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.

Vapor phase pyrolysis

NASA Technical Reports Server (NTRS)

Steurer, Wolfgang

1992-01-01

The vapor phase pyrolysis process is designed exclusively for the lunar production of oxygen. In this concept, granulated raw material (soil) that consists almost entirely of metal oxides is vaporized and the vapor is raised to a temperature where it dissociates into suboxides and free oxygen. Rapid cooling of the dissociated vapor to a discrete temperature causes condensation of the suboxides, while the oxygen remains essentially intact and can be collected downstream. The gas flow path and flow rate are maintained at an optimum level by control of the pressure differential between the vaporization region and the oxygen collection system with the aid of the environmental vacuum.

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.

Copper(II)-mediated thermolysis of alginates: a model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae

PubMed Central

Rowbotham, J. S.; Dyer, P. W.; Greenwell, H. C.; Selby, D.; Theodorou, M. K.

2013-01-01

Thermochemical processing methods such as pyrolysis are of growing interest as a means of converting biomass into fuels and commodity chemicals in a sustainable manner. Macroalgae, or seaweed, represent a novel class of feedstock for pyrolysis that, owing to the nature of the environments in which they grow coupled with their biochemistry, naturally possess high metal contents. Although the impact of metals upon the pyrolysis of terrestrial biomass is well documented, their influence on the thermochemical conversion of marine-derived feeds is largely unknown. Furthermore, these effects are inherently difficult to study, owing to the heterogeneous character of natural seaweed samples. The work described in this paper uses copper(II) alginate, together with alginic acid and sodium alginate as model compounds for exploring the effects of metals upon macroalgae thermolysis. A thermogravimetric analysis–Fourier transform infrared spectroscopic study revealed that, unusually, Cu2+ ions promote the onset of pyrolysis in the alginate polymer, with copper(II) alginate initiating rapid devolatilization at 143°C, 14°C lower than alginic acid and 61°C below the equivalent point for sodium alginate. Moreover, this effect was mirrored in a sample of wild Laminaria digitata that had been doped with Cu2+ ions prior to pyrolysis, thus validating the use of alginates as model compounds with which to study the thermolysis of macroalgae. These observations indicate the varying impact of different metal species on thermochemical behaviour of seaweeds and offer an insight into the pyrolysis of brown macroalgae used in phytoremediation of metal-containing waste streams. PMID:24427515

Deactivation of Multilayered MFI Nanosheet Zeolite during Upgrading of Biomass Pyrolysis Vapors

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

Xu, Mengze; Mukarakate, Calvin; Iisa, Kristiina

Here, the catalytic fast pyrolysis (CFP) of biomass is a promising technology for producing renewable transportation fuels and chemicals. MFI-type catalysts have shown promise for CFP because they produce gasoline range hydrocarbons from oxygenated pyrolysis compounds; however, rapid catalyst deactivation due to coking is one of the major technical barriers inhibiting the commercialization of this technology. Coke deposited on the surface of the catalysts blocks access to active sites in the micropores leading to rapid catalyst deactivation. Our strategy is to minimize rapid catalyst deactivation by adding mesoporosity through forming MFI nanosheet materials. The synthesized MFI nanosheet catalysts were fullymore » characterized and evaluated for cellulose pyrolysis vapor upgrading to produce olefins and aromatic hydrocarbons. The data obtained from pyrolysis-GCMS (py-GCMS), showed that fresh MFI nanosheets produced similar aromatic hydrocarbon and olefin yields compared to conventional HZSM-5. However, MFI nanosheets demonstrated a longer lifetime than HZSM-5 even though coke contents were also higher than for HZSM-5 because the mesopores enabled better accessibility to active acid sites. This conclusion was supported by results from post-reaction analysis of various spent catalysts collected at different points during the deactivation experiments.« less

Deactivation of Multilayered MFI Nanosheet Zeolite during Upgrading of Biomass Pyrolysis Vapors

DOE PAGES

Xu, Mengze; Mukarakate, Calvin; Iisa, Kristiina; ...

2017-05-02

Here, the catalytic fast pyrolysis (CFP) of biomass is a promising technology for producing renewable transportation fuels and chemicals. MFI-type catalysts have shown promise for CFP because they produce gasoline range hydrocarbons from oxygenated pyrolysis compounds; however, rapid catalyst deactivation due to coking is one of the major technical barriers inhibiting the commercialization of this technology. Coke deposited on the surface of the catalysts blocks access to active sites in the micropores leading to rapid catalyst deactivation. Our strategy is to minimize rapid catalyst deactivation by adding mesoporosity through forming MFI nanosheet materials. The synthesized MFI nanosheet catalysts were fullymore » characterized and evaluated for cellulose pyrolysis vapor upgrading to produce olefins and aromatic hydrocarbons. The data obtained from pyrolysis-GCMS (py-GCMS), showed that fresh MFI nanosheets produced similar aromatic hydrocarbon and olefin yields compared to conventional HZSM-5. However, MFI nanosheets demonstrated a longer lifetime than HZSM-5 even though coke contents were also higher than for HZSM-5 because the mesopores enabled better accessibility to active acid sites. This conclusion was supported by results from post-reaction analysis of various spent catalysts collected at different points during the deactivation experiments.« less

Pyrolysis characteristics of typical biomass thermoplastic composites

NASA Astrophysics Data System (ADS)

Cai, Hongzhen; Ba, Ziyu; Yang, Keyan; Zhang, Qingfa; Zhao, Kunpeng; Gu, Shiyan

The biomass thermoplastic composites were prepared by extrusion molding method with poplar flour, rice husk, cotton stalk and corn stalk. The thermo gravimetric analyzer (TGA) has also been used for evaluating the pyrolysis process of the composites. The results showed that the pyrolysis process mainly consists of two stages: biomass pyrolysis and the plastic pyrolysis. The increase of biomass content in the composite raised the first stage pyrolysis peak temperature. However, the carbon residue was reduced and the pyrolysis efficiency was better because of synergistic effect of biomass and plastic. The composite with different kinds of biomass have similar pyrolysis process, and the pyrolysis efficiency of the composite with corn stalk was best. The calcium carbonate could inhibit pyrolysis process and increase the first stage pyrolysis peak temperature and carbon residue as a filling material of the composite.

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...

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

Investigation of zinc recovery by hydrogen reduction assisted pyrolysis of alkaline and zinc-carbon battery waste.

PubMed

Ebin, Burçak; Petranikova, Martina; Steenari, Britt-Marie; Ekberg, Christian

2017-10-01

Zinc (Zn) recovery from alkaline and zinc-carbon (Zn-C) battery waste were studied by a laboratory scale pyrolysis process at a reaction temperature of 950°C for 15-60min residence time using 5%H 2(g) -N 2(g) mixture at 1.0L/min gas flow rate. The effect of different cooling rates on the properties of pyrolysis residue, manganese oxide particles, were also investigated. Morphological and structural characterization of the produced Zn particles were performed. The battery black mass was characterized with respect to the properties and chemical composition of the waste battery particles. The thermodynamics of the pyrolysis process was studied using the HSC Chemistry 5.11 software. A hydrogen reduction reaction of the battery black mass (washed with Milli-Q water) takes place at the chosen temperature and makes it possible to produce fine Zn particles by rapid condensation following the evaporation of Zn from the pyrolysis batch. The amount of Zn that can be separated from the black mass increases by extending the residence time. Recovery of 99.8% of the Zn was achieved at 950°C for 60min residence time using 1.0L/min gas flow rate. The pyrolysis residue contains MnO and Mn 2 O 3 compounds, and the oxidation state of manganese can be controlled by cooling rate and atmosphere. The Zn particles exhibit spherical and hexagonal particle morphology with a particle size varying between 200nm and 3µm. However the particles were formed by aggregation of nanoparticles which are primarily nucleated from the gas phase. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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.

Microbial conversion of pyrolytic products to biofuels: a novel and sustainable approach toward second-generation biofuels.

PubMed

Islam, Zia Ul; Zhisheng, Yu; Hassan, El Barbary; Dongdong, Chang; Hongxun, Zhang

2015-12-01

This review highlights the potential of the pyrolysis-based biofuels production, bio-ethanol in particular, and lipid in general as an alternative and sustainable solution for the rising environmental concerns and rapidly depleting natural fuel resources. Levoglucosan (1,6-anhydrous-β-D-glucopyranose) is the major anhydrosugar compound resulting from the degradation of cellulose during the fast pyrolysis process of biomass and thus the most attractive fermentation substrate in the bio-oil. The challenges for pyrolysis-based biorefineries are the inefficient detoxification strategies, and the lack of naturally available efficient and suitable fermentation organisms that could ferment the levoglucosan directly into bio-ethanol. In case of indirect fermentation, acid hydrolysis is used to convert levoglucosan into glucose and subsequently to ethanol and lipids via fermentation biocatalysts, however the presence of fermentation inhibitors poses a big hurdle to successful fermentation relative to pure glucose. Among the detoxification strategies studied so far, over-liming, extraction with solvents like (n-butanol, ethyl acetate), and activated carbon seem very promising, but still further research is required for the optimization of existing detoxification strategies as well as developing new ones. In order to make the pyrolysis-based biofuel production a more efficient as well as cost-effective process, direct fermentation of pyrolysis oil-associated fermentable sugars, especially levoglucosan is highlly desirable. This can be achieved either by expanding the search to identify naturally available direct levoglusoan utilizers or modify the existing fermentation biocatalysts (yeasts and bacteria) with direct levoglucosan pathway coupled with tolerance engineering could significantly improve the overall performance of these microorganisms.

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.

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

Processes for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil, and apparatuses for treating biomass-derived pyrolysis oil

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

Baird, Lance Awender; Brandvold, Timothy A.

Processes and apparatuses for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil are provided herein. An exemplary process for washing a spent ion exchange bed employed in purification of biomass-derived pyrolysis oil includes the step of providing a ion-depleted pyrolysis oil stream having an original oxygen content. The ion-depleted pyrolysis oil stream is partially hydrotreated to reduce the oxygen content thereof, thereby producing a partially hydrotreated pyrolysis oil stream having a residual oxygen content that is less than the original oxygen content. At least a portion of the partially hydrotreated pyrolysis oil stream is passed throughmore » the spent ion exchange bed. Water is passed through the spent ion exchange bed after passing at least the portion of the partially hydrotreated pyrolysis oil stream therethrough.« less

Characterization of Source Signatures of Fine Roadway Particles by Pyrolysis-GC-MS

NASA Astrophysics Data System (ADS)

van Bergen, S. K.; Holmén, B. A.

2001-12-01

Fine particulate matter, defined as particles with an aerodynamic diameter less than 2.5 μ m (PM2.5), is of growing concern due to its detrimental effects on human health and the environment. Roadway traffic generates a significant fraction of PM2.5 in urban areas. Since exposure to fine particles derived from mobile sources commonly occurs, understanding the physicochemical processes that contribute to the generation, transport and atmospheric reactivity of roadway PM is important. Factors that influence the properties of roadway PM include: the mass, number and size distribution of the particles as well as their chemical composition. These factors are partially determined by the sources of the roadway particles. The focus of this effort is to identify unique organic chemical profiles of known roadway sources of PM using a new rapid characterization technique. A pyrolysis GC-MS analytical method is being developed to uniquely characterize the sources of roadway PM2.5 such as brake dust, tire wear, and direct emissions from diesel and gasoline engines. The source profiles will be used in conjunction with measurements of the composition of ambient roadway PM to determine the importance of the various roadway sources. The advantages of this technique over conventional solvent extractions include: smaller (mg) sample mass requirements, short extraction times and minimal sample handing. Preliminary two-step pyrolysis results will be presented for PM samples from individual sources and an ambient roadway. Specific analytical issues that will be discussed include: modifications of commercial pyrolysis hardware to improve reproducibility; desorption versus pyrolysis; developing appropriate pyrolysis programs for heterogenous sample materials; and method detection limits.

Structural evolution of maize stalk/char particles during pyrolysis.

