contact time. The bio-oil has a practical yield of 35% and is rich in phytol. Besides, it is simpler than the corresponding to lignocellulosic biomass due to the absence of phenolic compounds. This property leads to a bio-oil relatively stable to storage. In addition, heterogeneous catalysts (Al-Fe/MCM-41, SBA-15 and Cu/SBA-15), in contact with algae during pyrolysis, are analyzed. The general trend is that the catalysts decrease the concentration of fatty alcohols and other high molecular weight products, since their mild acidity sites promote degradation reactions. Thus, the amount of light products increases upon the use of the catalysts. Particularly, acetol concentration in the bio-oils obtained from the catalytic pyrolysis with SBA-15 and Cu/SBA-15 is notably high. Copyright © 2016 Elsevier Ltd. All rights reserved.

Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

DOEpatents

Nicholas, Christopher P; Boldingh, Edwin P

2014-04-29

A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula. Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

DOEpatents

Nicholas, Christopher P; Boldingh, Edwin P

2013-12-17

A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

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

PubMed

Li, Dongbing; Briens, Cedric; Berruti, Franco

2015-01-01

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

Study on the Inference Factors of Huangling Coking Coal Pyrolysis

NASA Astrophysics Data System (ADS)

Du, Meili; Yang, Zongyi; Fan, Jinwen

2018-01-01

In order to reasonably and efficiently utilize Huangling coking coal resource, coal particle, heating rate, holding time, pyrolysis temperature and others factors were dicussed for the influence of those factor on Huangling coking coal pyrolysis products. Several kinds of coal blending for coking experiments were carried out with different kinds of coal such as Huangling coking coal, Xida coal with high ash low sufur, Xinghuo fat coal with hign sulfur, Zhongxingyi coking coal with high sulfur, Hucun lean coal, mixed meager and lean coal. The results shown that the optimal coal particle size distribution was 0.5~1.5mm, the optimal heating rate was 8°C/min, the optimal holding time was 15min, the optimal pyrolysis temperature was 800°C for Huangling coking coal pyrolysis, the tar yield increased from 4.7% to 11.2%. The maximum tar yield of coal blending for coking under the best single factor experiment condition was 10.65% when the proportio of Huangling coking coal was 52%.

Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process

NASA Astrophysics Data System (ADS)

Cui, Xin; Qi, Cong; Li, Liang; Li, Yimin; Li, Song

2017-08-01

In order to facilitate efficient and clean utilization of coal, a series of Ni-Co ternary molten salt crystals are explored and the catalytic pyrolysis mechanism of Datong coal is investigated. The reaction mechanisms of coal are achieved by thermal gravimetric analyzer (TGA), and a reactive kinetic model is constructed. The microcosmic structure and macerals are observed by scanning electron microscope (SEM). The catalytic effects of ternary molten salt crystals at different stages of pyrolysis are analyzed. The experimental results show that Ni-Co ternary molten salt catalysts have the capability to bring down activation energy required by pyrolytic reactions at its initial phase. Also, the catalysts exert a preferable catalytic action on macromolecular structure decomposition and free radical polycondensation reactions. Furthermore, the high-temperature condensation polymerization is driven to decompose further with a faster reaction rate by the additions of Ni-Co ternary molten salt crystal catalysts. According to pyrolysis kinetic research, the addition of catalysts can effectively decrease the activation energy needed in each phase of pyrolysis reaction.

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

PubMed

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.

Effects of reaction conditions on the emission behaviors of arsenic, cadmium and lead during sewage sludge pyrolysis.

PubMed

Han, Hengda; Hu, Song; Syed-Hassan, Syed Shatir A; Xiao, Yiming; Wang, Yi; Xu, Jun; Jiang, Long; Su, Sheng; Xiang, Jun

2017-07-01

Sewage sludge is an important class of bioresources whose energy content could be exploited using pyrolysis technology. However, some harmful trace elements in sewage sludge can escape easily to the gas phase during pyrolysis, increasing the potential of carcinogenic material emissions to the atmosphere. This study investigates emission characteristics of arsenic, cadmium and lead under different pyrolysis conditions for three different sewage sludge samples. The increased temperature (within 723-1123K) significantly promoted the cadmium and lead emissions, but its influence on arsenic emission was not pronounced. The releasing rate order of the three trace elements is volatile arsenic compounds>cadmium>lead in the beginning of pyrolysis. Fast heating rates promoted the emission of trace elements for the sludge containing the highest amount of ash, but exhibited an opposite effect for other studied samples. Overall, the high ash sludge released the least trace elements almost under all reaction conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermal pyrolysis characteristics of macroalgae Cladophora glomerata.

PubMed

Gao, Wenhua; Chen, Kefu; Zeng, Jinsong; Xu, Jun; Wang, Bin

2017-11-01

The Cladophora glomerata (C. glomerata) is a kind of widely distributed macroalgae in the freshwater ecosystems. It primarily consists of carbohydrates that can be converted into biofuel by pyrolysis. In this study, thermogravimetric analysis (TGA) was used to investigate the thermal behavior and kinetics of C. glomerata during the pyrolysis process. The results showed that heating rates slightly affect the decomposition properties of C. glomerata; with the heating rates increasing, the maximum peak of weight loss rate shifted to higher temperatures. The activation energies of C. glomerata pyrolysis reaction were 244.25 and 238.07kJ/mol, respectively, as calculated by Friedman and Kissinger-Akahira-Sunose (KAS) methods. The pre-exponential factor and reaction order were determined by Coats-Redfern model, and applied to simulate the pyrolysis process of C. glomerata. The model calculated data and experimental data were consistent. This study could provide theoretical supports for designing C. glomerata conversion processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic study of solid waste pyrolysis using distributed activation energy model.

PubMed

Bhavanam, Anjireddy; Sastry, R C

2015-02-01

The pyrolysis characteristics of municipal solid waste, agricultural residues such as ground nut shell, cotton husk and their blends are investigated using non-isothermal thermogravimetric analysis (TGA) with in a temperature range of 30-900 °C at different heating rates of 10 °C, 30 °C and 50 °C/min in inert atmosphere. From the thermograms obtained from TGA, it is observed that the maximum rate of degradation occurred in the second stage of the pyrolysis process for all the solid wastes. The distributed activation energy model (DAEM) is used to study the pyrolysis kinetics of the solid wastes. The kinetic parameters E (activation energy), k0 (frequency factor) are calculated from this model. It is found that the range of activation energies for agricultural residues are lower than the municipal solid waste. The activation energies for the municipal solid waste pyrolysis process drastically decreased with addition of agricultural residues. The proposed DAEM is successfully validated with TGA experimental data. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of biopretreatment on pyrolysis behaviors of corn stalk by methanogen.

PubMed

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

2014-07-01

The study investigated the effects of methanogen pretreatment on pyrolysis behaviors of corn stalk (CS) by using Py-GC/MS analysis and thermogravimetric analysis. Results indicated that biopretreatment changed considerably the pyrolysis behaviors of CS from four weight loss stages to two weight loss stages. Increasing biopretreatment time from 5 days to 25 days enhanced the kinds and contents of chemicals in volatile products. In pyrolysis products, the contents of sugars, linear ketones and furans decreased from 1.43%, 12.60% and 7.38% to 1.25%, 10.22% and 3.25%, respectively, and the contents of phenols increased from 15.08% to 27.84%. The most content change from 6.83% to 13.63% indicated that methanogen pretreatment improved the pyrolysis selectivity of CS to product the 4-VP, but it was disadvantageous to 5-hydroxymethyl furfural, levoglucose and furfural. The changes of chemical compositions and structure of CS after biopretreatment were the main reason of the differences. Copyright © 2014 Elsevier Ltd. All rights reserved.

Life cycle analysis of fuel production from fast pyrolysis of biomass.

PubMed

Han, Jeongwoo; Elgowainy, Amgad; Dunn, Jennifer B; Wang, Michael Q

2013-04-01

A well-to-wheels (WTW) analysis of pyrolysis-based gasoline was conducted and compared with petroleum gasoline. To address the variation and uncertainty in the pyrolysis pathways, probability distributions for key parameters were developed with data from literature. The impacts of two different hydrogen sources for pyrolysis oil upgrading and of two bio-char co-product applications were investigated. Reforming fuel gas/natural gas for H2 reduces WTW GHG emissions by 60% (range of 55-64%) compared to the mean of petroleum fuels. Reforming pyrolysis oil for H2 increases the WTW GHG emissions reduction up to 112% (range of 97-126%), but reduces petroleum savings per unit of biomass used due to the dramatic decline in the liquid fuel yield. Thus, the hydrogen source causes a trade-off between GHG reduction per unit fuel output and petroleum displacement per unit biomass used. Soil application of biochar could provide significant carbon sequestration with large uncertainty. Copyright © 2013 Elsevier Ltd. All rights reserved.

Understanding the stability of pyrolysis tars from biomass in a view point of free radicals.

PubMed

He, Wenjing; Liu, Qingya; Shi, Lei; Liu, Zhenyu; Ci, Donghui; Lievens, Caroline; Guo, Xiaofen; Liu, Muxin

2014-03-01

Fast pyrolysis of biomass has attracted increasing attention worldwide to produce bio-tars that can be upgraded into liquid fuels and chemicals. However, the bio-tars are usually poor in quality and stability and are difficult to be upgraded. To better understand the nature of the bio-tars, this work reveals radical concentration of tars derived from pyrolysis of two kinds of biomass. The tars were obtained by condensing the pyrolysis volatiles in 3s. It shows that the tars contain large amounts of radicals, at a level of 10(16)spins/g, and are able to generate more radicals at temperatures of 573K or higher, reaching a level of 10(19)spins/g at 673K in less than 30min. The radical generation in the tar samples is attributed to the formation of THF insoluble matters (coke), which also contain radicals. The radical concentrations of the aqueous liquids obtained in pyrolysis are also studied. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PubMed

Campisi, Tiziana; Samorì, Chiara; Torri, Cristian; Barbera, Giuseppe; Foschini, Anna; Kiwan, Alisar; Galletti, Paola; Tagliavini, Emilio; Pasteris, Andrea

2016-10-01

In view of the potential use of pyrolysis-based technologies, it is crucial to understand the environmental hazards of pyrolysis-derived products, in particular bio-oils. Here, three bio-oils were produced from fast pyrolysis of pine wood and intermediate pyrolysis of corn stalk and poultry litter. They were fully characterized by chemical analysis and tested for their biodegradability and their ecotoxicity on the crustacean Daphnia magna and the green alga Raphidocelis subcapitata. These tests were chosen as required by the European REACH regulation. These three bio-oils were biodegradable, with 40-60% of biodegradation after 28 days, and had EC50 values above 100mgL(-1) for the crustacean and above 10mgL(-1) for the alga, showing low toxicity to the aquatic life. The toxic unit approach was applied to verify whether the observed toxicity could be predicted from the data available for the substances detected in the bio-oils. The predicted values largely underestimated the experimental values. Copyright © 2016 Elsevier Inc. All rights reserved.

Thermogravimetric and kinetic study of Pinyon pine in the various gases.