PubMed

Fu, Peng; Hu, Song; Sun, Lushi; Xiang, Jun; Yang, Tao; Zhang, Anchao; Zhang, Junying

2009-10-01

The structural evolution characteristics of maize stalk/char particles during pyrolysis were investigated. The char was prepared by pyrolyzing at temperatures ranging from 200 to 900 degrees C. Maize stalk and chars were characterized by thermogravimetric analysis, ultimate analysis (TGA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), helium density measurement and N(2) adsorption/desorption method. The char yield decreased rapidly with increasing temperature until 400 degrees C. As temperature increased, the char became progressively more aromatic and carbonaceous. The hydroxyl, aliphatic C-H, carbonyl and olefinic C=C groups were lost at high temperatures. Below 500 degrees C, the removal of volatile matter made pore opening. High temperatures led to the occurrence of softening, melting, fusing and carbon structural ordering. The aromatization process started at approximately 350 degrees C and continued to higher temperatures. The shrinkage of carbon structure occurred above 500 degrees C, which was concurrent with the aromatization process.

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.

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

PubMed

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

2014-12-01

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

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

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.

Separating and Recycling Plastic, Glass, and Gallium from Waste Solar Cell Modules by Nitrogen Pyrolysis and Vacuum Decomposition.

PubMed

Zhang, Lingen; Xu, Zhenming

2016-09-06

Many countries have gained benefits through the solar cells industry due to its high efficiency and nonpolluting power generation associated with solar energy. Accordingly, the market of solar cell modules is expanding rapidly in recent decade. However, how to environmentally friendly and effectively recycle waste solar cell modules is seldom concerned. Based on nitrogen pyrolysis and vacuum decomposition, this work can successfully recycle useful organic components, glass, and gallium from solar cell modules. The results were summarized as follows: (i) nitrogen pyrolysis process can effectively decompose plastic. Organic conversion rate approached 100% in the condition of 773 K, 30 min, and 0.5 L/min N2 flow rate. But, it should be noted that pyrolysis temperature should not exceed 773 K, and harmful products would be increased with the increasing of temperature, such as benzene and its derivatives by GC-MS measurement; (ii) separation principle, products analysis, and optimization of vacuum decomposition were discussed. Gallium can be well recycled under temperature of 1123 K, system pressure of 1 Pa and reaction time of 40 min. This technology is quite significant in accordance with the "Reduce, Reuse, and Recycle Principle" for solid waste, and provides an opportunity for sustainable development of photovoltaic industry.

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...

Modeling and experimental characterization of Blackglas(TM) polymer pyrolysis to ceramic and thermodynamic characterization of Blackglas(TM) ceramic

NASA Astrophysics Data System (ADS)

Wang, Feng

2000-10-01

The transformation of Blackglas(TM) polymer to ceramic is characterized by TGA-RGA/MS, Si29 and C13 NMR. Si29 NMR reveals a dependence between the postcure temperature and the microstructure of the resin. The postcure temperature that appears to give optimal mechanical and oxidative properties of Blackglas(TM) ceramic is around 150°C. The pyrolysis processing models, which are the Lumped Parameters Model (LPM), the Mechanistic Kinetic Model (MKM) and the Redistribution Reaction Model (RRM), are developed to provide an effective window of processing parameters rather than a costly, time-consuming trial and error approach. The Lumped Parameters Model (LPM) is developed to study the effects of various parameters such as temperature, curing conditions and heating rates on mass loss during the pyrolysis of resin and green composites. It can be used for the model-predictive control of the pyrolysis process; The Mechanistic Kinetic Model (MKM) is developed on the basis of known chemistry and architecture of the polysiloxane for the transformation of Blackglas(TM) polymer to ceramic and the evolution of gases. The effects of various heating protocols on the outgassing kinetics have been studied to develop an optimum protocol for a rapid pyrolysis process which gives a composite with desirable mechanical properties; The Redistribution Reaction Model (RRM) is proposed to describe how the microcompositions of silicon oxycarbide change with respect to temperature, and to the ratio O/Si in the polymer precursor. A Thermodynamic Additivity Model (TAM) is developed to estimate the heat capacity, standard heat of formation and entropy of Blackglas(TM) ceramic by means of the Neumann Kopp rule and the available thermodynamic data of the Si-C and Si-O systems. Thermal stability of this ceramic is investigated by constructing predominance diagrams, and it is shown that the internal degradation reactions, which account for a significant loss of strength, will proceed further in the Blackglas(TM) matrix than in the Nicalon fibers. This probably will induce failure in the matrix at lower temperatures than in the fibers. The predominance diagrams also explain the high temperature oxidation, reduction and volatilization experiments on silicon and silicon carbide in high vacuum.

Development of a Glass Reactor Lining for Chlorocarbon-Supercritical Water Reactions.

DTIC Science & Technology

1995-08-09

by 1-chloro-3- phenylpropane which reacted rapidly and completely by both pyrolysis and with SW. The presence of SW produced only a minor shift in...aromatic chloride, 2 -chlorotoluene, over that of dry pyrolysis; metal chlorides were evident in the water layer and HCl was not detected in the SW

Pyrolysis-crystallinity relationships in cellulose

Treesearch

M. Weinstein; A. Broido

1970-01-01

During pyrolysis of pure cellulose, the Crystallinity Index (Crl) remained fairly constant over more than 50% weight loss before dropping rapidly as the X-ray pattern deteriorated. With samples first treated with trace quantities of inorganic salts, heating first increased the Crl—the results implying a preferentially catalyzed decomposition of the amorphous regions....

Method and apparatus for pyrolysis--porous layer open tubular column--cryoadsorption headspace sampling and analysis.

PubMed

Bruno, Thomas J; Nichols, Jessica E

2013-04-19

In previous work, dynamic headspace vapor collection on short, porous layer open tubular (PLOT) capillary columns maintained at low temperature was introduced. In this paper, that metrology is extended with the introduction of a small in situ pyrolysis platform that provides for rapid heating and rapid vapor capture for a wide variety of samples. The new approach is referred to as pyro-PLOT-cryo. The pyrolysis platform is made from two small copper lead wires that hold a basket formed from small diameter, high resistance stainless steel or NiCr wire. The basket is formed to accept a small sample, the mass of which can typically range from 0.2 to 0.05 mg. The pyrolysis is performed by use of a resistor capacitor circuit of the type used in spot welders. We have provided examples of the application of this technique with the analysis of facial cosmetics, plastic explosives, organometallic gasoline additives, polymers, and in micro scale chemical reactions. Additional modifications and future work are also discussed. Published by Elsevier B.V.

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.

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.

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.

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.

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

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.

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.

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

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.

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.

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.

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.

Conventional and fast pyrolysis of automobile shredder residues (ASR).

PubMed

Zolezzi, Marcello; Nicolella, Cristiano; Ferrara, Sebastiano; Iacobucci, Cesare; Rovatti, Mauro

2004-01-01

This work aims at comparing performance and product yields in conventional pyrolysis and fast pyrolysis of automotive shredded residues. In both processes, carbon conversion to gaseous and liquid products was more than 80%. Gas production was maximised in conventional pyrolysis (about 35% by weight of the initial ASR weight), while fast pyrolysis led to an oil yield higher than 55%. Higher heating values (HHV) of both conventional pyrolysis gas and fast pyrolysis oil increased from 8.8 to 25.07 MJ/Nm3 and from 28.8 and 36.27 MJ/kg with increasing pyrolysis temperature. Copyright 2004 Elsevier Ltd.

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.

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.

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.

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.

Co-pyrolysis characteristics of microalgae Isochrysis and Chlorella: Kinetics, biocrude yield and interaction.

PubMed

Zhao, Bingwei; Wang, Xin; Yang, Xiaoyi

2015-12-01

Co-pyrolysis characteristics of Isochrysis (high lipid) and Chlorella (high protein) were investigated qualitatively and quantitatively based on DTG curves, biocrude yield and composition by individual pyrolysis and co-pyrolysis. DTG curves in co-pyrolysis have been compared accurately with those in individual pyrolysis. An interaction has been detected at 475-500°C in co-pyrolysis based on biocrude yields, and co-pyrolysis reaction mechanism appear three-dimensional diffusion in comparison with random nucleation followed by growth in individual pyrolysis based on kinetic analysis. There is no obvious difference in the maximum biocrude yields for individual pyrolysis and co-pyrolysis, but carboxylic acids (IC21) decreased and N-heterocyclic compounds (IC12) increased in co-pyrolysis. Simulation results of biocrude yield by Components Biofuel Model and Kinetics Biofuel Model indicate that the processes of co-pyrolysis comply with those of individual pyrolysis in solid phase by and large. Variation of percentage content in co-pyrolysis and individual pyrolysis biocrude indicated interaction in gas phase. Copyright © 2015. Published by Elsevier Ltd.

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.

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.

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.

Rapid analysis of the chemical composition of agricultural fibers using near infrared spectroscopy and pyrolysis molecular beam mass spectrometry

Treesearch

Stephen S. Kelley; Roger M. Rowell; Mark Davis; Cheryl K. Jurich; Rebecca Ibach

2004-01-01

The chemical composition of a variety of agricultural biomass samples was analyzed with near infrared spectroscopy and pyrolysis molecular beam mass spectroscopy. These samples were selected from a wide array of agricultural residue samples and included residues that had been subjected to a variety of di2erent treatments including solvent extractions and chemical...

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.

Rapid identification of bacteria with miniaturized pyrolysis/GC analysis

NASA Astrophysics Data System (ADS)

Morgan, Catherine H.; Mowry, Curtis; Manginell, Ronald P.; Frye-Mason, Gregory C.; Kottenstette, Richard J.; Lewis, Patrick

2001-02-01

Identification of bacteria and other biological moieties finds a broad range of applications in the environmental, biomedical, agricultural, industrial, and military arenas. Linking these applications are biological markers such as fatty acids, whose mass spectral profiles can be used to characterize biological samples and to distinguish bacteria at the gram-type, genera, and even species level. Common methods of sample analysis require sample preparation that is both lengthy and labor intensive, especially for whole cell bacteria. The background technique relied on here utilizes chemical derivatization of fatty acids to the more volatile fatty acid methyl esters (FAMEs), which can be separated on a gas chromatograph column or input directly into a mass spectrometer. More recent publications demonstrate improved sample preparation time with in situ derivatization of whole bacterial samples using pyrolysis at the inlet; although much faster than traditional techniques, these systems still rely on bench-top analytical equipment and individual sample preparation. Development of a miniaturized pyrolysis/GC instrument by this group is intended to realize the benefits of FAME identification of bacteria and other biological samples while further facilitating sample handling and instrument portability. The technologies being fabricated and tested have the potential of achieving pyrolysis and FAME separation on a very small scale, with rapid detection time (1-10 min from introduction to result), and with a modular sample inlet. Performance results and sensor characterization will be presented for the first phase of instrument development, encompassing the microfabricated pyrolysis and gas chromatograph elements.

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.

Reprint of: Pyrolysis technologies for municipal solid waste: A review

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

Chen, Dezhen, E-mail: chendezhen@tongji.edu.cn; Yin, Lijie; Wang, Huan

2015-03-15

Highlights: • MSW pyrolysis reactors, products and environmental impacts are reviewed. • MSW pyrolysis still has to deal with flue gas emissions and products’ contamination. • Definition of standardized products is suggested to formalize MSW pyrolysis technology. • Syngas is recommended to be the target product for single MSW pyrolysis technology. - Abstract: 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 inmore » 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, SO{sub 2} and NH{sub 3}, 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.« less

Pyrolysis technologies for municipal solid waste: A review

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

Chen, Dezhen, E-mail: chendezhen@tongji.edu.cn; Yin, Lijie; Wang, Huan

2014-12-15

Highlights: • MSW pyrolysis reactors, products and environmental impacts are reviewed. • MSW pyrolysis still has to deal with flue gas emissions and products’ contamination. • Definition of standardized products is suggested to formalize MSW pyrolysis technology. • Syngas is recommended to be the target product for single MSW pyrolysis technology. - Abstract: 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 inmore » 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, SO{sub 2} and NH{sub 3}, 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.« 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.