PubMed

Kim, Seung-Soo; Shenoy, Alok; Agblevor, Foster A

2014-03-01

As a renewable resource, Pinyon pine can be converted into bio-oil, gas, and char through pyrolysis. It is known that recycling of the non-condensable gases, which are produced by fast pyrolysis, can increase liquid yield and decrease char yield. In this study, pyrolysis characteristics and kinetics of Pinyon pine were investigated in TGA using simulated non-condensable gases (N2, H2/N2, H2/CO2, and He/CO/H2). The apparent activation energy of Pinyon pine increased from 43.9 to 160.3kJ mol(-1) with increasing pyrolysis conversion from 5% to 95% in pure nitrogen, and reaction order was 1.35. When hydrogen (H2) and carbon monoxide (CO) mixtures were used as simulated gases, the maximum degradation temperature and activation energy decreased by 4-11°C and 6.1-10.2kJ/mol, respectively. The results show that recycling of non-condensable gases could positively influence the fast pyrolysis of biomass. Copyright © 2014 Elsevier Ltd. All rights reserved.

Organometallic Precursor Routes to Si-C-Al-O-N Ceramics

DTIC Science & Technology

1991-05-15

Pyrolysis Chemistry of Polymeric Precursors to SiC and Si3 N 4", Kluwer Academic Publishers, Dordrecht, NATO Workshop or Organometallic Polymers with Special...the polymer to a preceramic SiC . Thus the IR and H CRAMPS spectra confirm the decreasing concentration of hydrogen with increasing pyrolysis ...generality of this polymer pyrolysis route to nanocrystalline composites of refractory nitride and carbide ceramics. Investigation of AlN Precursors Our

Basic studies on the pyrolysis of lignin compounds

Treesearch

Byung-ho Hwang

2003-01-01

By pyrolyzing lignin model compounds 1-lV at 315°C, an investigation was carried out with some results. In the pyrolysis of lignin model compound I and 11, 0.47 mol of guaiacol, 0.57 mol of dimethoxyphenol (DMP), and 0.12 and 0.23 mol of dimethoxyaceton ophenone (DMAP) were produced respectively. In the pyrolysis of lignin model compound lll and lV, 0.26 mol of...

Generation of functional structures by laser pyrolysis of polysilazane

NASA Astrophysics Data System (ADS)

Krauss, Hans-Joachim; Otto, Andreas

2002-06-01

The pyrolysis of polysilazanes by laser power represents an innovative technique for the generation of ceramic-like coatings and structures. The dissolved polysilazanes can be easily applied by painting techniques such as dipping or spraying. In the following pyrolysis the polysilazane layer transforms into an amorphous ceramic-like coating. The laser power is absorbed in the precursor layer, which leads to the latter's ceramization without damaging the substrate by thermal load. While plane laser pyrolysis creates a protective coating, selective pyrolysis creates a raised and adherent ceramic-like structure that remains after the unexposed polymer layer has been removed. The flexibility of a writing laser system in conjunction with a suitable handling system makes it possible to inscribe any kind of 2D structure on nearly any complexly shaped part. Some of the chemical, magnetic, and electrical structure properties can be adjusted by the pyrolysis parameters and special types of filler particles. Especially the possibility to control electric conductivity should make it possible to create structure dielectric films or planar resistors, inductors or capacitors, which are basically written on the surface of the part. Because of their ceramic nature of the structures are resistant against high temperatures and corrosive media. Thus, this new additive structuring technique could finally strike a new path in creating corrosion resistant high- temperature sensors and control systems.

Formation characteristics of aerosol particles from pulverized coal pyrolysis in high-temperature environments.

PubMed

Chen, Wei-Hsin; Du, Shan-Wen; Yang, Hsi-Hsien; Wu, Jheng-Syun

2008-05-01

The formation characteristics of aerosol particles from pulverized coal pyrolysis in high temperatures are studied experimentally. By conducting a drop-tube furnace, fuel pyrolysis processes in industrial furnaces are simulated in which three different reaction temperatures of 1000, 1200, and 1400 degrees C are considered. Experimental observations indicate that when the reaction temperature is 1000 degrees C, submicron particles are produced, whereas the particle size is dominated by nanoscale for the temperature of 1400 degrees C. Thermogravimetric analysis of the aerosol particles stemming from the pyrolysis temperature of 1000 degrees C reveals that the thermal behavior of the aerosol is characterized by a three-stage reaction with increasing heating temperature: (1) a volatile-reaction stage, (2) a weak-reaction stage, and (3) a soot-reaction stage. However, with the pyrolysis temperature of 1400 degrees C, the volatile- and weak-reaction stages almost merge together and evolve into a chemical-frozen stage. The submicron particles (i.e., 1000 degrees C) are mainly composed of volatiles, tar, and soot, with the main component of the nanoscale particles (i.e., 1400 degrees C) being soot. The polycyclic aromatic hydrocarbons (PAHs) contained in the aerosols are also analyzed. It is found that the PAH content in generated aerosols decreases dramatically as the pyrolysis temperature increases.

Environmental impact of pyrolysis of mixed WEEE plastics part 2: Life cycle assessment.

PubMed

Alston, Sue M; Arnold, J Cris

2011-11-01

Waste electrical and electronic equipment (WEEE) contains up to 25% plastics. Extraction of higher quality fractions for recycling leaves a mix of plastic types contaminated with other materials, requiring the least environmentally harmful disposal route. Data from trials of pyrolysis, described in part 1 of this paper set, were used in a life cycle assessment of the treatment of WEEE plastics. Various levels of recycling of the sorted fraction were considered, and pyrolysis was compared with incineration (with energy recovery) and landfill for disposal of the remainder. Increased recycling gave reduced environmental impact in almost all categories considered, although inefficient recycling decreased that benefit. Significant differences between pyrolysis, incineration and landfill were seen in climate change impacts, carbon sent to landfill, resources saved, and radiation. There was no overall "best" option. Landfill had the least short-term impact on climate change so could be a temporary means of sequestering carbon. Incineration left almost no carbon to landfill, but produced the most greenhouse gases. Pyrolysis or incineration saved most resources, with the balance depending on the source of electricity replaced by incineration. Pyrolysis emerged as a strong compromise candidate since the gases and oils produced could be used as fuels and so provided significant resource saving without high impact on climate change or landfill space.

The effect of moisture on the release and enrichment of heavy metals during pyrolysis of municipal solid waste.

PubMed

Raclavská, Helena; Corsaro, Agnieszka; Hlavsová, Adéla; Juchelková, Dagmar; Zajonc, Ondřej

2015-03-01

The investigation of the effect of moisture on the release and enrichment of heavy metals during pyrolysis of municipal solid waste is essential. This is important owing to: (i) the increasing amount of metals in the solid product of pyrolysis beyond the normalised level; (ii) the effect of moisture on the overall cost of pyrolysis process; and (iii) the utilisation of pyrolysis products. Seven metals were selected for evaluation: arsenic, cadmium, chromium, mercury, nickel, lead, and vanadium. Pyrolysis experiments were conducted in a steel retort at 650 °C. The municipal solid waste samples with moisture contents of 0, 30, and 65 wt% were investigated. The relative enrichment index and release of heavy metals were evaluated individually for liquid and solid fractions. A consistent trend was observed for the majority of metals investigated. Reductions of relative enrichment index and release, i.e. an increase of volatility, were observed for arsenic, chromium, cadmium, nickel, and vanadium, with an increase of municipal solid waste moisture. Whereas divergent results were obtained for lead and mercury. The effect of moisture on the relative enrichment index and release was greater at 65 wt% moisture than at 30 wt% for lead, and more remarkable at 30 wt% than at 65 wt% for mercury. © The Author(s) 2015.

Polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs) mitigation in the pyrolysis process of waste tires using CO₂ as a reaction medium.

PubMed

Kwon, Eilhann E; Oh, Jeong-Ik; Kim, Ki-Hyun

2015-09-01

Our work reported the CO2-assisted mitigation of PAHs and VOCs in the thermo-chemical process (i.e., pyrolysis). To investigate the pyrolysis of used tires to recover energy and chemical products, the experiments were conducted using a laboratory-scale batch-type reactor. In particular, to examine the influence of the CO2 in pyrolysis of a tire, the pyrolytic products including C1-5-hydrocarbons (HCs), volatile organic carbons (VOCs), and polycyclic aromatic hydrocarbons (PAHs) were evaluated qualitatively by gas chromatography (GC) with mass spectroscopy (MS) as well as with a thermal conductivity detector (TCD). The mass balance of the pyrolytic products under various pyrolytic conditions was established on the basis of their weight fractions of the pyrolytic products. Our experimental work experimentally validated that the amount of gaseous pyrolytic products increased when using CO2 as a pyrolysis medium, while substantially altering the production of pyrolytic oil in absolute content (7.3-17.2%) and in relative composition (including PAHs and VOCs). Thus, the co-feeding of CO2 in the pyrolysis process can be considered an environmentally benign and energy efficient process. Copyright © 2015 Elsevier Ltd. All rights reserved.

Kinetic Modelling of the Pyrolysis of Biomass for the Development of Charcoal Briquette

NASA Astrophysics Data System (ADS)

Idris, Y. R.; Bayu, H. T.; Wintoko, J.; Murachman, B.; Yuliansyah, A. T.; Purwono, S.

2017-06-01

Waste of biomass can be utilized as an energy alternative such as a charcoal briquette. In the waste of biomass, there is carbon element bonded in the cellulose which can be utilized as an energy source of solid fuel. Charcoal briquette from waste of biomass can be developed via pyrolysis process. Terminalia Catappa L. and Myristica fragrans (nutmeg seeds shells) shells were used as raw material for the manufacture of charcoal briquettes. Pyrolysis process took place under isothermal conditions at a temperature of 350°C, 400°C, 450°C, 500°C, and 550°C with variation of times were 30 minutes, 60 minutes and 90 minutes. During the pyrolysis process, there were three main components observed, namely liquid (bio oil), gases and solids (char). Data obtained for measuring the kinetics of liquids and gases were taken in interval of 5 minutes. The results showed that the rise in temperature will increase the rate of pyrolysis process and increase the yield of gases and liquids as well as lowering the yield for solid. The best fitted kinetic model is the representation of biomass pyrolysis process involving secondary decomposition of the liquid. The results of briquette development showed that these two biomasses can be used as raw material of energy alternative.

Review of the pyrolysis platform for coproducing bio-oil and biochar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laird, David A.; Brown, Robert C.; Amonette, James E.

2009-09-01

Pyrolysis is a relatively simple, inexpensive, and robust thermochemical technology for transforming biomass into bio-oil, biochar, and syngas. The robust nature of the pyrolysis technology, which allows considerable flexibility in both the type and quality of the biomass feedstock, combined with a distributed network of small pyrolysis plants, would be compatible with existing agriculture and forestry infrastructure. Bio-oil can be used as a fuel in existing industrial boilers. Biochar can be used with existing infrastructure as a replacement for pulverized coal; however, use of biochar as a soil amendment results in significant environmental and agronomic benefits. Soil application of biocharmore » is a means of sequestering large amounts of C and may have other greenhouse gas benefits. Preliminary reports of the impact of soil biochar applications on crop yields indicate that biochar quality is very important. Biochar is an effective adsorbent for both nutrients and organic contaminants, hence the presence of biochar in soils has been shown to improve water quality in column leaching and field lysimeter studies and it is anticipated to do the same for agricultural watersheds. The pyrolysis platform for producing bio-oil and biochar from biomass appears to be a practical, effective, and environmentally sustainable means of producing large quantities of renewable bioenergy while simultaneously reducing emissions of greenhouse gases. At the present time, the pyrolysis platform is economically marginal because markets for bio-oil and biochar are highly competitive. However, if the USA adopts a program for controlling greenhouse gases, the pyrolysis platform would be highly competitive.« less

Role of iron modifier on boron atomization process using graphite furnace-atomic absorption spectrometry based on speciation of iron using X-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Yamamoto, Yuhei; Tagami, Azusa; Shiarasaki, Toshihiro; Yonetani, Akira; Yamamoto, Takashi; Imai, Shoji

2018-04-01

The role of an Fe modifier on boron atomization process using graphite furnace-atomic absorbance spectrometry was investigated using a spectroscopic approach. The initial state of the Fe modifier in a pyrolytic graphite (PG) furnace was trivalent. With an increase in pyrolysis temperature, the Fe modifier was reduced in a stepwise manner. Fe2O3 and Fe3O4 were dominant at pyrolysis temperatures below 1300 K. From 1300 to 1500 K, FeO was dominant. At temperatures higher than 1700 K, Fe metal was dominant. After a drying step, 17.7% of the initial B remained in the PG furnace. After the pyrolysis step at 773 K, the residual fraction of B was similar to that after the drying step. After the pyrolysis step at a temperature of 1073 K, the residual fraction was 11.7%. At pyrolysis temperatures > 1738 K, the residual fraction was <3.3% (

Reduction of Bromate by Cobalt-Impregnated Biochar Fabricated via Pyrolysis of Lignin Using CO2 as a Reaction Medium.

PubMed

Cho, Dong-Wan; Kwon, Gihoon; Ok, Yong Sik; Kwon, Eilhann E; Song, Hocheol

2017-04-19

In this study, pyrolysis of lignin impregnated with cobalt (Co) was conducted to fabricate a Co-biochar (i.e., Co/lignin biochar) for use as a catalyst for bromate (BrO 3 - ) reduction. Carbon dioxide (CO 2 ) was employed as a reaction medium in the pyrolysis to induce desired effects associated with CO 2 ; (1) the enhanced thermal cracking of volatile organic compounds (VOCs) evolved from the thermal degradation of biomass, and (2) the direct reaction between CO 2 and VOCs, which resulted in the enhanced generation of syngas (i.e., H 2 and CO). This study placed main emphases on three parts: (1) the role of impregnated Co in pyrolysis of lignin in the presence of CO 2 , (2) the characterization of Co/lignin biochar, and (3) evaluation of catalytic capability of Co-lignin biochar in BrO 3 - reduction. The findings from the pyrolysis experiments strongly evidenced that the desired CO 2 effects were strengthened due to catalytic effect of impregnated Co in lignin. For example, the enhanced generation of syngas from pyrolysis of Coimpregnated lignin in CO 2 was more significant than the case without Co impregnation. Moreover, pyrolysis of Coimpregnated lignin in CO 2 led to production of biochar of which surface area (599 m 2 g -1 ) is nearly 100 times greater than the biochar produced in N 2 (6.6 m 2 g -1 ). Co/lignin biochar produced in CO 2 also showed a great performance in catalyzing BrO 3 - reduction as compared to the biochar produced in N 2 .

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

DOE PAGES

Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; ...

2016-07-05

Cycloheptatrienyl (tropyl) radical, C 7H 7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. In this study, the pyrolysis products resulting from C 7H 7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C 7H 7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals domore » not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C 7H 7) radicals but rather only benzyl (C 6H 5CH 2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C 6H 5CH 2, C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2. Finally, analysis of the temperature dependence for the pyrolysis of the isotopic species (C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buckingham, Grant T.; National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden Colorado 80401; Porterfield, Jessica P.

2016-07-07

Cycloheptatrienyl (tropyl) radical, C{sub 7}H{sub 7}, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C{sub 7}H{sub 7} were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C{sub 7}H{sub 7} are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize tomore » benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C{sub 7}H{sub 7}) radicals but rather only benzyl (C{sub 6}H{sub 5}CH{sub 2}). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C{sub 6}H{sub 5}CH{sub 2}, C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less

The stabilization of tannery sludge and the character of humic acid-like during low temperature pyrolysis.

PubMed

Ma, Hongrui; Gao, Mao; Hua, Li; Chao, Hao; Xu, Jing

2015-11-01

Tannery sludge contained plenty of organic matter, and the organic substance stability had direct impact on its derived chars' utilization. In this paper, the stabilization of tannery sludge and the variation of humic acid-like (HAL) extracted by different methods were investigated in a magnetic stirring reactor under low temperature pyrolysis of 100-400 °C. Results showed that the aromatic structure of pyrolysis chars increased with the increase of temperature and time. The char contained highly aromatic structure and relatively small dissolved organic matters (DOM) at 300 °C. The similar behaviors appeared in two HAL series by different extraction methods. The N content, H/C value, and aliphatic structures of HAL decreased with the increase of pyrolysis temperature, while the C/N value and aromatic structures increased with the rise of pyrolysis temperature. The composition and functional groups of HAL were similar with the purchased humic acid (HA). The fluorescence spectra revealed that two main peaks were found at Ex/Em = 239/363-368 nm and 283/359-368 nm in each HAL series from raw and 100 °C pyrolysis tannery sludge, representing a protein-like matter. The new peak appeared at Ex/Em = 263-283/388 nm in each HAL series from 200 °C pyrolysis tannery sludge-represented humic acid-like matter. The fluorescence intensity increased strongly compared to the other two peak intensity. Therefore, the humification of organic matter was increased by pyrolyzing. Notably, the HAL from 200 °C pyrolysis tannery sludge contained simple molecular structure, and the polycondensation increased but with a relative lower humification degree compared to soil HAL and purchased HA. Therefore, the sludge needs further oxidation. The humic substance was negligible by direct extraction when the temperature was 300 and 400 °C.

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCormick, Robert L.; Baldwin, Robert M.; Arbogast, Stephen

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

High-Pressure Liquid Chromatograph with Mass Spectrometric Detection for Analysis of Supercritical Fuels Pyrolysis Products

DTIC Science & Technology

2006-08-01

conditions will necessarily be supercritical fluids . These temperatures and pressures will also cause the fuel to undergo pyrolytic reactions, which...Spectrometric Detection for 5a. CONTRACT NUMBER Analysis of Supercritical Fuels Pyrolysis Products 5b. GRANT NUMBER FA9550-05-1-0253 5c... supercritical pyrolysis experiments with the model fuels 1-methylnaphthalene and toluene. The HPLC/UV/MS instrument facilitated the identification of fifteen 5

Production of valuable hydrocarbons by flash pyrolysis of oil shale

DOEpatents

Steinberg, M.; Fallon, P.T.

1985-04-01

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

Fatigue Behavior of a SiC/SiC Composite at 1000 deg C in Air and in Steam

DTIC Science & Technology

2010-12-01

SiC dual-layer interphase. The composite was manufactured by a Polymer Infiltration and Pyrolysis (PIP... Polymer Infiltration and Pyrolysis (PIP) process. A seal coat of SiC and elemental boron was applied to the test specimens after machining. The tensile...manufactured by a Polymer Infiltration and Pyrolysis (PIP) process. A seal coat of SiC and elemental boron was applied to the test specimens

Pyrolysis of Cyclopentadienone: Mechanistic Insights from a Direct Measurement of Product Branching Ratios

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ormond, Thomas K.; Scheer, Adam M.; Nimlos, Mark R.

2015-07-16

The thermal decomposition of cyclopentadienone (C5H4-O) has been studied in a flash pyrolysis continuous flow microreactor. Passing dilute samples of o-phenylene sulfite (C6H4O2SO) in He through the microreactor at elevated temperatures yields a relatively clean source of C5H4-O. The pyrolysis of C5H4-O was investigated over the temperature range 1000-2000 K.

Evaluation of the energy transfer in the char zone during ablation. Part 2: In-depth response of ablative composites, volume 1. Ph.D. Thesis, 1975. Final Report

NASA Technical Reports Server (NTRS)

Pike, R. W.; Delvalle, E. G.

1974-01-01

The decomposition of ablative composites is described along with the transport phenomena of pyrolysis gases which result from the decomposition of these plastics as they flow through the porous char of char-forming ablators. The pyrolysis products are those formed by the thermal degradation of nylon-phenolic resin and silicone elastomer composites. Emphasis is placed on the nature and extent of chemical reactions of the pyrolysis products and the char, along with the energy absorbed by the combined pyrolysis and char zone. Chemical reactions with thermodynamically consistent kinetic data are determined in order to develop a realistic analysis for predicting the thermal performance of ablative heat shields.

Pyrolysis-high resolution gas chromatography and pyrolysis gas chromatography-mass spectrometry of kerogens and kerogen precursors

NASA Technical Reports Server (NTRS)

Van De Meent, D.; Brown, S. C.; Philp, R. P.; Simoneit, B. R. T.

1980-01-01

A series of kerogens and kerogen precursors isolated from DSDP samples, oil shales and recent algal mats have been examined by Curie point pyrolysis-high resolution gas chromatography and gas chromatography-mass spectrometry. This study has shown that the three main types of kerogens (marine, terrestrial and mixtures of both) can be characterized using these techniques. The marine (algal) kerogens yield principally aliphatic products and the terrestrial kerogens yield more aromatic and phenolic products with some n-alkanes and n-alkenes. The yields of n-alkanes and n-alkenes increase and phenols decrease with increasing geologic age, however, pyrolysis-GC cannot be used to characterize the influence of short term diagenesis on the kerogen structure.

Performance of rotary kiln reactor for the elephant grass pyrolysis.

PubMed

De Conto, D; Silvestre, W P; Baldasso, C; Godinho, M

2016-10-01

The influence of process conditions (rotary speed/temperature) on the performance of a rotary kiln reactor for non-catalytic pyrolysis of a perennial grass (elephant grass) was investigated. The product yields, the production of non-condensable gases as well as the biochar properties were evaluated. The maximum H2 yield was close to that observed for catalytic pyrolysis processes, while the bio-oil yield was higher than reported for pyrolysis of other biomass in rotary kiln reactors. A H2/CO ratio suitable for Fischer-Tropsch synthesis (FTS) was obtained. The biochars presented an alkaline pH (above 10) and interesting contents of nutrients, as well as low electrical conductivity, indicating a high potential as soil amendment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pyrolysis of softwood carbohydrates in a fluidized bed reactor.

PubMed

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.

Pyrolysis of Softwood Carbohydrates in a Fluidized Bed Reactor

PubMed Central

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

2008-01-01

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 °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. PMID:19325824

Identification and discrimination of oral asaccharolytic Eubacterium spp. by pyrolysis mass spectrometry and artificial neural networks.