Oil shale derived pollutant control materials and methods and apparatuses for producing and utilizing the same

DOEpatents

Boardman, Richard D.; Carrington, Robert A.

2010-05-04

Pollution control substances may be formed from the combustion of oil shale, which may produce a kerogen-based pyrolysis gas and shale sorbent, each of which may be used to reduce, absorb, or adsorb pollutants in pollution producing combustion processes, pyrolysis processes, or other reaction processes. Pyrolysis gases produced during the combustion or gasification of oil shale may also be used as a combustion gas or may be processed or otherwise refined to produce synthetic gases and fuels.

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.

Pyrolysis Strategies for Effective Utilization of Lignocellulosic and Algal Biomass

NASA Astrophysics Data System (ADS)

Maddi, Balakrishna

Pyrolysis is a processing technique involving thermal degradation of biomass in the absence of oxygen. The bio-oils obtained following the condensation of the pyrolysis vapors form a convenient starting point for valorizing the major components of lignocellulosic as well as algal biomass feed stocks for the production of fuels and value-added chemicals. Pyrolysis can be implemented on whole biomass or on residues left behind following standard fractionation methods. Microalgae and oil seeds predominantly consist of protein, carbohydrate and triglycerides, whereas lignocellulose is composed of carbohydrates (cellulose and hemicellulose) and lignin. The differences in the major components of these two types of biomass will necessitate different pyrolysis strategies to derive the optimal benefits from the resulting bio-oils. In this thesis, novel pyrolysis strategies were developed that enable efficient utilization of the bio-oils (and/or their vapors) from lignocellulose, algae, as well as oil seed feed stocks. With lignocellulosic feed stocks, pyrolysis of whole biomass as well as the lignin residue left behind following well-established pretreatment and saccharification (i.e., depolymerization of cellulose and hemicellulose to their monomeric-sugars) of the biomass was studied with and without catalysts. Following this, pyrolysis of (lipid-deficient) algae and lignocellulosic feed stocks, under similar reactor conditions, was performed for comparison of product (bio-oil, gas and bio-char) yields and composition. In spite of major differences in component bio-polymers, feedstock properties relevant to thermo-chemical conversions, such as overall C, H and O-content, C/O and H/C molar ratio as well as calorific values, were found to be similar for algae and lignocellulosic material. Bio-oil yields from algae and some lignocellulosic materials were similar; however, algal bio-oils were compositionally different and contained several N-compounds (most likely from protein degradation). Algal bio-char also had a significantly higher N-content. Overall, our results suggest that it is feasible to convert algal cultures deficient in lipids, such as nuisance algae obtained from natural blooms, into liquid fuels by thermochemical methods. Next, pyrolysis characteristics of each of the major components present in lignocellulosic as well as algal biomass were studied independently in a thermo-gravimetric analyzer, using model compounds. From those studies, we have established that, with algae and oil seed feed stocks, triglycerides degrade at distinctly higher temperatures (T>350 C) compared to both protein and carbohydrate fractions (T ~ 250-350 C). Similar trend was not seen for lignocellulosic biomass, where degradation temperature interval of lignin overlapped with that of carbohydrates. This unique trend observed for algal biomass (and oil seeds) can be exploited in multiple ways. First, it permits to separately collect high value triglyceride degradation products not contaminated with N-compounds from protein and oxygenates from carbohydrates; this observation formed the basis of a novel "pyrolytic fractionation technique" developed in this thesis. Second, it led to the development of a new and simple analytical method for rapid estimation of the triglyceride content of oleaginous feed stocks. Pyrolytic fractionation is a two-step pyrolysis approach that can be implemented for oleaginous feed stocks (algae and oil-seeds) to separately recover triglyceride degradation products as a "high-quality" bio-oil fraction. The first step is a low-temperature pyrolysis (T ~ 300-320 C) to produce bio-oils from degradation of protein and carbohydrate fractions. Solid residues left behind can subsequently be subjected to a second higher temperature pyrolysis (T ~ 420-430 C) to volatilize and/or degrade triglycerides to produce fatty acids and their derivatives (such as mono-, di- and tri-glycerides) and long chain hydrocarbons. Proof-of-concept micro-pyrolyser (Pyroprobe) and lab-scale fixed-bed experiments were performed using oleaginous algae (Chlorella Sp.) to establish pyrolytic fractionation technique and also to determine the yields of triglyceride-specific bio-oils. As expected, triglyceride-specific bio-oils have hydrocarbons and free fatty acids that were nearly free of water, organic acids and carbohydrate degradation products. Another unique feature of the fractional pyrolysis method is that it allows upgrading of the triglyceride-specific bio-oil vapors via in situ gas-phase hydro-deoxygenation to drop-in fuels (hydrocarbons), without the need to condense the vapors. Similarly, these vapors can also be converted to other value-added products such as fatty acid methyl esters and amides though efficient catalytic and non-catalytic in situ gas-phase conversion methods. Energy requirements for this new pyrolytic fractionation method were also assessed, using energy estimates for the individual steps obtained via differential scanning calorimetry experiments. A comparison of these energy needs against those of alternative thermal processing methods of algae (hydro-thermal processing) proposed in the literature established the viability of this new method. Finally, a new TGA-based analytical method was developed in this thesis for rapid quantification of the triglyceride content of oleaginous feed stocks, by exploiting the non-overlapping thermal degradation range of triglycerides and the other major components.

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.

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.

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

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.

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.

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.

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.

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.

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

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.

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.

The Consequences of Surface Confinement on Free Radical Chemistry

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

Birtt, P.F.; Buchanan, A.C., III

1999-08-22

Mass transport limitations impact the thermochemical processing of fossil and renewable energy resources, which involves the breakdown of cross-linked, macromolecular networks. To Investigate the molecular level details of the consequences of molecular confinement on high temperature (275-500°C) free-radical reaction pathways, we have been examining the pyrolysis of model compounds attached to the surface of non-porous silica nanoparticles through a thermally robust Si-O-C aryl, tetha. Pyrolysis of silica-immobilized diphenylalkanes and related ethers have been studied in detail and compared with the corresponding behavior in fluid phases. The diffusional constraints can lead to reduced rates of radical termination on the surface, andmore » enhancement of neophyl-like rearrangements, cyclization-dehydrogenation pathways, and ipso- aromatic substitutions. Furthermore, studies of two-component surfaces have revealed the importance of a radical relay mechanism involving rapid serial hydrogen transfer steps resulting from the molecular pre-organization on the low fractal dimension silica surface. Key findings are reviewed in this paper, and the implications of these results for fuel processing are described.« less

Initiation reactions in acetylene pyrolysis

DOE PAGES

Zador, Judit; Fellows, Madison D.; Miller, James A.

2017-05-10

In gas-phase combustion systems the interest in acetylene stems largely from its role in molecular weight growth processes. The consensus is that above 1500 K acetylene pyrolysis starts mainly with the homolytic fission of the C–H bond creating an ethynyl radical and an H atom. However, below ~1500 K this reaction is too slow to initiate the chain reaction. It has been hypothesized that instead of dissociation, self-reaction initiates this process. Nevertheless, rigorous theoretical or direct experimental evidence is lacking, to an extent that even the molecular mechanism is debated in the literature. In this work we use rigorous abmore » initio transition-state theory master equation methods to calculate pressure- and temperature-dependent rate coefficients for the association of two acetylene molecules and related reactions. We establish the role of vinylidene, the high-energy isomer of acetylene in this process, compare our results with available experimental data, and assess the competition between the first-order and second-order initiation steps. As a result, we also show the effect of the rapid isomerization among the participating wells and highlight the need for time-scale analysis when phenomenological rate coefficients are compared to observed time scales in certain experiments.« less

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.

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.

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.

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.

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.

Method for the determination of lignin content of a sample by flash pyrolysis in an atmosphere of hydrogen or helium and method therefor

NASA Technical Reports Server (NTRS)

Shakkottai, Parthasarathy (Inventor); Kwack, Eug Y. (Inventor); Lawson, Daniel D. (Inventor)

1991-01-01

The lignin content of wood, paper pulp or other material containing lignin (such as filter paper soaked in black liquor) is more readily determined by flash pyrolysis of the sample at approximately 550.degree. C. in a reducing atmosphere of hydrogen or in an inert atmosphere of helium followed by a rapid analysis of the product gas by a mass spectrometer. The heated pyrolysis unit as fabricated comprises a small platinum cup welded to an electrically-heated stainless steel ribbon with control means for programmed short duration (1.5 sec, approximately) heating and means for continuous flow of hydrogen or helium. The pyrolysis products enter an electron-ionization mode mass spectrometer for spectral evaluation. Lignin content is obtained from certain ratios of integrated ion currents of many mass spectral lines, the ratios being linearly related to the Kappa number of Klason lignin.

Broadband Microwave Study of Reaction Intermediates and Products Through the Pyrolysis of Oxygenated Biofuels

NASA Astrophysics Data System (ADS)

Abeysekera, Chamara; Hernandez-Castillo, Alicia O.; Fritz, Sean; Zwier, Timothy S.

2017-06-01

The rapidly growing list of potential plant-derived biofuels creates a challenge for the scientific community to provide a molecular-scale understanding of their combustion. Development of accurate combustion models rests on a foundation of experimental data on the kinetics and product branching ratios of their individual reaction steps. Therefore, new spectroscopic tools are necessary to selectively detect and characterize fuel components and reactive intermediates generated by pyrolysis and combustion. Substituted furans, including furanic ethers, are considered second-generation biofuel candidates. Following the work of the Ellison group, an 8-18 GHz microwave study was carried out on the unimolecular and bimolecular decomposition of the smallest furanic ether, 2-methoxy furan, and it`s pyrolysis intermediate, the 2-furanyloxy radical, formed in a high-temperature pyrolysis source coupled to a supersonic expansion. Details of the experimental setup and analysis of the spectrum of the radical will be discussed.

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...

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.

Integrated coke, asphalt and jet fuel production process and apparatus

DOEpatents

Shang, Jer Y.

1991-01-01

A process and apparatus for the production of coke, asphalt and jet fuel m a feed of fossil fuels containing volatile carbon compounds therein is disclosed. The process includes the steps of pyrolyzing the feed in an entrained bed pyrolyzing means, separating the volatile pyrolysis products from the solid pyrolysis products removing at least one coke from the solid pyrolysis products, fractionating the volatile pyrolysis products to produce an overhead stream and a bottom stream which is useful as asphalt for road pavement, condensing the overhead stream to produce a condensed liquid fraction and a noncondensable, gaseous fraction, and removing water from the condensed liquid fraction to produce a jet fuel-containing product. The disclosed apparatus is useful for practicing the foregoing process. the process provides a useful method of mass producing and jet fuels from materials such as coal, oil shale and tar sands.

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.

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.

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.

A Comprehensive Study on Pyrolysis Mechanism of Substituted β-O-4 Type Lignin Dimers.

PubMed

Jiang, Xiaoyan; Lu, Qiang; Hu, Bin; Liu, Ji; Dong, Changqing; Yang, Yongping

2017-11-09

In order to understand the pyrolysis mechanism of β- O -4 type lignin dimers, a pyrolysis model is proposed which considers the effects of functional groups (hydroxyl, hydroxymethyl and methoxyl) on the alkyl side chain and aromatic ring. Furthermore, five specific β- O -4 type lignin dimer model compounds are selected to investigate their integrated pyrolysis mechanism by density functional theory (DFT) methods, to further understand and verify the proposed pyrolysis model. The results indicate that a total of 11 pyrolysis mechanisms, including both concerted mechanisms and homolytic mechanisms, might occur for the initial pyrolysis of the β- O -4 type lignin dimers. Concerted mechanisms are predominant as compared with homolytic mechanisms throughout unimolecular decomposition pathways. The competitiveness of the eleven pyrolysis mechanisms are revealed via different model compounds, and the proposed pyrolysis model is ranked in full consideration of functional groups effects. The proposed pyrolysis model can provide a theoretical basis to predict the reaction pathways and products during the pyrolysis process of β- O -4 type lignin dimers.