PubMed

Goodacre, R; Hiom, S J; Cheeseman, S L; Murdoch, D; Weightman, A J; Wade, W G

1996-02-01

Curie-point pyrolysis mass spectra were obtained from 29 oral asaccharolytic Eubacterium strains and 6 abscess isolates previously identified as Peptostreptococcus heliotrinreducens. Pyrolysis mass spectrometry (PyMS) with cluster analysis was able to clarify the taxonomic position of this group of organisms. Artificial neural networks (ANNS) were then trained by supervised learning (with the back-propagation algorithm) to recognize the strains from their pyrolysis mass spectra; all Eubacterium strains were correctly identified, and the abscess isolates were identified as un-named Eubacterium taxon C2 and were distinct from the type strain of P. heliotrinreducens. These results demonstrate that the combination of PyMS and ANNs provides a rapid and accurate identification technique.

Analytical pyrolysis experiments of Titan aerosol analogues in preparation for the Cassini Huygens mission

NASA Technical Reports Server (NTRS)

Ehrenfreund, P.; Boon, J. J.; Commandeur, J.; Sagan, C.; Thompson, W. R.; Khare, B.

1995-01-01

Comparative pyrolysis mass spectrometric data of Titan aerosol analogs, called 'tholins', are presented. The Titan tholins were produced in the laboratory at Cornell by irradiation of simulated Titan atmospheres with high energy electrons in plasma discharge. Mass-spectrometry measurements were performed at FOM of the solid phase of various tholins by Curie-point pyrolysis Gas-Chromatography/Mass-Spectrometry (GCMS) and by temperature resolved in-source Pyrolysis Mass-Spectrometry to reveal the composition and evolution temperature of the dissociation products. The results presented here are used to further define the ACP (Aerosol Collector Pyrolyser)-GCMS experiment and provide a basis for modelling of aerosol composition on Titan and for the iterpretation of Titan atmosphere data from the Huygens probe in the future.

Application of mesoporous Al-MCM-48 material to the conversion of lignin.

PubMed

Lee, Hyung Won; Lee, In-Gu; Park, Sung Hoon; Jeon, Jong-Ki; Suh, Dong Jin; Jung, Jinho; Park, Young-Kwon

2014-04-01

Al-MCM-48 was applied to the catalytic pyrolysis of lignin for the first time. The pyrolysis reaction and in-situ product were analyzed by pyrolysis gas chromatography/mass spectrometry. The main products of the non-catalytic pyrolysis of lignin were phenols. The use of Al-MCM-48 increased the production of light phenols considerably. The yields of high-value-added compounds, such as hydrocarbons and aromatics, were also increased by catalytic upgrading. Al-MCM-48 is believed to promote cracking, aromatization and deoxygenation, such as decarbonylation. On the other hand, Si-MCM-48, which has no acid sites, showed lower deoxygenation efficiency than Al-MCM-48. Al-MCM-48 could be regenerated by calcining in air.

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.

PubMed

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 internal standard method. This work provides the ground for further analysis of pyrolysis oils of diverse sources for a rational design of both their production and utilization process. Copyright © 2010 Elsevier B.V. All rights reserved.

Characterization of Coconut Shell Liquid Volatile Matter (CS-LVM) by Using Gas Chomatroghaphy

NASA Astrophysics Data System (ADS)

Jahiding, Muhammad; Mashuni; Ilmawati, WOS; Ermawati; Rahmat; Arsyad, Jumiati; Riskayanti, S. S.

2017-05-01

Generally, the coconut shell is only used for the fuel of furnace or is just burnt in which this will just create pollution. One way of solving this problem is by re-processing the coconut shell as raw materials for making liquid volatile matter (LVM) by pyrolysis method. Coconut shell is part of the coconut fruit at which having biological function to protect fruit core and is located on the inner side of the fiber with a thickness ranging from 3-6 mm. Coconut shell is classified as hardwood, mainly composed of lignin, cellulose, and hemicellulose, with water content of approximately 6-9 %. Coconut shell is more suitable for pyrolysis process, since they contain less amount of ash, more amount of volatile matter and available with lower cost in rural areas during all the sessions of the year. This research was aimed at determining the influence of pyrolysis temperature towards the LVM volume of coconut shell. LVM was made of condensing the smoke of pyrolysis result from the coconut shell while the analysis of compound composition of LVMcoconut shell used Gas Chromatography. Based on the result of the research, it was known that the pyrolysis, at the temperatures of 400°C, 500°C, 600°C and 700°C can create LVM volume as many as 204.167 mL kg-1, 208,33 mL kg-1 and 216.67 mL kg-1. The LVM created from the pyrolysis at 400°C was made of ammonia (12. 41%), acetic acid (37.27%), phenol (31.66%), furfural (4.16%), and alcohol (5.01%). The LVM created from the pyrolysis at 500°C was made ofammonia (12.22%), hydrazine (5.61%), acetic acid (40.96%), phenol (32.82%), and alcohol (3.10%), furfural (5.30%). The LVM created from the pyrolysis at 600°C was made of ammonia (15.49%)), acetic acid (36,01%), phenol (32.85%)), alcohol (6.75%)), and furfural (4.62%). The LVM created from the pyrolysis at 700°C was made of ammonia (15,.), acetic acid (35.20%), phenol (22.60%), alcohol (5.07%), and furfural (4,90%). From this result, it can be seen that LVM has big advantages for food flavor and other specific flavor as well as for preservative because of its antimicrobe and anti-oxidant characteristics.

Scrap tyre pyrolysis: Modified chemical percolation devolatilization (M-CPD) to describe the influence of pyrolysis conditions on product yields.

PubMed

Tan, Vincent; De Girolamo, Anthony; Hosseini, Tahereh; Alhesan, Jameel Aljariri; Zhang, Lian

2018-03-16

This paper attempts to develop a modified chemical percolation devolatilization (M-CPD) model that can include heat transfer, primary pyrolysis and the secondary cracking reactions of volatiles together to describe the pyrolysis of waste scrap tyre chip, as well as to examine the influence of operating conditions on the scrap tyre pyrolysis product yields. Such a study has yet to be conducted in the past, thereby leading to a large knowledge gap failing to understand the pyrolysis of the coarse feedstock appropriately. To validate the developed model, a number of operating parameters including reactor configurations, carrier gas compositions (argon and argon blended with CO 2 and/or steam), scrap tyre chip size (0.5-15.0 mm), terminal pyrolysis temperature (400-800 °C) and heating rate (10 °C/min and 110 °C/min) were examined in a lab-scale fixed-bed pyrolyser, with a particular focus on the secondary cracking extents of the liquid tar. Through both experimental investigation and modelling approach, it was found that significant secondary cracking extent occurred upon the increase in the feedstock size, heating rate and residence time. Upon the fast pyrolysis, the average temperature gap between the centres of the coarse particle and reactor wall could reach a maximum of 115 °C for the tyre chips of 6-15 mm. Consequently, its primary volatiles underwent the secondary cracking reaction at an overall extent of 17% at a terminal temperature of 600 °C and a fast heating rate of 110 °C/min. Consequently, the yield of light gases including methane was increased remarkably. The flow rate of inert carrier gas was also influential in the secondary cracking, in which a maximum tar yield (54 wt%) was reached at a carrier gas flow rate of 1.5  L/min. This indicates the occurrence of secondary cracking has been largely minimised. At a pyrolysis temperature of 600 °C, the addition of CO 2 in the carrier gas had an insignificant effect on the product yield distribution under the slow heating scheme. In contrast, the addition of steam resulted in a slight increase of carbon monoxide, presumably due to the occurrence of gasification reaction. Copyright © 2018 Elsevier Ltd. All rights reserved.

Release behavior and formation mechanism of polycyclic aromatic hydrocarbons during coal pyrolysis.

PubMed

Gao, Meiqi; Wang, Yulong; Dong, Jie; Li, Fan; Xie, Kechang

2016-09-01

Polycyclic aromatic hydrocarbons (PAHs) are major environmental pollutants. They have attracted considerable attention due to their severe potential carcinogenic, mutagenic and genotoxic effects on human health. In this study, five different rank coals from China were pyrolyzed using pyro-probe CDS 5250 and the release behavior of 16 PAHs under different pyrolysis conditions were studied by Gas Chromatography-Mass Spectrometer (GC-MS). The structural characteristics of the five coals were determined by Cross-Polarization/Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS (13)C NMR) spectroscopy, and then the factors influencing the formation of PAHs during coal pyrolysis were discussed together with the coal structural data. It was shown that the amount of PAHs generated during coal pyrolysis was largely related to coal rank and followed the order of medium metamorphic coal > low metamorphic coal > high metamorphic coal. The amount of total PAHs varied as the temperature was increased from 400 °C to 1200 °C, which showed a trend of first increasing and then decreasing, with the maximum value at 800 °C. Moreover, the species of PAHs released varied with pyrolysis temperatures. When the temperature was lower than 800 °C, the small ring PAHs were the most abundant, while the proportion of heavy rings increased at higher temperature. The results indicate that the formation of PAHs during coal pyrolysis depends on the structure of the coal. The species and amounts of PAHs generated during coal pyrolysis are closely related to the contents of protonated aromatic carbons and bridging ring junction aromatic carbons present in the coal structure. Copyright © 2016 Elsevier Ltd. All rights reserved.

Method for Hot Real-Time Sampling of Pyrolysis Vapors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pomeroy, Marc D

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 beforemore » 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.« less

Characterization of products obtained from pyrolysis and steam gasification of wood waste, RDF, and RPF.

PubMed

Hwang, In-Hee; Kobayashi, Jun; Kawamoto, Katsuya

2014-02-01

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products. The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500°C but the polycyclic aromatic hydrocarbons became the major compounds at 900°C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700°C under steam gasification condition. For WBC, both char utilization by pyrolysis at low temperature (500°C) and syngas recovery by steam gasification at higher temperature (900°C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500°C) might be one of viable options. Steam gasification at 900°C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered. Copyright © 2013 Elsevier Ltd. All rights reserved.

Numerical Approach to Wood Pyrolysis in Considerating Heat Transfer in Reactor Chamber

NASA Astrophysics Data System (ADS)

Idris, M.; Novalia, U.

2017-03-01

Pyrolysis is the decomposition process of solid biomass into gas, tar and charcoal through thermochemical methods. The composition of biomass consists of cellulose hemi cellulose and lignin, which each will decompose at different temperatures. Currently pyrolysis has again become an important topic to be discussed. Many researchers make and install the pyrolysis reactor to convert biomass waste into clean energy hardware that can be used to help supply energy that has a crisis. Additionally the clean energy derived from biomass waste is a renewable energy, in addition to abundant source also reduce exhaust emissions of fossil energy that causes global warming. Pyrolysis is a method that has long been known by humans, but until now little is known about the phenomenon of the pyrolysis process that occurs in the reactor. One of the Pyrolysis’s phenomena is the heat transfer process from the temperature of the heat source in the reactor and heat the solid waste of biomass. The solid waste of biomass question in this research is rubber wood obtained from one of the company’s home furnishings. Therefore, this study aimed to describe the process of heat transfer in the reactor during the process. ANSYS software was prepared to make the simulation of heat transfer phenomena at the pyrolysis reactor. That’s the numerical calculation carried out for 1200 seconds. Comparison of temperature performed at T1, T2 and T3 to ensure that thermal conductivity is calculated by numerical accordance with experimental data. The distribution of temperature in the reactor chamber specifies the picture that excellent heat conduction effect of the wood near or attached to wooden components, cellulose, hemicellulose and lignin down into gas.