A Comprehensive Study on Pyrolysis Mechanism of Substituted β-O-4 Type Lignin Dimers

PubMed Central

Jiang, Xiaoyan; Lu, Qiang; Hu, Bin; Liu, Ji; Dong, Changqing; Yang, Yongping

2017-01-01

In order to understand the pyrolysis mechanism of β-O-4 type lignin dimers, a pyrolysis model is proposed which considers the effects of functional groups (hydroxyl, hydroxymethyl and methoxyl) on the alkyl side chain and aromatic ring. Furthermore, five specific β-O-4 type lignin dimer model compounds are selected to investigate their integrated pyrolysis mechanism by density functional theory (DFT) methods, to further understand and verify the proposed pyrolysis model. The results indicate that a total of 11 pyrolysis mechanisms, including both concerted mechanisms and homolytic mechanisms, might occur for the initial pyrolysis of the β-O-4 type lignin dimers. Concerted mechanisms are predominant as compared with homolytic mechanisms throughout unimolecular decomposition pathways. The competitiveness of the eleven pyrolysis mechanisms are revealed via different model compounds, and the proposed pyrolysis model is ranked in full consideration of functional groups effects. The proposed pyrolysis model can provide a theoretical basis to predict the reaction pathways and products during the pyrolysis process of β-O-4 type lignin dimers. PMID:29120350

High-throughput differentiation of heparin from other glycosaminoglycans by pyrolysis mass spectrometry.

PubMed

Nemes, Peter; Hoover, William J; Keire, David A

2013-08-06

Sensors with high chemical specificity and enhanced sample throughput are vital to screening food products and medical devices for chemical or biochemical contaminants that may pose a threat to public health. For example, the rapid detection of oversulfated chondroitin sulfate (OSCS) in heparin could prevent reoccurrence of heparin adulteration that caused hundreds of severe adverse events including deaths worldwide in 2007-2008. Here, rapid pyrolysis is integrated with direct analysis in real time (DART) mass spectrometry to rapidly screen major glycosaminoglycans, including heparin, chondroitin sulfate A, dermatan sulfate, and OSCS. The results demonstrate that, compared to traditional liquid chromatography-based analyses, pyrolysis mass spectrometry achieved at least 250-fold higher sample throughput and was compatible with samples volume-limited to about 300 nL. Pyrolysis yielded an abundance of fragment ions (e.g., 150 different m/z species), many of which were specific to the parent compound. Using multivariate and statistical data analysis models, these data enabled facile differentiation of the glycosaminoglycans with high throughput. After method development was completed, authentically contaminated samples obtained during the heparin crisis by the FDA were analyzed in a blinded manner for OSCS contamination. The lower limit of differentiation and detection were 0.1% (w/w) OSCS in heparin and 100 ng/μL (20 ng) OSCS in water, respectively. For quantitative purposes the linear dynamic range spanned approximately 3 orders of magnitude. Moreover, this chemical readout was successfully employed to find clues in the manufacturing history of the heparin samples that can be used for surveillance purposes. The presented technology and data analysis protocols are anticipated to be readily adaptable to other chemical and biochemical agents and volume-limited samples.

Producing Quantum Dots by Spray Pyrolysis

NASA Technical Reports Server (NTRS)

Banger, Kulbinder; Jin, Michael H.; Hepp, Aloysius

2006-01-01

An improved process for making nanocrystallites, commonly denoted quantum dots (QDs), is based on spray pyrolysis. Unlike the process used heretofore, the improved process is amenable to mass production of either passivated or non-passivated QDs, with computer control to ensure near uniformity of size.

Standard Rubbers for Chemical Defense Research. Volume 1. Formulation and Properties

DTIC Science & Technology

1989-01-01

by the military services. There is a growing need to determine the susceptibility of diese materials to the chemical threats anticipated from the...leading to a very weak signal which contains little spectral information. An alternative method involves very rapid pyrolysis of the rubber specimen to...After nitrogen gas purge of the pyrolysis cell, a small chunk of the rubber compound was heated at 600’C for 60 seconds by use of a Foxboro Pyro

Soil carbon content and character in an old-growth forest in northwestern Pennsylvania: a case study introducing pyrolysis molecular beam mass spectrometry (py-MBMS)

Treesearch

C.M. Hoover; K.A. Magrini; R.J. Evans

2002-01-01

This study was conducted to: (1) test the utility of a new and rapid analytical method, pyrolysis molecular beam mass spectrometry (py-MBMS), for the measurement and characterization of carbon in forest soils, and (2) examine the effects of natural disturbance on soil carbon dynamics. An additional objective was to test the ability of py-MBMS to distinguish recent from...

Impact of pyrolysis conditions on polycyclic aromatic hydrocarbons (PAHs) formation in particulate matter (PM) during sewage sludge pyrolysis.

PubMed

Ko, Jae Hac; Wang, Jingchen; Xu, Qiyong

2018-05-21

Polycyclic aromatic hydrocarbons (PAHs) not only present a risk to human health when released into the air, but also can be precursors to form particulate matter (PM) during sewage sludge pyrolysis. In this study, 16 EPA PAHs in PM (ΣPAH PM ) during sewage sludge pyrolysis were investigated with increasing temperature (200 o C-1000 °C) and holding time under different operation conditions [inert gas flow rate (IGFR) (200-800 mL/min) and heating rate (5-20 °C/min)]. ΣPAH PM varied with temperature, IGFR, and heating rate, and ranged from 597 (±41) μg/g to 3240 (±868) μg/g. ΣPAH PM decreased with increasing IGFR but increased with rapid heating rate. Among PAHs species in PM, naphthalene (Nap) was commonly detected at low temperature ranges in all tested conditions. Chrysene (CHR), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd] pyrene (IND), and benzo[g,h,i]perylene (BghiP) in PM became abundant at high temperature with a low IGFR. At high temperature ranges with high volatile conditions (rapid heating rate and low IGFR), PAH formation and growth reactions were considerable, resulting in the formation of heavy PAHs in PM. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hydrous pyrolysis/oxidation process for in situ destruction of chlorinated hydrocarbon and fuel hydrocarbon contaminants in water and soil

DOEpatents

Knauss, Kevin G.; Copenhaver, Sally C.; Aines, Roger D.

2000-01-01

In situ hydrous pyrolysis/oxidation process is useful for in situ degradation of hydrocarbon water and soil contaminants. Fuel hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, petroleum distillates and other organic contaminants present in the soil and water are degraded by the process involving hydrous pyrolysis/oxidation into non-toxic products of the degradation. The process uses heat which is distributed through soils and water, optionally combined with oxygen and/or hydrocarbon degradation catalysts, and is particularly useful for remediation of solvent, fuel or other industrially contaminated sites.

Natural rubber, a potential alternative source for the synthesis of renewable fuels via Hydrous Pyrolysis

NASA Astrophysics Data System (ADS)

Ahmad, N.; Dayana, S. A. S.; Abnisa, F.; Mohd, W. A. W. D.

2018-03-01

Natural rubber is a humid agricultural harvest, which mostly contains hydrocarbon cis-1, 4-Poly isoprene. Through depolymerisation technology, the natural rubber can be changed into liquid product, and then it can be subsequently utilized as a fuel or chemical feedstock. This article aims to provide an outlook on the natural rubber and its sources, which are available globally. Numerous depolymerisation processes, which include pyrolysis, gasification, chemical degradation, catalytic cracking and hydrogenation, were introduced in this paper, while the focus of discussion was emphasized on the hydrous pyrolysis process. Many studies have shown that the use of hydrous pyrolysis able to improve the depolymerisation process, e.g. the raw material can be feed without drying, the process can be carried out at lower temperature, only the water is used as the reaction medium, and it is easy to separate the water from oil product. The effect of operating parameters such as temperature, water to rubber mass ratio, reaction time and type of gases on the product yield and composition were reviewed in this paper. In addition, this paper also highlighted the eco-friendly and economic viability of the hydrous pyrolysis process.

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.

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.

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

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

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.

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

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.

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) "

Research and demonstration results for a new "Double-Solution" technology for municipal solid waste treatment.

PubMed

Erping, Li; Haoyun, Chen; Yanyang, Shang; Jun, Pan; Qing, Hu

2017-11-01

In this paper, the pyrolysis characteristics of six typical components in municipal solid waste (MSW) were investigated through a TG-FTIR combined technique and it was concluded that the main pyrolysis process of the biomass components (including food residues, sawdust and paper) occurred at 150-600°C. The main volatiles were multi-component gas including H 2 O, CO 2 , and CO. The main pyrolysis temperatures of three artificial products (PP, PVC and leather) was ranged from 200to 500°C. The wavelength of small molecule gases (CH 4 , CO 2 and CO) and the the chemical bonds (CO and CC) were observed in the infrared spectrum Based on the pyrolysis temperature interval and volatile constituent, a new "double-solution" process of pyrolysis and oxygen-enrichment decomposition MSW was designed. To achieve this process, a double-solution project was built for the direct treatment of MSW (10t/d). The complete setup of equipment and analysis of the byproducts has been reported in this paper to indicate the performance of this process. Energy balance and economic benefits were analysed for the process supporting. It was successfully demonstrated that the double-solution process was the environmentally friendly alternative method for MSW treatment in Chinese rural areas. Copyright © 2017 Elsevier Ltd. All rights reserved.

One-dimensional biomass fast pyrolysis model with reaction kinetics integrated in an Aspen Plus Biorefinery Process Model

DOE PAGES

Humbird, David; Trendewicz, Anna; Braun, Robert; ...

2017-01-12

A biomass fast pyrolysis reactor model with detailed reaction kinetics and one-dimensional fluid dynamics was implemented in an equation-oriented modeling environment (Aspen Custom Modeler). Portions of this work were detailed in previous publications; further modifications have been made here to improve stability and reduce execution time of the model to make it compatible for use in large process flowsheets. The detailed reactor model was integrated into a larger process simulation in Aspen Plus and was stable for different feedstocks over a range of reactor temperatures. Sample results are presented that indicate general agreement with experimental results, but with higher gasmore » losses caused by stripping of the bio-oil by the fluidizing gas in the simulated absorber/condenser. Lastly, this integrated modeling approach can be extended to other well-defined, predictive reactor models for fast pyrolysis, catalytic fast pyrolysis, as well as other processes.« less

Electrochemical Upgrading of Bio-Oil

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

Elangovan, S.; Larsen, Dennis; Bay, Insoo

Bio-oil produced by fast pyrolysis of biomass is a potential source of low carbon, renewable hydrocarbon fuel. However, the properties such as low heating value, incomplete volatility, acidity, instability, and incompatibility with standard fuels restrict its use. The undesirable properties of pyrolysis oil result from its chemical composition that mostly consists of different classes of oxygenated organic compounds. Current process of Hydrodeoxygenation to remove oxygen involves high-temperature, high-pressure processing in the presence of hydrogen and catalyst. An alternative process of deoxygenation of bio-oil using solid-state, oxygen conductor based electrochemical cell is under investigation. The electrolysis process removes oxygen from themore » oxygenated organic molecule as well from steam to produce hydrogen in-situ allowing for a distributed, small scale integrated upgrading unit. Mixtures of model compounds and a slip stream of pyrolysis vapor were tested. The results show the potential for integrating a pyrolyzer and an electrochemical device for stabilizing pyrolysis oil.« less

One-dimensional biomass fast pyrolysis model with reaction kinetics integrated in an Aspen Plus Biorefinery Process Model

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

Humbird, David; Trendewicz, Anna; Braun, Robert

A biomass fast pyrolysis reactor model with detailed reaction kinetics and one-dimensional fluid dynamics was implemented in an equation-oriented modeling environment (Aspen Custom Modeler). Portions of this work were detailed in previous publications; further modifications have been made here to improve stability and reduce execution time of the model to make it compatible for use in large process flowsheets. The detailed reactor model was integrated into a larger process simulation in Aspen Plus and was stable for different feedstocks over a range of reactor temperatures. Sample results are presented that indicate general agreement with experimental results, but with higher gasmore » losses caused by stripping of the bio-oil by the fluidizing gas in the simulated absorber/condenser. Lastly, this integrated modeling approach can be extended to other well-defined, predictive reactor models for fast pyrolysis, catalytic fast pyrolysis, as well as other processes.« less

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

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.