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

PubMed

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

2016-01-01

Fermentable sugars are important intermediates in the biological conversion of biomass. Hemicellulose and amorphous cellulose are easily hydrolyzed to fermentable sugars in dilute acid, whereas crystalline cellulose is more difficult to be hydrolyzed. Cellulose fast pyrolysis is an alternative method to liberate valuable fermentable sugars from biomass. The amount of levoglucosan generated from lignocellulose by fast pyrolysis is usually lower than the theoretical yield based on the cellulose fraction. Pretreatment is a promising route to improve the yield of levoglucosan from lignocellulose. The integration of dilute sulfuric acid hydrolysis and fast pyrolysis to obtain fermentable sugars was evaluated in this study. Dilute sulfuric acid hydrolysis could remove more than 95.1 and 93.4 % of xylan (the main component of hemicellulose) from sugarcane bagasse and corncob with high yield of xylose. On the other hand, dilute sulfuric acid hydrolysis was also an effective pretreatment to enhance levoglucosan yield from lignocellulose. Dilute acid hydrolysis could accumulate glucan (the component of cellulose) and remove most of the alkali and alkaline earth metals which were powerful catalysts during fast pyrolysis. Further increase in dilute acid concentration (from 0 to 2 %) in pretreatment could promote the yield of levoglucosan in fast pyrolysis. The acid pretreated sugarcane bagasse and corncob gave levoglucosan yields of 43.8 and 35.2 % which were obvious higher than those of raw sugarcane bagasse (12.0 %) and corncob (7.0 %). Obtaining fermentable sugars by combination dilute acid hydrolysis of xylan and fast pyrolysis of glucan could make full utilization of biomass, and get fermentable sugars economically from biomass for bio-refinery.

Effect of pyrolysis temperature and air flow on toxicity of gases from a polycarbonate polymer

NASA Technical Reports Server (NTRS)

Hilado, C. J.; Brick, V. E.; Brauer, D. P.

1978-01-01

A polycarbonate polymer was evaluated for toxicity of pyrolysis gases generated at various temperatures without forced air flow and with 1 L/min air flow, using the toxicity screening test method developed at the University of San Francisco. Time to various animal responses decreased with increasing pyrolysis temperature over the range from 500 C to 800 C. There appeared to be no significant toxic effects at 400 C and lower temperatures.

Design, Synthesis, and Chemical Processing of Hierarchical Ceramic Structures for Aerospace Applications

DTIC Science & Technology

1993-03-30

Massachusetts Institute of Technology, Cambridge, MA 02139I ABSTRACT polysilanes." Pyrolysis of these polymers usually The decomposition of polymeric SiC ...of soluble polymeric solids. Pyrolysis of these polymers in argon yielded The precursors were prepared by adding a TiC/A120 3 composite at 12501C...formation of soluble polymeric solids. Pyrolysis described an approach for synthesizing AI2O/ SiC of these polymers in argon yielded TiC/AI203

Synthesis and Useful Reactions of Organosilicon Polymeric Precursors for Ceramics

DTIC Science & Technology

1992-04-05

composites are hot pressing, chemical vapor infiltration , reaction bonding and polymer infiltration / pyrolysis . Thus the inorganic or organometallic...to prepare preceramic polymers whose D; pyrolysis gives -99% SiC , -99.5% Si 3 N4 , or any mixture of the two by appropriate manipulation of the...the standard furnace pyrolysis of the polymer gave a ceramic of composition 96.6% SiC , 1.7% ZrC and 1.7% Si in 71% yield. Finally, (71-C

Zone heating for fluidized bed silane pyrolysis

NASA Technical Reports Server (NTRS)

Iya, Sridhar K. (Inventor)

1987-01-01

An improved heated fluidized bed reactor and method for the production of high purity polycrystalline silicon by silane pyrolysis wherein silicon seed particles are heated in an upper heating zone of the reactor and admixed with particles in a lower reaction zone, in which zone a silane-containing gas stream, having passed through a lower cooled gas distribution zone not conducive to silane pyrolysis, contacts the heated seed particles whereon the silane is heterogeneously reduced to silicon.

An algorithm for the kinetics of tire pyrolysis under different heating rates.

PubMed

Quek, Augustine; Balasubramanian, Rajashekhar

2009-07-15

Tires exhibit different kinetic behaviors when pyrolyzed under different heating rates. A new algorithm has been developed to investigate pyrolysis behavior of scrap tires. The algorithm includes heat and mass transfer equations to account for the different extents of thermal lag as the tire is heated at different heating rates. The algorithm uses an iterative approach to fit model equations to experimental data to obtain quantitative values of kinetic parameters. These parameters describe the pyrolysis process well, with good agreement (r(2)>0.96) between the model and experimental data when the model is applied to three different brands of automobile tires heated under five different heating rates in a pure nitrogen atmosphere. The model agrees with other researchers' results that frequencies factors increased and time constants decreased with increasing heating rates. The model also shows the change in the behavior of individual tire components when the heating rates are increased above 30 K min(-1). This result indicates that heating rates, rather than temperature, can significantly affect pyrolysis reactions. This algorithm is simple in structure and yet accurate in describing tire pyrolysis under a wide range of heating rates (10-50 K min(-1)). It improves our understanding of the tire pyrolysis process by showing the relationship between the heating rate and the many components in a tire that depolymerize as parallel reactions.

Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hao, Naijia; Bezerra, Tais Lacerda; Wu, Qiong

Pyrolysis is a promising method for converting biomass to biofuels. However, some of pyrolysis oil's physiochemical properties still limit its commercial applications. Here, the autohydrolysis pretreatment at 175 ± 3 °C for 40 min was conducted to improve the resulting pine pyrolysis oil’s properties as a fuel. During autohydrolysis, deacetylation and decomposition of hemicellulose was observed by ion-exchange chromatography and Fourier transform infrared spectroscopy (FT-IR). Additionally, the cleavage of lignin ether bonds was clearly determined by 13C cross-polarization/magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR). Phosphitylation followed by 31P NMR analysis of the heavy oils gave detailed structural information ofmore » the hydroxyl groups; the results revealed that autohydrolysis pretreatment led to a reduction of carboxyl acids in the heavy oils generated at all three pyrolysis temperatures (400, 500, and 600 °C). The 31P NMR analysis also revealed that autohydrolysis pretreatment led to a reduction of condensed phenolic hydroxyl groups in the heavy oils produced at 600 °C. 1H- 13C heteronuclear single-quantum correlation (HSQC) NMR analysis showed that at a pyrolysis temperature of 600 °C, the pretreated pine produced lower methoxy group constituents. In both 31P and HSQC NMR results indicated that autohydrolysis pretreatment increased levoglucosan yields in the bio-oils.« less

Removal of lead (Pb2+) from aqueous medium by using chars from co-pyrolysis.

PubMed

Bernardo, Maria; Mendes, Sandra; Lapa, Nuno; Gonçalves, Margarida; Mendes, Benilde; Pinto, Filomena; Lopes, Helena; Fonseca, Isabel

2013-11-01

The effectiveness of chars from the co-pyrolysis of pine, used tires and plastic wastes for the removal of lead (Pb(2+)) from aqueous medium, was investigated. The chars were predominantly of macroporous nature, but the introduction of tires in the pyrolysis feedstock enhanced their mesoporous content as well as surface area. Pb(2+) sorption with the chars was a slow and unstable process in which sorption-desorption seems to be competing. The highest Pb(2+) removal (88%) was attained by the char resulting from the pyrolysis of a mixture composed by equal mass ratios of used tires and plastics, at 48 h of contact time. This char was also the one with the overall better performance for Pb(2+) sorption, achieving almost 100% of Pb(2+) removal on the study of the effect of adsorbent dose. Mixing the three raw materials for pyrolysis had no advantage for the resulting char concerning the removal efficiency of Pb(2+). The sorption mechanisms varied according to the pyrolysis feedstock: in chars from feedstock with pine, chemisorption involving complexation with oxygenated surface functional groups followed by cation exchange was the presumable mechanism. In tire rubber derived chars, cation exchange with Ca(2+), K(+), and Zn(2+) played the major role on Pb(2+) sorption. Copyright © 2013 Elsevier Inc. All rights reserved.

The Search for Hesperian Organic Matter on Mars: Pyrolysis Studies of Sediments Rich in Sulfur and Iron

PubMed Central

Najorka, Jens; Watson, Jonathan S.; Sephton, Mark A.

2018-01-01

Abstract Jarosite on Mars is of significant geological and astrobiological interest, as it forms in acidic aqueous conditions that are potentially habitable for acidophilic organisms. Jarosite can provide environmental context and may host organic matter. The most common extraction technique used to search for organic compounds on the surface of Mars is pyrolysis. However, thermal decomposition of jarosite releases oxygen into pyrolysis ovens, which degrades organic signals. Jarosite has a close association with the iron oxyhydroxide goethite in many depositional/diagenetic environments. Hematite can form by dehydration of goethite or directly from jarosite under certain aqueous conditions. Goethite and hematite are significantly more amenable than jarosite for pyrolysis experiments employed to search for organic matter. Analysis of the mineralogy and organic chemistry of samples from a natural acidic stream revealed a diverse response for organic compounds during pyrolysis of goethite-rich layers but a poor response for jarosite-rich or mixed jarosite-goethite samples. Goethite units that are associated with jarosite, but do not contain jarosite themselves, should be targeted for organic detection pyrolysis experiments on Mars. These findings are extremely timely, as exploration targets for Mars Science Laboratory include Vera Rubin Ridge (formerly known as “Hematite Ridge”), which may have formed from goethite precursors. Key Words: Mars—Pyrolysis—Jarosite—Goethite—Hematite—Biosignatures. Astrobiology 18, 454–464. PMID:29298093

Changes of chromium speciation and organic matter during low-temperature pyrolysis of tannery sludge.

PubMed

Zhou, Jianjun; Ma, Hongrui; Gao, Mao; Sun, Wenyue; Zhu, Chao; Chen, Xiangping

2018-01-01

The application or disposal of char derived from tannery sludge is directly influenced by the mobility and bioavailability of Cr during pyrolysis process. This study focused on the changes of Cr speciation and organic matter in tannery sludge during low-temperature pyrolysis (100-400 °C) to evaluate the toxicity of char in terms of the leaching possibility of Cr. The results showed that (1) lower char yield and more porous structure were observed after pyrolysis. (2) Higher pyrolysis temperature increased Cr content in the char; however, Cr in this case was converted into the residual fraction which minimized its bioavailability therefore lowers its potential risk to the environment. (3) Organic matters in the acid and alkali leachates were mainly humic acid-like substance, and condensed organic matter might appear at 200 °C and then destruct. (4) Despite the comparatively high content of Cr in the char, the leaching toxicity of char was within the security range according to the national standard of China. The Cr content in the acid and alkali leachates decreased to the range of 16.5-35.3 and 0.2-6.8 mg/L, respectively. It was suggested that the potential toxicity of tannery sludge from Cr could be reduced before utilization or disposal by pyrolysis, especially under 400 °C.

Thermodynamic analyses of hydrogen production from sub-quality natural gas. Part I: Pyrolysis and autothermal pyrolysis

NASA Astrophysics Data System (ADS)

Huang, Cunping; T-Raissi, Ali

Sub-quality natural gas (SQNG) is defined as natural gas whose composition exceeds pipeline specifications of nitrogen, carbon dioxide (CO 2) and/or hydrogen sulfide (H 2S). Approximately one-third of the U.S. natural gas resource is sub-quality gas [1]. Due to the high cost of removing H 2S from hydrocarbons using current processing technologies, SQNG wells are often capped and the gas remains in the ground. We propose and analyze a two-step hydrogen production scheme using SQNG as feedstock. The first step of the process involves hydrocarbon processing (via steam-methane reformation, autothermal steam-methane reformation, pyrolysis and autothermal pyrolysis) in the presence of H 2S. Our analyses reveal that H 2S existing in SQNG is stable and can be considered as an inert gas. No sulfur dioxide (SO 2) and/or sulfur trioxide (SO 3) is formed from the introduction of oxygen to SQNG. In the second step, after the separation of hydrogen from the main stream, un-reacted H 2S is used to reform the remaining methane, generating more hydrogen and carbon disulfide (CS 2). Thermodynamic analyses on SQNG feedstock containing up to 10% (v/v) H 2S have shown that no H 2S separation is required in this process. The Part I of this paper includes only thermodynamic analyses for SQNG pyrolysis and autothermal pyrolysis.

Auto shredder residue recycling: Mechanical separation and pyrolysis.

PubMed

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

2012-05-01

Directive 2000/53/EC 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. Copyright © 2011 Elsevier Ltd. All rights reserved.

Effect of autohydrolysis pretreatment on biomass structure and the resulting bio-oil from a pyrolysis process

DOE PAGES

Hao, Naijia; Bezerra, Tais Lacerda; Wu, Qiong; ...

2017-06-29

Pyrolysis is a promising method for converting biomass to biofuels. However, some of pyrolysis oil's physiochemical properties still limit its commercial applications. Here, the autohydrolysis pretreatment at 175 ± 3 °C for 40 min was conducted to improve the resulting pine pyrolysis oil’s properties as a fuel. During autohydrolysis, deacetylation and decomposition of hemicellulose was observed by ion-exchange chromatography and Fourier transform infrared spectroscopy (FT-IR). Additionally, the cleavage of lignin ether bonds was clearly determined by 13C cross-polarization/magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR). Phosphitylation followed by 31P NMR analysis of the heavy oils gave detailed structural information ofmore » the hydroxyl groups; the results revealed that autohydrolysis pretreatment led to a reduction of carboxyl acids in the heavy oils generated at all three pyrolysis temperatures (400, 500, and 600 °C). The 31P NMR analysis also revealed that autohydrolysis pretreatment led to a reduction of condensed phenolic hydroxyl groups in the heavy oils produced at 600 °C. 1H- 13C heteronuclear single-quantum correlation (HSQC) NMR analysis showed that at a pyrolysis temperature of 600 °C, the pretreated pine produced lower methoxy group constituents. In both 31P and HSQC NMR results indicated that autohydrolysis pretreatment increased levoglucosan yields in the bio-oils.« less

Comprehensive model for predicting elemental composition of coal pyrolysis products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ricahrds, Andrew P.; Shutt, Tim; Fletcher, Thomas H.

Large-scale coal combustion simulations depend highly on the accuracy and utility of the physical submodels used to describe the various physical behaviors of the system. Coal combustion simulations depend on the particle physics to predict product compositions, temperatures, energy outputs, and other useful information. The focus of this paper is to improve the accuracy of devolatilization submodels, to be used in conjunction with other particle physics models. Many large simulations today rely on inaccurate assumptions about particle compositions, including that the volatiles that are released during pyrolysis are of the same elemental composition as the char particle. Another common assumptionmore » is that the char particle can be approximated by pure carbon. These assumptions will lead to inaccuracies in the overall simulation. There are many factors that influence pyrolysis product composition, including parent coal composition, pyrolysis conditions (including particle temperature history and heating rate), and others. All of these factors are incorporated into the correlations to predict the elemental composition of the major pyrolysis products, including coal tar, char, and light gases.« less

The impacts of biomass properties on pyrolysis yields, economic and environmental performance of the pyrolysis-bioenergy-biochar platform to carbon negative energy.

PubMed

Li, Wenqin; Dang, Qi; Brown, Robert C; Laird, David; Wright, Mark M

2017-10-01

This study evaluated the impact of biomass properties on the pyrolysis product yields, economic and environmental performance for the pyrolysis-biochar-bioenergy platform. We developed and applied a fast pyrolysis, feedstock-sensitive, regression-based chemical process model to 346 different feedstocks, which were grouped into five types: woody, stalk/cob/ear, grass/plant, organic residue/product and husk/shell/pit. The results show that biomass ash content of 0.3-7.7wt% increases biochar yield from 0.13 to 0.16kg/kg of biomass, and decreases biofuel yields from 87.3 to 40.7 gallons per tonne. Higher O/C ratio (0.88-1.12) in biomass decreases biochar yield and increases biofuel yields within the same ash content level. Higher ash content of biomass increases minimum fuel selling price (MFSP), while higher O/C ratio of biomass decreases MFSP within the same ash content level. The impact of ash and O/C ratio of biomass on GHG emissions are not consistent for all feedstocks. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catalytic properties of mesoporous Al–La–Mn oxides prepared via spray pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Goun; Jung, Kyeong Youl; Lee, Choul-Ho

Highlights: • Al–La–Mn oxides were prepared using spray pyrolysis. • Al–La–Mn oxides exhibit large and uniform pore sizes. • Mesoporous Al–La–Mn oxides were compared with those prepared by conventional precipitation. • Mesoporous Al–La–Mn oxides show superior activity in decomposition of hydrogen peroxide. - Abstract: Mesoporous Al–La–Mn oxides are prepared via spray pyrolysis and are applied to the catalytic decomposition of hydrogen peroxide. The characteristics of the mesoporous Al–La–Mn oxides are examined using N{sub 2} adsorption, X-ray diffraction, and X-ray fluorescence measurements. The surface area and pore size of the Al–La–Mn oxides prepared via spray pyrolysis are larger than those ofmore » the Al–La–Mn oxides prepared using a precipitation method. The catalytic performance of the materials during the decomposition of hydrogen peroxide is examined in a pulse-injection reactor. It is confirmed that the mesoporous Al–La–Mn oxides prepared via spray pyrolysis exhibit higher catalytic activity and stability in the decomposition of hydrogen peroxide than Al–La–Mn oxides prepared using a conventional precipitation method.« less

Experimental study of thermal conductivity of pyrolysised materials by means of a flat layer

NASA Astrophysics Data System (ADS)

Vaniushkin, V. D.; Popov, S. K.; Sidenkov, D. V.

2017-11-01

Recycling of tires is currently a very important task. One of the areas of recycling tires is their low-temperature pyrolysis to produce marketable products - liquid fraction and a solid coke residue. For the development of the pyrolysis installation it is important to know the thermal conductivity of the coke residue at different temperatures of pyrolysis of initial material. As a property of matter, thermal conductivity depends in general on temperature and pressure. For materials with some structure, such as porous materials, the thermal conductivity depends on the characteristics of the structure. The thermal conductivity of the porous coke residue at pyrolysis temperatures of 300 0C, 400 0C, 500 0C and atmospheric pressure was studied experimentally at the laboratory unit of the department of “Theoretical basis of heat engineering” using the method of the flat layer in the temperature range 5…100 0C. Experimentally proved temperature dependencies of the coefficient of thermal conductivity of the coke residue are built to improve the accuracy of calculations of constructive and regime parameters of the pyrolysis installation.

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

PubMed

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

2017-02-01

In this study, production of bio-oil and biochar from soapstock via microwave-assisted co-catalytic fast pyrolysis combining the advantages of in-situ and ex-situ catalysis was performed. The effects of catalyst and pyrolysis temperature on product fractional yields and bio-oil chemical compositions were investigated. From the perspective of bio-oil yield, the optimal pyrolysis temperature was 550°C. The use of catalysts reduced the water content, and the addition of bentonite increased the bio-oil yield. Up to 84.16wt.% selectivity of hydrocarbons in the bio-oil was obtained in the co-catalytic process. In addition, the co-catalytic process can reduce the proportion of oxygenates in the bio-oil to 15.84wt.% and eliminate the N-containing compounds completely. The addition of bentonite enhanced the BET surface area of bio-char. In addition, the bio-char removal efficiency of Cd 2+ from soapstock pyrolysis in presence of bentonite was 27.4wt.% higher than without bentonite. Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of Pyrolysis Temperature on Physico-Chemical Properties of Corn Stover (Zea mays L.) Biochar and Feasibility for Carbon Capture and Energy Balance.

PubMed

Rafiq, Muhammad Khalid; Bachmann, Robert Thomas; Rafiq, Muhammad Tariq; Shang, Zhanhuan; Joseph, Stephen; Long, Ruijun

2016-01-01

This study examined the influence of pyrolysis temperature on biochar characteristics and evaluated its suitability for carbon capture and energy production. Biochar was produced from corn stover using slow pyrolysis at 300, 400 and 500°C and 2 hrs holding time. The experimental biochars were characterized by elemental analysis, BET, FTIR, TGA/DTA, NMR (C-13). Higher heating value (HHV) of feedstock and biochars was measured using bomb calorimeter. Results show that carbon content of corn stover biochar increased from 45.5% to 64.5%, with increasing pyrolysis temperatures. A decrease in H:C and O:C ratios as well as volatile matter, coupled with increase in the concentration of aromatic carbon in the biochar as determined by FTIR and NMR (C-13) demonstrates a higher biochar carbon stability at 500°C. It was estimated that corn stover pyrolysed at 500°C could provide of 10.12 MJ/kg thermal energy. Pyrolysis is therefore a potential technology with its carbon-negative, energy positive and soil amendment benefits thus creating win- win scenario.

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

DOE PAGES

Klinger, Jordan; Bar-Ziv, Ezra; Shonnard, David; ...

2015-12-12

Pyrolysis has the potential to create a biocrude oil from biomass sources that can be used as fuel or as feedstock for subsequent upgrading to hydrocarbon fuels or other chemicals. The product distribution/composition, however, is linked to the biomass source. This work investigates the products formed from pyrolysis of woody biomass with a previously developed chemical kinetics model. Different woody feedstocks reported in prior literature are placed on a common basis (moisture, ash, fixed carbon free) and normalized by initial elemental composition through ultimate analysis. Observed product distributions over the full devolatilization range are explored, reconstructed by the model, andmore » verified with independent experimental data collected with a microwave-assisted pyrolysis system. These trends include production of permanent gas (CO, CO 2), char, and condensable (oil, water) species. Elementary compositions of these streams are also investigated. As a result, close agreement between literature data, model predictions, and independent experimental data indicate that the proposed model/method is able to predict the ideal distribution from fast pyrolysis given reaction temperature, residence time, and feedstock composition.« less

Comparison of cadmium and lead sorption by Phyllostachys pubescens biochar produced under a low-oxygen pyrolysis atmosphere.