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

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.

Electrical Characteristics and Preparation of Nanostructured Pb(Zr0.5Ti0.5)O3 Films by Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Koo, Horng-Show; Chen, Mi; Hotta, Yoichi; Kawai, Tomoji

2007-07-01

Nanostructured thin films of Pb(Zr0.5Ti0.5)O3 on Pt (1000 Å)/Ti (100 Å)/SiO2 (2000 Å)/Si substrates are prepared by spray pyrolysis and subsequently rapid thermal annealing. Lead nitrate, zirconium nitrate and titanium isopropoxide are used as starting material with ethylene glycol as solvent. The crystal structure of the as-sprayed films are transformed from the amorphous, pyrochlore and multiple phases of pyrochlore and perovskite to the single phase of perovskite as the annealing temperature is increased up to 500 °C. For the formation of single phase perovskite, excess lead of 10 mol % is required to compensate the loss of lead during the processing of the primitive films. The physical characteristics of the resultant films show the dielectric constant (\\varepsilonr) of 400, remanent polarization (2Pr) of 30.0 μC/cm2 and coercive field (2Ec) of 70.0 kV/cm, respectively.

Low-temperature co-pyrolysis behaviours and kinetics of oily sludge: effect of agricultural biomass.

PubMed

Zhou, Xiehong; Jia, Hanzhong; Qu, Chengtun; Fan, Daidi; Wang, Chuanyi

2017-02-01

Pyrolysis is potentially an effective treatment of oily sludge for oil recovery, and its kinetics and efficiency are expected to be affected by additives. In the present study, the pyrolysis parameters, including heating rate, final pyrolysis temperature, and pyrolysis time of oily sludge in the presence of agricultural biomass, apricot shell, were systematically explored. As a result, maximum oil recovery is achieved when optimizing the pyrolysis conditionas15 K/min, 723 K, and 3 h for heating rate, final pyrolysis temperature, and pyrolysis time, respectively. Thermogravimetric experiments of oily sludge samples in the presence of various biomasses conducted with non-isothermal temperature programmes suggest that the pyrolysis process contains three stages, and the main decomposition reaction occurs in the range of 400-740 K. Taking Flynn-Wall-Ozawa analysis of the derivative thermogravimetry and thermogravimetry results, the activation energy (E a ) values for the pyrolysis of oily sludge in the presence and absence of apricot shell were derived to be 35.21 and 39.40 kJ mol -1 , respectively. The present work supports that the presence of biomass promotes the pyrolysis of oily sludge, implying its great potential as addictive in the industrial pyrolysis of oily sludge.

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.

Analysis of the combustion and pyrolysis of dried sewage sludge by TGA and MS.

PubMed

Magdziarz, Aneta; Werle, Sebastian

2014-01-01

In this study, the combustion and pyrolysis processes of three sewage sludge were investigated. The sewage sludge came from three wastewater treatment plants. Proximate and ultimate analyses were performed. The thermal behaviour of studied sewage sludge was investigated by thermogravimetric analysis with mass spectrometry (TGA-MS). The samples were heated from ambient temperature to 800 °C at a constant rate 10 °C/min in air (combustion process) and argon flows (pyrolysis process). The thermal profiles presented in form of TG/DTG curves were comparable for studied sludges. All TG/DTG curves were divided into three stages. The main decomposition of sewage sludge during the combustion process took place in the range 180-580 °C with c.a. 70% mass loss. The pyrolysis process occurred in lower temperature but with less mass loss. The evolved gaseous products (H2, CH4, CO2, H2O) from the decomposition of sewage sludge were identified on-line. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

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.

Experimental toxicology of pyrolysis and combustion hazards.

PubMed Central

Cornish, H H; Hahn, K J; Barth, M L

1975-01-01

Data are presented on the acute toxicity (mortality only) of the thermal degradation products of polymers obtained by two methods of degradation. One system utilized a slowly increasing temperature (5 degrees C/min) and gradual degradation of the polymer with the rats being exposed to degradation products as they were evolved. In this system the more toxic polymers included wool, polypropylene, poly(vinyl chloride), and urethane foam. The second system utilized conditions of rapid combustion and exposure of rats to the total products of combustion for a period of 4 hr. In this system the more toxic materials included red oak, cotton, acrylonitrile-butadiene-styrene (ABS), and styrene-acrylonitrile. It is of interest to note that the natural product wool is among the least toxic under these rapid combustion conditions and among the most toxic under slow pyrolysis conditions. Other materials also vary in the comparative toxicity of their thermal degradation products, depending upon the conditions of degradation and animal exposure. The two experimental techniques presented here may well represent the two extreme conditions of rapid combustion versus slow pyrolysis. Intermediate types of fire situations might be expected to result in relative acute toxicities somewhere between these two extremes. This report deals with acute toxicity on the basis of mortality data only and does not include other parameters of toxicity such as organ weights and histopathology. PMID:1175552

Numerical simulation of vortex pyrolysis reactors for condensable tar production from biomass

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

Miller, R.S.; Bellan, J.

1998-08-01

A numerical study is performed in order to evaluate the performance and optimal operating conditions of vortex pyrolysis reactors used for condensable tar production from biomass. A detailed mathematical model of porous biomass particle pyrolysis is coupled with a compressible Reynolds stress transport model for the turbulent reactor swirling flow. An initial evaluation of particle dimensionality effects is made through comparisons of single- (1D) and multi-dimensional particle simulations and reveals that the 1D particle model results in conservative estimates for total pyrolysis conversion times and tar collection. The observed deviations are due predominantly to geometry effects while directional effects frommore » thermal conductivity and permeability variations are relatively small. Rapid ablative particle heating rates are attributed to a mechanical fragmentation of the biomass particles that is modeled using a critical porosity for matrix breakup. Optimal thermal conditions for tar production are observed for 900 K. Effects of biomass identity, particle size distribution, and reactor geometry and scale are discussed.« less

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.

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...

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.

Process for preparing phenolic formaldehyde resole resin products derived from fractionated fast-pyrolysis oils

DOEpatents

Chum, Helena L.; Kreibich, Roland E.

1992-01-01

A process for preparing phenol-formaldehyde resole resins and adhesive compositions in which portions of the phenol normally contained in said resins are replaced by a phenol/neutral fractions extract obtained from fractionating fast-pyrolysis oils.

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

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.

Optimization of the pyrolysis process of empty fruit bunch (EFB) in a fixed-bed reactor through a central composite design (CCD)

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

Mohamed, Alina Rahayu; Hamzah, Zainab; Daud, Mohamed Zulkali Mohamed

2014-07-10

The production of crude palm oil from the processing of palm fresh fruit bunches in the palm oil mills in Malaysia hs resulted in a huge quantity of empty fruit bunch (EFB) accumulated. The EFB was used as a feedstock in the pyrolysis process using a fixed-bed reactor in the present study. The optimization of process parameters such as pyrolysis temperature (factor A), biomass particle size (factor B) and holding time (factor C) were investigated through Central Composite Design (CCD) using Stat-Ease Design Expert software version 7 with bio-oil yield considered as the response. Twenty experimental runs were conducted. Themore » results were completely analyzed by Analysis of Variance (ANOVA). The model was statistically significant. All factors studied were significant with p-values < 0.05. The pyrolysis temperature (factor A) was considered as the most significant parameter because its F-value of 116.29 was the highest. The value of R{sup 2} was 0.9564 which indicated that the selected factors and its levels showed high correlation to the production of bio-oil from EFB pyrolysis process. A quadratic model equation was developed and employed to predict the highest theoretical bio-oil yield. The maximum bio-oil yield of 46.2 % was achieved at pyrolysis temperature of 442.15 °C using the EFB particle size of 866 μm which corresponded to the EFB particle size in the range of 710–1000 μm and holding time of 483 seconds.« less

Optimization of the pyrolysis process of empty fruit bunch (EFB) in a fixed-bed reactor through a central composite design (CCD)

NASA Astrophysics Data System (ADS)

Mohamed, Alina Rahayu; Hamzah, Zainab; Daud, Mohamed Zulkali Mohamed

2014-07-01

The production of crude palm oil from the processing of palm fresh fruit bunches in the palm oil mills in Malaysia hs resulted in a huge quantity of empty fruit bunch (EFB) accumulated. The EFB was used as a feedstock in the pyrolysis process using a fixed-bed reactor in the present study. The optimization of process parameters such as pyrolysis temperature (factor A), biomass particle size (factor B) and holding time (factor C) were investigated through Central Composite Design (CCD) using Stat-Ease Design Expert software version 7 with bio-oil yield considered as the response. Twenty experimental runs were conducted. The results were completely analyzed by Analysis of Variance (ANOVA). The model was statistically significant. All factors studied were significant with p-values < 0.05. The pyrolysis temperature (factor A) was considered as the most significant parameter because its F-value of 116.29 was the highest. The value of R2 was 0.9564 which indicated that the selected factors and its levels showed high correlation to the production of bio-oil from EFB pyrolysis process. A quadratic model equation was developed and employed to predict the highest theoretical bio-oil yield. The maximum bio-oil yield of 46.2 % was achieved at pyrolysis temperature of 442.15 °C using the EFB particle size of 866 μm which corresponded to the EFB particle size in the range of 710-1000 μm and holding time of 483 seconds.

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.

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.

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.

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.

Electrochemical and/or microbiological treatment of pyrolysis wastewater.

PubMed

Silva, José R O; Santos, Dara S; Santos, Ubiratan R; Eguiluz, Katlin I B; Salazar-Banda, Giancarlo R; Schneider, Jaderson K; Krause, Laiza C; López, Jorge A; Hernández-Macedo, Maria L

2017-10-01

Electrochemical oxidation may be used as treatment to decompose partially or completely organic pollutants (wastewater) from industrial processes such as pyrolysis. Pyrolysis is a thermochemical process used to obtain bio-oil from biomasses, generating a liquid waste rich in organic compounds including aldehydes and phenols, which can be submitted to biological and electrochemical treatments in order to minimize its environmental impact. Thus, electrochemical systems employing dimensionally stable anodes (DSAs) have been proposed to enable biodegradation processes in subsurface environments. In order to investigate the organic compound degradation from residual coconut pyrolysis wastewater, ternary DSAs containing ruthenium, iridium and cerium synthetized by the 'ionic liquid method' at different calcination temperatures (500, 550, 600 and 700 °C) for the pretreatment of these compounds, were developed in order to allow posterior degradation by Pseudomonas sp., Bacillus sp. or Acinetobacter sp. bacteria. The electrode synthesized applying 500 °C displayed the highest voltammetric charge and was used in the pretreatment of pyrolysis effluent prior to microbial treatment. Regarding biological treatment, the Pseudomonas sp. exhibited high furfural degradation in wastewater samples electrochemically pretreated at 2.0 V. On the other hand, the use of Acinetobacter efficiently degraded phenolic compounds such as phenol, 4-methylphenol, 2,5-methylphenol, 4-ethylphenol and 3,5-methylphenol in both wastewater samples, with and without electrochemical pretreatment. Overall, the results indicate that the combination of both processes used in this study is relevant for the treatment of pyrolysis wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Determination of the energy potential of gases produced in the pyrolysis processes of the vegetal carbon manufacture industry.