PubMed

Zhang, Chao; Shan, Baoqing; Tang, Wenzhong; Zhu, Yaoyao

2017-08-01

Phyllostachys pubescens (PP) biochars produced under a low oxygen pyrolysis atmosphere (oxygen content 1-4%) were prepared as sorbents for investigating the mechanisms of cadmium and lead sorption. A low-oxygen pyrolysis atmosphere increased biochar ash and specific surface area, promoting heavy metal precipitation and complexation. The maximum sorption capacity (Q m ) of Pb 2+ obtained from the Langmuir model was 67.4mg·g -1 , while Q m of Cd 2+ was 14.7mg·g -1 . The contribution of each mechanism varied with increasing oxygen content at a low pyrolysis temperature. Mineral precipitation with Pb 2+ was the predominant mechanism for Pb 2+ removal and the contribution proportion significantly increased from 17.2% to 71.7% as pyrolysis oxygen atmosphere increased from 0% to 4%. The results showed that cadmium sorption primarily involved coordination with π electrons, at 54.1-82.6% of the total adsorption capacity. The PP biochar shows potential for application in removing heavy metal contaminants, especially Pb 2+ . Copyright © 2017 Elsevier Ltd. All rights reserved.

Pyrolysis of oil palm mesocarp fiber catalyzed with steel slag-derived zeolite for bio-oil production.

PubMed

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

2018-02-01

The pyrolysis of oil palm mesocarp fiber (OPMF) was catalyzed with a steel slag-derived zeolite (FAU-SL) in a slow-heating fixed-bed reactor at 450 °C, 550 °C, and 600 °C. The catalytic pyrolysis of OPMF produced a maximum yield of 47 wt% bio-oil at 550 °C, and the crude pyrolysis vapor (CPV) of this process yielded crude pyrolysis oil with broad distribution of bulky oxygenated organic compounds. The bio-oil composition produced at 550 °C contained mainly light and stable acid-rich carbonyls at a relative abundance of 48.02% peak area and phenolic compounds at 12.03% peak area. The FAU-SL high mesoporosity and strong surface acidity caused the conversion of the bulky CPV molecules into mostly light acid-rich carbonyls and aromatics through secondary reactions. The secondary reactions mechanisms facilitated by FAU-SL reduced the distribution of the organic compounds in the bio-oil to mostly acid-rich carbonyls and aromatic in contrast to other common zeolite. Copyright © 2017. Published by Elsevier Ltd.

Effect of pyrolysis temperature on chemical form, behavior and environmental risk of Zn, Pb and Cd in biochar produced from phytoremediation residue.

PubMed

Huang, Hui; Yao, Wenlin; Li, Ronghua; Ali, Amjad; Du, Juan; Guo, Di; Xiao, Ran; Guo, Zhanyu; Zhang, Zengqiang; Awasthi, Mukesh Kumar

2018-02-01

This study aimed to evaluate the chemical forms, behavior and environmental risk of heavy metal (HMs) Zn, Pb and Cd in phytoremediation residue (PMR) pyrolyzed at 350 °C, 550 °C and 750 °C, respectively. The behavior of HMs variation during the PMR pyrolysis process was analyzed and the potential HMs environmental risk of phytoremediation residue biochars (PMB) was assessed which was seldom investigated before. The results showed that the pyrolysis temperature increase decreased the soluble/exchangeable HMs fraction and alleviated the HMs bioavailability. When the temperature was over 550 °C, the adsorbed Zn(II), Pb(II) and Cd(II) were turned into oxides forms and concentrated in PMB with more stable forms exhibiting lower risk assessment code and potential ecological risk index. The ecotoxicity test showed higher pyrolysis temperature favored the reduction of PMB ecotoxicity. It is suggested that pyrolysis temperature above 550°C may be suitable for thermal treatment of PMR with acceptable environmental risk. Copyright © 2017 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCown, F.E.

UCC Research Corporation, along with most of the companies involved in coal development, initially was thinking in terms of high pressure systems, flash pyrolysis, and hydrogenation. Most goverment funding has also been provided for projects using these techniques. However, information from several sources, only recently available to UCC Research Corporation, has effected a change in our recommended direction on the subject project. First, information being obtained in-house at UCC Research on another project using low temperature/pressure pyrolysis looked very favorable. Secondly, the initial review of the design, cost and capabilities of the pyrolysis equipment originally proposed indicated that substantial advantagesmore » could be gained at only a modest increase in cost, by changing to a low pressure unit. Finally, it was discovered that a company in England, using almost identical pyrolysis conditions as those being used at UCC Research, was producing coal liquids commercially, and had been in business many years. In consideration of the above information, UCC Research is recommending that the pyrolysis system for the subject project be changed to a low pressure/temperature design, utilizing the information obtained via our in-house research and from the company in England.« less

Confined-Pyrolysis as an Experimental Method for Hydrothermal Organic Synthesis

NASA Technical Reports Server (NTRS)

Leif, Roald N.; Simoneit, Bernd R. T.

1995-01-01

A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic and the competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.

Effect of high-pressure on pine sawdust pyrolysis: Products distribution and characteristics

NASA Astrophysics Data System (ADS)

Xu, Baiqing; Li, Aimin

2017-08-01

In this work, the pressurized pyrolysis of pine sawdust was performed with a self-made pressurized pyrolysis reactor to investigatethe influence of pyrolysis pressure in the range of 0-5 MPa on products distribution and characteristics. The combustion feature and microstructure of bio-char had analyzed by thermogravimetric (TG) and scanning electron microscopy (SEM), respectively. Elemental analyzer and Fourier transform infrared spectroscopy (FTIR) were used to confirm the identities of bio-oil. The results indicated the pressure had a notable impact on the biomass pyrolysis, which promoted the secondary cracking of bio-oil to produce more gaseous products and bio-char. The minimum bio-oil yield of 20.24% was obtained at the pressure of 5 MPa. Furthermore, the pressure improved the products characteristics. The increasing of pressure was favour to the deoxygenation and dehydrogenation reactions of bio-oil, which led to the increase of CH4, H2 and CO2 in gas. At the same time, under the influence of pressure, the surface structure and compactedness of the bio-char were obviously improved.

Microwave pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production.

PubMed

Lei, Hanwu; Ren, Shoujie; Wang, Lu; Bu, Quan; Julson, James; Holladay, John; Ruan, Roger

2011-05-01

Microwave pyrolysis of distillers dried grain with solubles (DDGS) was investigated to determine the effects of pyrolytic conditions on the yields of bio-oil, syngas, and biochar. Pyrolysis process variables included reaction temperature, time, and power input. Microwave pyrolysis of DDGS was analyzed using response surface methodology to find out the effect of process variables on the biofuel (bio-oil and syngas) conversion yield and establish prediction models. Bio-oil recovery was in the range of 26.5-50.3 wt.% of the biomass. Biochar yields were 23.5-62.2% depending on the pyrolysis conditions. The energy content of DDGS bio-oils was 28 MJ/kg obtained at the 650°C and 8 min, which was about 66.7% of the heating value of gasoline. GC/MS analysis indicated that the biooil contained a series of important and useful chemical compounds: aliphatic and aromatic hydrocarbons. At least 13% of DDGS bio-oil was the same hydrocarbon compounds found in regular unleaded gasoline. Copyright © 2011 Elsevier Ltd. All rights reserved.

A kinetic study of pyrolysis and combustion of microalgae Chlorella vulgaris using thermo-gravimetric analysis.

PubMed

Agrawal, Ankit; Chakraborty, Saikat

2013-01-01

This work uses thermo-gravimetric, differential thermo-gravimetric and differential thermal analyses to evaluate the kinetics of pyrolysis (in inert/N(2) atmosphere) and (oxidative) combustion of microalgae Chlorella vulgaris by heating from 50 to 800 °C at heating rates of 5-40 °C/min. This study shows that combustion produces higher biomass conversion than pyrolysis, and that three stages of decomposition occur in both cases, of which, the second one--consisting of two temperature zones--is the main stage of devolatization. Proteins and carbohydrates are decomposed in the first of the two zones at activation energies of 51 and 45 kJ/mol for pyrolysis and combustion, respectively, while lipids are decomposed in its second zone at higher activation energies of 64 and 63 kJ/mol, respectively. The kinetic expressions of the reaction rates in the two zones for pyrolysis and combustion have been obtained and it has been shown that increased heating rates result in faster and higher conversion. Copyright © 2012 Elsevier Ltd. All rights reserved.

Nitrogen conversion under rapid pyrolysis of two types of aquatic biomass and corresponding blends with coal.

PubMed

Yuan, Shuai; Chen, Xue-li; Li, Wei-feng; Liu, Hai-feng; Wang, Fu-chen

2011-11-01

Rapid pyrolysis of two types of aquatic biomass (blue-green algae and water hyacinth), and their blends with two coals (bituminous and anthracite) was carried out in a high-frequency furnace. Nitrogen conversions during rapid pyrolysis of the two biomass and the interactions between the biomass and coals on nitrogen conversions were investigated. Results show that little nitrogen retained in char after the biomass pyrolysis, and NH(3) yields were higher than HCN. During co-pyrolysis of biomass and coal, interactions between biomass and coal decreased char-N yields and increased volatile-N yields, but the total yields of NH(3)+HCN in volatile-N were decreased in which HCN formations were decreased consistently, while NH(3) formations were only decreased in the high-temperature range but promoted in the low-temperature range. Interactions between blue-green algae and coals are stronger than those between water hyacinth and coal, and interactions between biomass and bituminous are stronger than those between biomass and anthracite. Copyright © 2011 Elsevier Ltd. All rights reserved.

Microwave pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lei, Hanwu; Ren, Shoujie; Wang, Lu

2011-05-01

Microwave pyrolysis of distillers dried grain with solubles (DDGS) was investigated to determine the effects of pyrolytic conditions on the yields of bio-oil, syngas, and biochar. Pyrolysis process variables included reaction temperature, time, and power input. Microwave pyrolysis of DDGS was analyzed using response surface methodology to find out the effect of process variables on the biofuel (bio-oil and syn- gas) conversion yield and establish prediction models. Bio-oil recovery was in the range of 26.5–50.3 wt.% of the biomass. Biochar yields were 23.5–62.2% depending on the pyrolysis conditions. The energy con- tent of DDGS bio-oils was 28 MJ/kg obtained atmore » the 650 oC and 8 min, which was about 66.7% of the heat- ing value of gasoline. GC/MS analysis indicated that the biooil contained a series of important and useful chemical compounds: aliphatic and aromatic hydrocarbons. At least 13% of DDGS bio-oil was the same hydrocarbon compounds found in regular unleaded gasoline.« less

Kinetic and energy production analysis of pyrolysis of lignocellulosic biomass using a three-parallel Gaussian reaction model.