PubMed

Gañan, J; González, J F; González-García, C M; Cuerda-Correa, E M; Macías-García, A

2006-03-01

In this work, a pyrolysis plant located in Valverde de Leganes, Badajoz (SW Spain) was studied. At present, only the solid phase obtained by pyrolysis finds an application as domestic fuel. In order to analyze the feasibility of a further energetic exploitation of the plant under study, the gases flowing through the chimneys were collected at different times throughout the pyrolysis process. Next, they were characterized and quantified by gas chromatography, the energy potential of each of the gases being determined. According to the results obtained in this study, a total energy potential of 5.6 x 10(7) MJ (i.e., 1.78 MW(t)) might be generated yearly. Hence, considering an overall process yield equal to 20%, up to 358 KW(e) would be produced. This power would supply enough electric energy to the industry, the remaining being added to the common electric network.

Hydrogen production from switchgrass via a hybrid pyrolysis-microbial electrolysis process

DOE PAGES

Lewis, Alex J.; Ren, Shoujie; Ye, Philip; ...

2015-06-30

A new approach to hydrogen production using a hybrid pyrolysis-microbial electrolysis process is described. The aqueous stream generated during pyrolysis of switchgrass was used as a substrate for hydrogen production in a microbial electrolysis cell, achieving a maximum hydrogen production rate of 4.3 L H2/L-day at a loading of 10 g COD/L-anode-day. Hydrogen yields ranged from 50 3.2% to76 0.5% while anode coulombic efficiency ranged from 54 6.5% to 96 0.21%, respectively. Significant conversion of furfural, organic acids and phenolic molecules was observed under both batch and continuous conditions. The electrical and overall energy efficiency ranged from 149-175% and 48-63%,more » respectively. The results demonstrate the potential of the pyrolysis-microbial electrolysis process as a sustainable and efficient route for production of renewable hydrogen with significant implications for hydrocarbon production from biomass.« less

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

PubMed

Fan, Liangliang; Zhang, Yaning; Liu, Shiyu; Zhou, Nan; Chen, Paul; Cheng, Yanling; Addy, Min; Lu, Qian; Omar, Muhammad Mubashar; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Anderson, Erik; Peng, Peng; Lei, Hanwu; Ruan, Roger

2017-10-01

Effects of process parameters on the yield and chemical profile of bio-oil from fast pyrolysis of lignin and the processes for lignin-derived bio-oil upgrading were reviewed. Various process parameters including pyrolysis temperature, reactor types, lignin characteristics, residence time, and feeding rate were discussed and the optimal parameter conditions for improved bio-oil yield and quality were concluded. In terms of lignin-derived bio-oil upgrading, three routes including pretreatment of lignin, catalytic upgrading, and co-pyrolysis of hydrogen-rich materials have been investigated. Zeolite cracking and hydrodeoxygenation (HDO) treatment are two main methods for catalytic upgrading of lignin-derived bio-oil. Factors affecting zeolite activity and the main zeolite catalytic mechanisms for lignin conversion were analyzed. Noble metal-based catalysts and metal sulfide catalysts are normally used as the HDO catalysts and the conversion mechanisms associated with a series of reactions have been proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Should biochar be used in container substrates?

USDA-ARS?s Scientific Manuscript database

Biochar is charred organic matter that remains after a process called pyrolysis. Pyrolysis is a thermochemical decomposition of organic matter. In this process, organic matter is subjected to extremely high temperatures (200 to 800 °C) in the absence of oxygen. The history of biochar use begins i...

Process Analysis of Lignite Circulating Fluidized Bed Boiler Coupled with Pyrolysis Topping

NASA Astrophysics Data System (ADS)

Wang, Baoqun; Dong, Li; Wang, Yin; Matsuzawa, Y.; Xu, Guangwen

We developed a comprehensive process model in ASPEN Plus to simulate the energy and mass balances of a lignite-fueled atmospheric circulating fluidized bed (CFB) boiler integrated with coal predrying and pyrolysis topping. In this model, it is assumed that the heat from exhausted flue gas was employed for coal predrying, and the sensible heat derived from circulated bed material was used for the pyrolysis topping (endothermic process). The simulation was conducted with respectto the Yunnan Kaiyuan CFB boiler, and two representative lignite coals from Xiao Long Tan (XLT) and Xin Shao (XS) were considered. The result shows that the predrying of coal with the sensible heat of above 363 K from flue gas, the amount of coal consumed in the boiler can be reduced by 3.5% and 5.3% for XLT lignite and XS lignite, respectively. It was also found that integration of pyrolysis topping with the boiler increased the coal consumption of the boiler, and the extent of consumption-increase varies with the yields of tar and gas in the pyrolysis topping process. For agas yield of 5.2% and a tar yield of 5-6%, the consumption of XS lignite increased by about 20% comparing to that in the case without topping.

East Europe Report, Economic and Industrial Affairs, No. 2448.

DTIC Science & Technology

1983-09-14

investment was postponed); equipment for the food processing industry—refrigerators, production lines for soups, tomato puree and the like; mining equipment...processes based primarily on components derived from pyrolysis and reformation fractions which currently are still not used on a wide scale. 11,023...chemical processes, coking and pyrolysis furnace gases, combustible wastes from raw and other materials, physical heat from processes, heat from

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.

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.

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

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.

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.

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.

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.

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

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...

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

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.

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.

Hydrothermal carbonization of biomass residuals: A comparative review of the chemistry, processes and applications of wet and dry pyrolysis

USDA-ARS?s Scientific Manuscript database

This paper reviews chemistry, processes and application of hydrothermcally carbonized biomass wastes. Potential feedstock for the hydrothermal carbonization (HTC) includes variety of the non-traditional renewable wet agricultural and municipal waste streams. Pyrolysis and HTC show a comparable calor...

Processing And Patterning Of Thin Film Superconductors Formed By Metallo-Organic Deposition

NASA Astrophysics Data System (ADS)

Micheli, Adolph L.; Mantese, Joseph V.; Hamdi, Aboud H.

1990-04-01

Thin film superconductors of Y-Ba-Cu and Yb-Ba-Cu were formed by the pyrolysis of neodecanoate solutions of Y, Yb, Ba and Cu which had been deposited onto <100> SrTiO3 substrates [1]. Rapid thermal annealing, in oxygen, of the as-deposited films produced high T films having superconducting onset temperatures above 90 K and zero resistance at 8g K. Scanning Electron Microscopy (SEM) revealed enhancements in grain growth, compared to furnace annealed films, by a factor of 4. X-ray diffraction analysis showed preferred epitaxial grain growth with the c-axis of the films oriented both perpendicular and parallel to the substrate surface. Separate Rutherford Backscattering Spectrometry (RBS) channeling experiments confirmed the formation of preferred epitaxial grain growth. Film composition was determined by RBS and Inductively Coupled Plasma Emission Spectrometry (ICPES). Selective patterning was accomplished by focused beam exposure of the metal neodecanoate films [2-4]. The exposure rendered the neodecanoate film locally insoluble in xylene, thus permitting selective area patterning prior to pyrolysis. Electron, ion and laser beams were used to pattern films on <100> SrTiO3. The finest lines, approximately 5 #m in width and 26 nm thick, were patterned using electron beams whose lines had superconducting onsets above 90 K and zero resistance at 69 K after rapid thermal annealing. Both ion beam and laser patterning had similar superconducting onsets and zero resistance. Neodecanoates of Y, Yb, Ba, and Cu were formed, as previously described [5], by reacting the metal acetates of these materials with either ammonium neodecanoate or tetramethyl ammonium neodecanoate. The carboxylates formed from these reactions were then dissolved in a solution of xylene and pyridine. The individual chemical constituents were combined to produce solutions, Ln:Ba:Cu, in the ratio 1:2:4. Here, Ln is a rare-earth element. Details of the preparation of the metal carboxylates may be found elsewhere [6]. Thin films of Y-Ba-Cu and Yb-Ba-Cu were deposited onto <100> SrTiO by flooding the substrates with the appropriate neodecanoate solutions, then spin drying them at 2000 rpm for 30 s. The substrates were heated rapidly to 500?°C for 5 min in an air oven to pyrolize the metallo organics to their oxides. This process produces thin films about 200 nm thick. The spin coating process was repeated 3-6 times if thicker films were desired. X-ray diffraction analysis of films pyrolized at 500?°C shoed the presence of only microcrystallites. Room temperature resistivities of lx10 0-cm were measured for these films. No superconducting behavior was observed. After the 500?°C pyrolysis the films were further processed by RTA in flowing oxygen. The substrates were placed upon oxidized silicon wafers, rapidly heated to 850?°C for 60 s using infrared radiation produced by a bank of quartz lamps then allowed to cool to room temperature. A second rapid annealing was then performed at 920?°C for 30 s in oxygen. Thin film superconductors formed in the manner described above were very uniform in structure and thickness across the surface of the film. The grains are approximately 1 #m wide and 2 #m long, a factor of 4 larger than the grains found in furnace annealed films formed by MOD [5].

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.

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.

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.

Pyrolysis process for the treatment of scrap tyres: preliminary experimental results.

PubMed

Galvagno, S; Casu, S; Casabianca, T; Calabrese, A; Cornacchia, G

2002-01-01

The aim of this work is the evaluation, on a pilot scale, of scrap tyre pyrolysis process performance and the characteristics of the products under different process parameters, such as temperature, residence time, pressure, etc. In this frame, a series of tests were carried out at varying process temperatures between 550 and 680 degrees C, other parameters being equal. Pyrolysis plant process data are collected by an acquisition system; scrap tyre samples used for the treatment, solid and liquid by-products and produced syngas were analysed through both on-line monitoring (for gas) and laboratory analyses. Results show that process temperature, in the explored range, does not seem to seriously influence the volatilisation reaction yield, at least from a quantitative point of view, while it observably influences the distribution of the volatile fraction (liquid and gas) and by-products characteristics.

Intelligent Processing of Ferroelectric Thin Films

DTIC Science & Technology

1993-09-03

the acetate precursors. The results from these experiments involving coprecipitation, hydrothermal , spray pyrolysis and freeze drying have shown that...Spray Pyrolysis (SP) D. Hydrothermal Processing (HP) The powder produced by each process was characterized by X-ray diffraction (XRD) and scanning...precursors were used as described above. Instead of ammonia solution, an oxalic acid solution was used as the3 precipitating agent. The precipitants

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.

A comparative study of nitrogen conversion during pyrolysis of coconut fiber, its corresponding biochar and their blends with lignite.

PubMed

Liu, Zhengang; Balasubramanian, Rajasekhar

2014-01-01

In the present study, the conversion of fuel-N to HCN and NH3 was investigated during rapid pyrolysis of raw biomass (coconut fiber), its corresponding biochar and their blends with lignite within a temperature range of 600-900°C. The results showed that the raw biomass and the biochar showed totally different nitrogen partitioning between NH3 and HCN. HCN was the dominant nitrogen pollutant from pyrolysis of raw biomass, while for the biochar pyrolysis the yield of NH3 was slightly higher than that of HCN. Synergistic interactions occurred within both raw biomass/lignite and biochar/lignite blends, especially for the biochar/lignite blend, and resulted in reduced yields of HCN and NH3, decreased the total nitrogen percentage retained in the char and promoted harmless N2 formation. These findings suggest that biochar/lignite co-firing for energy production may have the enhanced benefit of reduced emissions of nitrogen pollutants than raw biomass/lignite. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

Frederick G. Baddour | NREL

Science.gov Websites

hydrodeoxygenation of guaiacol under ex situ catalytic fast pyrolysis conditions," Top. Catal. (2015) " ;Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A

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.

Coal Producer's Rubber Waste Processing Development

NASA Astrophysics Data System (ADS)

Makarevich, Evgeniya; Papin, Andrey; Nevedrov, Alexander; Cherkasova, Tatyana; Ignatova, Alla

2017-11-01

A large amount of rubber-containing waste, the bulk of which are worn automobile tires and conveyor belts, is produced at coal mining and coal processing enterprises using automobile tires, conveyor belts, etc. The volume of waste generated increases every year and reaches enormous proportions. The methods for processing rubber waste can be divided into three categories: grinding, pyrolysis (high and low temperature), and decomposition by means of chemical solvents. One of the known techniques of processing the worn-out tires is their regeneration, aimed at producing the new rubber substitute used in the production of rubber goods. However, the number of worn tires used for the production of regenerate does not exceed 20% of their total quantity. The new method for processing rubber waste through the pyrolysis process is considered in this article. Experimental data on the upgrading of the carbon residue of pyrolysis by the methods of heavy media separation, magnetic and vibroseparation, and thermal processing are presented.