PubMed

Chen, Tianju; Zhang, Jinzhi; Wu, Jinhu

2016-07-01

The kinetic and energy productions of pyrolysis of a lignocellulosic biomass were investigated using a three-parallel Gaussian distribution method in this work. The pyrolysis experiment of the pine sawdust was performed using a thermogravimetric-mass spectroscopy (TG-MS) analyzer. A three-parallel Gaussian distributed activation energy model (DAEM)-reaction model was used to describe thermal decomposition behaviors of the three components, hemicellulose, cellulose and lignin. The first, second and third pseudocomponents represent the fractions of hemicellulose, cellulose and lignin, respectively. It was found that the model is capable of predicting the pyrolysis behavior of the pine sawdust. The activation energy distribution peaks for the three pseudo-components were centered at 186.8, 197.5 and 203.9kJmol(-1) for the pine sawdust, respectively. The evolution profiles of H2, CH4, CO, and CO2 were well predicted using the three-parallel Gaussian distribution model. In addition, the chemical composition of bio-oil was also obtained by pyrolysis-gas chromatography/mass spectrometry instrument (Py-GC/MS). Copyright © 2016 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Estimation of risks by chemicals produced during laser pyrolysis of tissues

NASA Astrophysics Data System (ADS)

Weber, Lothar W.; Spleiss, Martin

1995-01-01

Use of laser systems in minimal invasive surgery results in formation of laser aerosol with volatile organic compounds of possible health risk. By use of currently identified chemical substances an overview on possibly associated risks to human health is given. The class of the different identified alkylnitriles seem to be a laser specific toxicological problem. Other groups of chemicals belong to the Maillard reaction type, the fatty acid pyrolysis type, or even the thermally activated chemolysis. In relation to the available different threshold limit values the possible exposure ranges of identified substances are discussed. A rough estimation results in an exposure range of less than 1/100 for almost all substances with given human threshold limit values without regard of possible interactions. For most identified alkylnitriles, alkenes, and heterocycles no threshold limit values are given for lack of, until now, practical purposes. Pyrolysis of anaesthetized organs with isoflurane gave no hints for additional pyrolysis products by fragment interactions with resulting VOCs. Measurements of pyrolysis gases resulted in detection of small amounts of NO additionally with NO2 formation at plasma status.

Catalytic fast co-pyrolysis of biomass and food waste to produce aromatics: Analytical Py-GC/MS study.

PubMed

Zhang, Bo; Zhong, Zhaoping; Min, Min; Ding, Kuan; Xie, Qinglong; Ruan, Roger

2015-01-01

In this study, catalytic fast co-pyrolysis (co-CFP) of corn stalk and food waste (FW) was carried out to produce aromatics using quantitative pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and ZSM-5 zeolite in the hydrogen form was employed as the catalyst. Co-CFP temperature and a parameter called hydrogen to carbon effective ratio (H/C(eff) ratio) were examined for their effects on the relative content of aromatics. Experimental results showed that co-CFP temperature of 600 °C was optimal for the formation of aromatics and other organic pyrolysis products. Besides, H/C(eff) ratio had an important influence on product distribution. The yield of total organic pyrolysis products and relative content of aromatics increased non-linearly with increasing H/C(eff) ratio. There was an apparent synergistic effect between corn stalk and FW during co-CFP process, which promoted the production of aromatics significantly. Co-CFP of biomass and FW was an effective method to produce aromatics and other petrochemicals. Copyright © 2015. Published by Elsevier Ltd.

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

PubMed

Oh, Seung-Jin; Jung, Su-Hwa; Kim, Joo-Sik

2013-09-01

Corncob was pyrolyzed using ZnCl2 in a pyrolysis plant equipped with a fluidized bed reactor to co-produce furfural and acetic acid. The effects of reaction conditions, the ZnCl2 content and contacting method of ZnCl2 with corncob on the yields of furfural and acetic acid were investigated. The pyrolysis was performed within the temperature range between 310 and 410°C, and the bio-oil yield were 30-60 wt% of the product. The furfural yield increased up to 8.2 wt%. The acetic acid yield was maximized with a value of 13.1 wt%. A lower feed rate in the presence of ZnCl2 was advantageous for the production of acetic acid. The fast pyrolysis of a smaller corncob sample mechanically mixed with 20 wt% of ZnCl2 gave rise to a distinct increase in furfural. A high selectivity for furfural and acetic acid in bio-oil would make the pyrolysis of corncob with ZnCl2 very economically attractive. Copyright © 2013 Elsevier Ltd. All rights reserved.

Pyrolysis of plastic packaging waste: A comparison of plastic residuals from material recovery facilities with simulated plastic waste.

PubMed

Adrados, A; de Marco, I; Caballero, B M; López, A; Laresgoiti, M F; Torres, A

2012-05-01

Pyrolysis may be an alternative for the reclamation of rejected streams of waste from sorting plants where packing and packaging plastic waste is separated and classified. These rejected streams consist of many different materials (e.g., polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), aluminum, tetra-brik, and film) for which an attempt at complete separation is not technically possible or economically viable, and they are typically sent to landfills or incinerators. For this study, a simulated plastic mixture and a real waste sample from a sorting plant were pyrolyzed using a non-stirred semi-batch reactor. Red mud, a byproduct of the aluminum industry, was used as a catalyst. Despite the fact that the samples had a similar volume of material, there were noteworthy differences in the pyrolysis yields. The real waste sample resulted, after pyrolysis, in higher gas and solid yields and consequently produced less liquid. There were also significant differences noted in the compositions of the compared pyrolysis products. Copyright © 2011 Elsevier Ltd. All rights reserved.

Effects of pyrolysis temperature on the physicochemical properties of empty fruit bunch and rice husk biochars.

PubMed

Claoston, N; Samsuri, A W; Ahmad Husni, M H; Mohd Amran, M S

2014-04-01

Biochar has received great attention recently due to its potential to improve soil fertility and immobilize contaminants as well as serving as a way of carbon sequestration and therefore a possible carbon sink. In this work, a series of biochars were produced from empty fruit bunch (EFB) and rice husk (RH) by slow pyrolysis at different temperatures (350, 500, and 650°C) and their physicochemical properties were analysed. The results indicate that porosity, ash content, electrical conductivity (EC), and pH value of both EFB and RH biochars were increased with temperature; however, yield, cation exchange capacity (CEC), and H, C, and N content were decreased with increasing pyrolysis temperature. The Fourier transform IR spectra were similar for both RH and EFB biochars but the functional groups were more distinct in the EFB biochar spectra. There were reductions in the amount of functional groups as pyrolysis temperature increased especially for the EFB biochar. However, total acidity of the functional groups increased with pyrolysis temperature for both biochars.

Thermal behavior and kinetic study for catalytic co-pyrolysis of biomass with plastics.

PubMed

Zhang, Xuesong; Lei, Hanwu; Zhu, Lei; Zhu, Xiaolu; Qian, Moriko; Yadavalli, Gayatri; Wu, Joan; Chen, Shulin

2016-11-01

The present study aims to investigate the thermal decomposition behaviors and kinetics of biomass (cellulose/Douglas fir sawdust) and plastics (LDPE) in a non-catalytic and catalytic co-pyrolysis over ZSM-5 catalyst by using a thermogravimetric analyzer (TGA). It was found that there was a positive synergistic interaction between biomass and plastics according to the difference of weight loss (ΔW), which could decrease the formation of solid residue at the end of the experiment. The first order reaction model well fitted for both non-catalytic and catalytic co-pyrolysis of biomass with plastics. The activation energy (E) of Cellulose-LDPE-Catalyst and DF-LDPE-Catalyst are only 89.51 and 54.51kJ/mol, respectively. The kinetics analysis showed that adding catalyst doesn't change the decomposition mechanism. As a result, the kinetic study on catalytic co-pyrolysis of biomass with plastics was suggested that the catalytic co-pyrolysis is a promising technique that can significantly reduce the energy input. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions.

PubMed

Zhou, Hui; Wu, Chunfei; Onwudili, Jude A; Meng, Aihong; Zhang, Yanguo; Williams, Paul T

2015-02-01

The formation of 2-4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. The results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PubMed

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

2017-12-01

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

Pyrolysis of the mixture of MSWI fly ash and sewage sludge for co-disposal: Effect of ferrous/ferric sulfate additives.

PubMed

Hu, Yuyan; Yang, Fan; Chen, Fangfang; Feng, Yuheng; Chen, Dezhen; Dai, Xiaohu

2018-05-01

Co-pyrolysis with sewage sludge was proved to be an efficient pre-treatment for sanitary landfill of municipal solid waste incineration (MSWI) fly ash (FA). In this study, to improve the stabilization effect of heavy metals, mixed ferrous/ferric sulfate was added into the FA/SS mixture before pyrolysis. To examine the feasibility of the landfill of co-pyrolysis char, toxicity characteristic leaching procedure (HJ/T300) was conducted. In addition, physio-chemical characteristics of char were also tested to explain the stability of heavy metals, including the speciation, mineralogical composition and the morphological features of them. The results indicated that within the range that the obtained char could meet the standard for landfill (GB16889-2008), the appropriate addition of mixed ferrous/ferric sulfates benefit to raising the FA ratio in the FA/SS mixture. The maximum ratio of 67 wt% is achieved when the additive was 1.5 wt% of dried SS (based on iron element) and the pyrolysis temperature was 500 °C. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

PubMed

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

2017-10-01

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

Pyrolysis reaction models of waste tires: Application of Master-Plots method for energy conversion via devolatilization.

PubMed

Irmak Aslan, Dilan; Parthasarathy, Prakash; Goldfarb, Jillian L; Ceylan, Selim

2017-10-01

Land applied disposal of waste tires has far-reaching environmental, economic, and human health consequences. Pyrolysis represents a potential waste management solution, whereby the solid carbonaceous residue is heated in the absence of oxygen to produce liquid and gaseous fuels, and a solid char. The design of an efficient conversion unit requires information on the reaction kinetics of pyrolysis. This work is the first to probe the appropriate reaction model of waste tire pyrolysis. The average activation energy of pyrolysis was determined via iso-conversional methods over a mass fraction conversion range between 0.20 and 0.80 to be 162.8±23.2kJmol -1 . Using the Master Plots method, a reaction order of three was found to be the most suitable model to describe the pyrolytic decomposition. This suggests that the chemical reactions themselves (cracking, depolymerization, etc.), not diffusion or boundary layer interactions common with carbonaceous biomasses, are the rate-limiting steps in the pyrolytic decomposition of waste tires. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pyrolysis gas chromatography-mass spectrometry to characterize organic matter and its relationship to uranium content of Appalachian Devonian black shales

USGS Publications Warehouse

Leventhal, J.S.

1981-01-01

Gas Chromatographic analysis of volatile products formed by stepwise pyrolysis of black shales can be used to characterize the kerogen by relating it to separated, identified precursors such as land-derived vitrinite and marine-source Tasmanites. Analysis of a Tasmanites sample shows exclusively n-alkane and -alkene pyrolysis products, whereas a vitrinite sample shows a predominance of one- and two-ring substituted aromatics. For core samples from northern Tennessee and for a suite of outcrop samples from eastern Kentucky, the organic matter type and the U content (<10-120ppm) show variations that are related to precursor organic materials. The samples that show a high vitrinite component in their pyrolysis products are also those samples with high contents of U. ?? 1981.