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,

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

Upgrading of Intermediate Bio-Oil Produced by Catalytic Pyrolysis

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

Abdullah, Zia; Chadwell, Brad; Taha, Rachid

2015-06-30

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

Detoxification of corn stover and corn starch pyrolysis liquors by Pseudomonas putida and Streptomyces setonii suspended cells and plastic compost support biofilms.

PubMed

Khiyami, Mohammad A; Pometto Iii, Anthony L; Brown, Robert C

2005-04-20

Plant biomass can be liquefied into fermentable sugars (levoglucosan then to glucose) for the production of ethanol, lactic acid, enzymes, and more by a process called pyrolysis. During the process microbial inhibitors are also generated. Pseudomonas putida (ATCC 17484) and Streptomyces setonii75Vi2 (ATCC 39116) were employed to degrade microbial inhibitors in diluted corn stover (Dcs) and diluted corn starch (Dst) pyrolysis liquors. The detoxification process evaluation included measuring total phenols and changes in UV spectra, a GC-MS analysis, and a bioassay, which employed Lactobacillus casei subsp. rhamosus (ATCC 11443) growth as an indicator of detoxification. Suspended-cell cultures illustrated limited detoxification ability of Dcs and Dst. P. putida and S. setoniiplastic compost support (PCS) biofilm continuous-stirred-tank-reactor pure cultures detoxified 10 and 25% (v/v) Dcs and Dst, whereas PCS biofilm mixed culture also partially detoxified 50% (v/v) Dcs and Dst in repeated batch culture. Therefore, PCS biofilm mixed culture is the process of choice to detoxify diluted pyrolysis liquors.

Hydrogen production from switchgrass via an integrated pyrolysis-microbial electrolysis process.

PubMed

Lewis, A J; Ren, S; Ye, X; Kim, P; Labbe, N; Borole, A P

2015-11-01

A new approach to hydrogen production using an integrated pyrolysis-microbial electrolysis process is described. The aqueous stream generated during pyrolysis of switchgrass was used as a substrate for hydrogen production in a microbial electrolysis cell, achieving a maximum hydrogen production rate of 4.3 L H2/L anode-day at a loading of 10 g COD/L-anode-day. Hydrogen yields ranged from 50±3.2% to 76±0.5% while anode Coulombic efficiency ranged from 54±6.5% to 96±0.21%, respectively. Significant conversion of furfural, organic acids and phenolic molecules was observed under both batch and continuous conditions. The electrical and overall energy efficiency ranged from 149-175% and 48-63%, respectively. The results demonstrate the potential of the pyrolysis-microbial electrolysis process as a sustainable and efficient route for production of renewable hydrogen with significant implications for hydrocarbon production from biomass. Copyright © 2015 Elsevier Ltd. All rights reserved.

Two-step gasification of cattle manure for hydrogen-rich gas production: Effect of biochar preparation temperature and gasification temperature.

PubMed

Xin, Ya; Cao, Hongliang; Yuan, Qiaoxia; Wang, Dianlong

2017-10-01

Two-step gasification process was proposed to dispose cattle manure for hydrogen rich gas production. The effect of temperature on product distribution and biochar properties were first studied in the pyrolysis-carbonization process. The steam gasification of biochar derived from different pyrolysis-carbonization temperatures was then performed at 750°C and 850°C. The biochar from the pyrolysis-carbonization temperatures of 500°C had high carbon content and low volatiles content. According to the results of gasification stage, the pyrolysis-carbonization temperature of 500°C and the gasification temperature of 850°C were identified as the suitable conditions for hydrogen production. We obtained 1.61m 3 /kg of syngas production, 0.93m 3 /kg of hydrogen yield and 57.58% of hydrogen concentration. This study shows that two-step gasification is an efficient waste-to-hydrogen energy process. Copyright © 2017 Elsevier Ltd. All rights reserved.

JP-8 and Other Military Fuels

DTIC Science & Technology

2011-12-01

Fermentation Jet Fuel-Like Product sugarcane Alcohol Oligomerization Conventional Refinery ProcessesSugar switchgrass Dehydration Pyrolysis Fermentation...PolymerizationOlefins Lignocellulose corn stover forest waste Jet Fuel-Like ProductBio-CrudePyrolysis Hydroprocessing Unclassified Back Up Slides

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

Research on pyrolysis behavior of Camellia sinensis branches via the Discrete Distributed Activation Energy Model.

PubMed

Zhou, Bingliang; Zhou, Jianbin; Zhang, Qisheng

2017-10-01

This study aims at investigating the pyrolysis behavior of Camellia sinensis branches by the Discrete Distributed Activation Energy Model (DAEM) and thermogravimetric experiments. Then the Discrete DAEM method is used to describe pyrolysis process of Camellia sinensis branches dominated by 12 characterized reactions. The decomposition mechanism of Camellia sinensis branches and interaction with components are observed. And the reaction at 350.77°C is a significant boundary of the first and second reaction range. The pyrolysis process of Camellia sinensis branches at the heating rate of 10,000°C/min is predicted and provides valuable references for gasification or combustion. The relationship and function between four typical indexes and heating rates from 10 to 10,000°C/min are revealed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Process for oil shale retorting

DOEpatents

Jones, John B.; Kunchal, S. Kumar

1981-10-27

Particulate oil shale is subjected to a pyrolysis with a hot, non-oxygenous gas in a pyrolysis vessel, with the products of the pyrolysis of the shale contained kerogen being withdrawn as an entrained mist of shale oil droplets in a gas for a separation of the liquid from the gas. Hot retorted shale withdrawn from the pyrolysis vessel is treated in a separate container with an oxygenous gas so as to provide combustion of residual carbon retained on the shale, producing a high temperature gas for the production of some steam and for heating the non-oxygenous gas used in the oil shale retorting process in the first vessel. The net energy recovery includes essentially complete recovery of the organic hydrocarbon material in the oil shale as a liquid shale oil, a high BTU gas, and high temperature steam.

Examination and evaluation of the use of screen heaters for the measurement of the high temperature pyrolysis kinetics of polyethene and polypropene

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

Westerhout, R.W.J.; Balk, R.H.P.; Meijer, R.

1997-08-01

A screen heater with a gas sweep was developed and applied to study the pyrolysis kinetics of low density polyethene (LDPE) and polypropene (PP) at temperatures ranging from 450 to 530 C. The aim of this study was to examine the applicability of screen heaters to measure these kinetics. On-line measurement of the rate of volatiles formation using a hydrocarbon analyzer was applied to enable the determination of the conversion rate over the entire conversion range on the basis of a single experiment. Another important feature of the screen heater used in this study is the possibility to measure pyrolysismore » kinetics under nearly isothermal conditions. The kinetic constants for LDPE and PP pyrolysis were determined, using a first order model to describe the conversion rate in the 70--90% conversion range and the random chain dissociation model for the entire conversion range. In addition to the experimental work two single particle models have been developed which both incorporate a mass and a (coupled) enthalpy balance, which were used to assess the influence of internal and external heat transfer processes on the pyrolysis process. The first model assumes a variable density and constant volume during the pyrolysis process, whereas the second model assumes a constant density and a variable volume. An important feature of these models is that they can accommodate kinetic models for which no analytical representation of the pyrolysis kinetics is available.« less

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.

Methane Pyrolysis and Disposing Off Resulting Carbon

NASA Technical Reports Server (NTRS)

Sharma, P. K.; Rapp, D.; Rahotgi, N. K.

1999-01-01

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is wasteful of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduced the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (1) recover hydrogen from the excess methane produced by the S/E process, (2) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (3) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. Hydrogen may be obtained from methane by pyrolysis in the temperature range 10000-12000C. The main reaction products are hydrogen and carbon, though very small amounts of higher hydrocarbons, including aromatic hydrocarbons are formed. The conversion efficiency is about 95% at 12000C. One needs to distinguish between thermodynamic equilibrium conversion and conversion limited by kinetics in a finite reactor.

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.

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.

Producing Hydrogen by Plasma Pyrolysis of Methane

NASA Technical Reports Server (NTRS)

Atwater, James; Akse, James; Wheeler, Richard

2010-01-01

Plasma pyrolysis of methane has been investigated for utility as a process for producing hydrogen. This process was conceived as a means of recovering hydrogen from methane produced as a byproduct of operation of a life-support system aboard a spacecraft. On Earth, this process, when fully developed, could be a means of producing hydrogen (for use as a fuel) from methane in natural gas. The most closely related prior competing process - catalytic pyrolysis of methane - has several disadvantages: a) The reactor used in the process is highly susceptible to fouling and deactivation of the catalyst by carbon deposits, necessitating frequent regeneration or replacement of the catalyst. b) The reactor is highly susceptible to plugging by deposition of carbon within fixed beds, with consequent channeling of flow, high pressure drops, and severe limitations on mass transfer, all contributing to reductions in reactor efficiency. c) Reaction rates are intrinsically low. d) The energy demand of the process is high.

Effect of heating rate on toxicity of pyrolysis gases from some synthetic polymers

NASA Technical Reports Server (NTRS)

Hilado, C. J.; Soriano, J. A.; Kosola, K. L.

1977-01-01

The effect of heating rate on the toxicity of the pyrolysis gases from some synthetic polymers was investigate, using a screening test method. The synthetic polymers were polyethylene, polystyrene, polymethyl methacrylate, polycarbonate, ABS, polyaryl sulfone, polyether sulfone, and polyphenylene sulfide. The toxicants from the sulfur-containing polymers appeared to act more rapidly than the toxicants from the other polymers. It is not known whether this effect is due primarily to differences in concentration or in the nature of the toxicants. The carbon monoxide concentrations found do not account for the observed results.

Large-scale synthesis of high-purity well-aligned carbon nanotubes using pyrolysis of iron(II) phthalocyanine and acetylene

NASA Astrophysics Data System (ADS)

Liu, B. C.; Lee, T. J.; Lee, S. H.; Park, C. Y.; Lee, C. J.

2003-08-01

Well-aligned carbon nanotubes (CNTs) with high purity have been produced by pyrolysis of iron(II) phthalocyanine and acetylene at 800 °C. The synthesized CNTs have a length of 75 μm and diameters ranging from 20 to 60 nm. The CNTs have a bamboo-like structure and exhibit good crystallinity of graphite sheets. The growth rate of the CNTs was rapidly increased with adding C 2H 2. Our results demonstrate that the proposed growth method is suitable to large-scale synthesis of high-purity well-aligned CNTs on various substrates.

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

Detering, B.A.; Kong, P.C.; Thomas, C.P.

This paper describes the experimental demonstration of a process for direct conversion of methane to acetylene in a thermal plasma. The process utilizes a thermal plasma to dissociate methane and form an equilibrium mixture of acetylene followed by a supersonic expansion of the hot gas to preserve the produced acetylene in high yield. The high translational velocities and rapid cooling result in an overpopulation of atomic hydrogen which persists throughout the expansion process. The presence of atomic hydrogen shifts the equilibrium composition by inhibiting complete pyrolysis of methane and acetylene to solid carbon. This process has the potential to reducemore » the cost of producing acetylene from natural gas. Acetylene and hydrogen produced by this process could be used directly as industrial gases, building blocks for synthesis of industrial chemicals, or oligomerized to long chain liquid hydrocarbons for use as fuels. This process produces hydrogen and ultrafine carbon black in addition to acetylene.« less

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

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.

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.

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

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.

Integrated biomass pyrolysis with organic Rankine cycle for power generation

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Methane Pyrolysis and Disposing Off Resulting Carbon

NASA Technical Reports Server (NTRS)

Sharma, P. K.; Rapp, D.; Rahotgi, N. K.

1999-01-01

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is a waste of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduce the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (i) recover hydrogen from the excess methane produced by the S/E process, (ii) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (iii) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. The goals of a research program on recovery of hydrogen from methane are (in descending priority order): 1) Study the kinetics of pyrolysis to arrive at a pyrolysis reactor design that produces high yields in a confined volume at the lowest possible operating temperature; 2) Study the kinetics of carbon burnoff to determine whether high yields can be obtained in a confined volume at acceptable operating temperatures; and 3) Investigate catalytic techniques for depositing carbon as a fine soot which can be physically separated from the reactor. In the JPL program, we have made significant measurements in regard to goal 1, cursory measurements in regard to goal 2, and would plan to pursue goal 3 if additional resources are secured.

An Evaluation of the Functionality of Advanced Fuel Research Prototype Dry Pyrolyzer for Destruction of Solid Wastes

NASA Technical Reports Server (NTRS)

Fisher, John; Wignarajah, K.; Howard, Kevin; Serio, Mike; Kroo, Eric

2004-01-01

The prototype dry pyrolyser delivered to Ames Research Center is the end-product of a Phase I1 Small Business Initiative Research (SBIR) project. Some of the major advantages of pyrolysis for processing solid wastes are that it can process solid wastes, it permits elemental recycling while conserving oxygen use, and it can function as a pretreatment for combustion processes. One of the disadvantages of pyrolysis is the formation of tars. By controlling the rate of heating, tar formation can be minimized. This paper presents data on the pyrolysis of various space station wastes. The performance of the pyrolyser is also discussed and appropriate modifications suggested to improve the performance of the dry pyrolyzer.

Numerical investigation of the staged gasification of wet wood

NASA Astrophysics Data System (ADS)

Donskoi, I. G.; Kozlov, A. N.; Svishchev, D. A.; Shamanskii, V. A.

2017-04-01

Gasification of wooden biomass makes it possible to utilize forestry wastes and agricultural residues for generation of heat and power in isolated small-scale power systems. In spite of the availability of a huge amount of cheap biomass, the implementation of the gasification process is impeded by formation of tar products and poor thermal stability of the process. These factors reduce the competitiveness of gasification as compared with alternative technologies. The use of staged technologies enables certain disadvantages of conventional processes to be avoided. One of the previously proposed staged processes is investigated in this paper. For this purpose, mathematical models were developed for individual stages of the process, such as pyrolysis, pyrolysis gas combustion, and semicoke gasification. The effect of controlling parameters on the efficiency of fuel conversion into combustible gases is studied numerically using these models. For the controlling parameter are selected heat inputted into a pyrolysis reactor, the excess of oxidizer during gas combustion, and the wood moisture content. The process efficiency criterion is the gasification chemical efficiency accounting for the input of external heat (used for fuel drying and pyrolysis). The generated regime diagrams represent the gasification efficiency as a function of controlling parameters. Modeling results demonstrate that an increase in the fraction of heat supplied from an external source can result in an adequate efficiency of the wood gasification through the use of steam generated during drying. There are regions where it is feasible to perform incomplete combustion of the pyrolysis gas prior to the gasification. The calculated chemical efficiency of the staged gasification is as high as 80-85%, which is 10-20% higher that in conventional single-stage processes.

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

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.

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

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

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.

Kinetic compensation effect in logistic distributed activation energy model for lignocellulosic biomass pyrolysis.

PubMed

Xu, Di; Chai, Meiyun; Dong, Zhujun; Rahman, Md Maksudur; Yu, Xi; Cai, Junmeng

2018-06-04

The kinetic compensation effect in the logistic distributed activation energy model (DAEM) for lignocellulosic biomass pyrolysis was investigated. The sum of square error (SSE) surface tool was used to analyze two theoretically simulated logistic DAEM processes for cellulose and xylan pyrolysis. The logistic DAEM coupled with the pattern search method for parameter estimation was used to analyze the experimental data of cellulose pyrolysis. The results showed that many parameter sets of the logistic DAEM could fit the data at different heating rates very well for both simulated and experimental processes, and a perfect linear relationship between the logarithm of the frequency factor and the mean value of the activation energy distribution was found. The parameters of the logistic DAEM can be estimated by coupling the optimization method and isoconversional kinetic methods. The results would be helpful for chemical kinetic analysis using DAEM. Copyright © 2018 Elsevier Ltd. All rights reserved.

Grid-connected integrated community energy system. Phase II, Stage 2, final report. Preliminary design pyrolysis facility. [Andco-Torrax system

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

Not Available

The University of Minnesota is studying and planning a grid connected integrated community energy system to include disposal of wastes from health centers and utilizing the heat generated. The University of Minnesota has purchased the so called Southeast Generating Station from the Northern States Power Company. This plant contains two coal-fired boilers that will be retrofitted to burn low-sulfur Montana coal. Building modifications and additions will be made to support the components of the Andco-Torrax system and integrate the system with the rest of the plant. The Andco-Torrax system is a new high-temperature refuse-conversion process known technically as slagging pyrolysis.more » Although the pyrolysis of solid waste is a relatively new innovation, pyrolysis processes have been used for years by industry. This report covers the preliminary design and operation of the system. (MCW)« less

Molecular characterisation of a bio-based active packaging containing Origanum vulgare L. essential oil using pyrolysis gas chromatography-mass spectrometry.

PubMed

Llana-Ruíz-Cabello, María; Pichardo, Silvia; Jiménez-Morillo, Nicasio T; Bermúdez, José M; Aucejo, Susana; González-Vila, Francisco J; Cameán, Ana M; González-Pérez, José A

2016-07-01

Environmental, economic and safety challenges motivate shift towards safer materials for food packaging. New bioactive packaging techniques, i.e. addition of essential plant oils (EOs), are gaining attention by creating barriers to protect products from spoilage. Analytical pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) was used to fingerprint a bioactive polylactic acid (PLA) with polybutylene succinate (PBS) (950 g kg(-1) :50 g kg(-1) ) film extruded with variable quantities (0, 20, 50 and 100 g kg(-1) ) of Origanum vulgare EO. Main PLA:PBS pyrolysis products were lactide enantiomers and monomer units from the major PLA fraction and succinic acid anhydride from the PBS fraction. Oregano EO pyrolysis released cymene, terpinene and thymol/carvacrol peaks as diagnostic peaks for EO. In fact, linear correlation coefficients better than 0.950R(2) value (P < 0.001) were found between the chromatographic area of the diagnostic peaks and the amount of oregano EO in the bioplastic. The pyrolytic behaviour of a bio-based active package polymer including EO is studied in detail. Identified diagnostic compounds provide a tool to monitor the quantity of EO incorporated into the PLA:PBS polymeric matrix. Analytical pyrolysis is proposed as a rapid technique for the identification and quantification of additives within bio-based plastic matrices. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

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.

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.

Pyrolysis process for producing condensed stabilized hydrocarbons utilizing a beneficially reactive gas

DOEpatents

Durai-Swamy, Kandaswamy

1982-01-01

In a process for recovery of values contained in solid carbonaceous material, the solid carbonaceous material is comminuted and then subjected to pyrolysis, in the presence of a carbon containing solid particulate source of heat and a beneficially reactive transport gas in a transport flash pyrolysis reactor, to form a pyrolysis product stream. The pyrolysis product stream contains a gaseous mixture and particulate solids. The solids are separated from the gaseous mixture to form a substantially solids-free gaseous stream which comprises volatilized hydrocarbon free radicals newly formed by pyrolysis. Preferably the solid particulate source of heat is formed by oxidizing part of the separated particulate solids. The beneficially reactive transport gas inhibits the reactivity of the char product and the carbon-containing solid particulate source of heat. Condensed stabilized hydrocarbons are obtained by quenching the gaseous mixture stream with a quench fluid which contains a capping agent for stabilizing and terminating newly formed volatilized hydrocarbon free radicals. The capping agent is partially depleted of hydrogen by the stabilization and termination reaction. Hydrocarbons of four or more carbon atoms in the gaseous mixture stream are condensed. A liquid stream containing the stabilized liquid product is then treated or separated into various fractions. A liquid containing the hydrogen depleted capping agent is hydrogenated to form a regenerated capping agent. At least a portion of the regenerated capping agent is recycled to the quench zone as the quench fluid. In another embodiment capping agent is produced by the process, separated from the liquid product mixture, and recycled.

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.

Laboratory Measurements of Gas Phase Pyrolysis Products from Southern Wildland Fuels using Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Scharko, N.; Safdari, S.; Danby, T. O.; Howarth, J.; Beiswenger, T. N.; Weise, D.; Myers, T. L.; Fletcher, T. H.; Johnson, T. J.

2017-12-01

Combustion is an oxidation reaction that occurs when there is less fuel available than oxidizers, while pyrolysis is a thermal decomposition process that occurs under "fuel rich" conditions where all of the available oxidizers are consumed leaving some fuel(s) either unreacted or partially reacted. Gas-phase combustion products from biomass burning experiments have been studied extensively; less is known, however, about pyrolysis processes and products. Pyrolysis is the initial reaction occurring in the burning process and generates products that are subsequently oxidized during combustion, yielding highly-oxidized chemicals. This laboratory study investigates the pyrolysis processes by using an FTIR spectrometer to detect and quantify the gas-phase products from thermal decomposition of intact understory fuels from forests in the southeastern United States. In particular, a laboratory flat-flame burner operating under fuel rich conditions (no oxygen) was used to heat individual leaves to cause decomposition. The gas-phase products were introduced to an 8 meter gas cell coupled to an infrared spectrometer were used to monitor the products. Trace gas emissions along with emission ratios, which are calculated by dividing the change in the amount of the trace gas by the change in the amount of CO, for the plant species, gallberry (Ilex glabra) and swampbay (Persea palustris) were determined. Preliminary measurements observed species such as CO2, CO, C2H2, C2H4, HCHO, CH3OH, isoprene, 1,3-butadiene, phenol and NH3 being produced as part of the thermal decomposition process. It is important to note that FTIR will not detect H2.

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.

Renewable energy from corn residues by thermochemical conversion

NASA Astrophysics Data System (ADS)

Yu, Fei

Declining fossil oil reserve, skyrocket price, unsecured supplies, and environment pollution are among the many energy problems we are facing today. It is our conviction that renewable energy is a solution to these problems. The long term goal of the proposed research is to develop commercially practical technologies to produce energy from renewable resources. The overall objective of my research is to study and develop thermochemical processes for converting bulky and low-energy-density biomass materials into bio-fuels and value-added bio-products. The rationale for the proposed research is that, once such processes are developed, processing facility can be set up on or near biomass product sites, reducing the costs associated with transport of bulky biomass which is a key technical barrier to biomass conversion. In my preliminary research, several conversion technologies including atmospheric pressure liquefaction, high pressure liquefaction, and microwave pyrolysis have been evaluated. Our data indicated that microwave pyrolysis had the potential to become a simple and economically viable biomass conversion technology. Microwave pyrolysis is an innovative process that provides efficient and uniform heating, and are robust to type, size and uniformity of feedstock and therefore suitable for almost any waste materials without needing to reduce the particle size. The proposed thesis focused on in-depth investigations of microwave pyrolysis of corn residues. My first specific aim was to examine the effects of processing parameters on product yields. The second specific research aim was to characterize the products (gases, bio-oils, and solid residues), which was critical to process optimization and product developments. Other research tasks included conducting kinetic modeling and preliminary mass and energy balance. This study demonstrated that microwave pyrolysis could be optimized to produce high value syngas, liquid fuels and pyrolytic carbons, and had a great potential to become a commercial process according to the mass and energy balance. One-step global model and two-step consecutive-reaction kinetic model offered a clue to the key mechanistic steps in the overall pyrolysis of corn residues. These results should have a positive impact on advancing renewable energy technologies and establishing the University's leadership status in the area of renewable energy development.

Valorisation of waste tyre by pyrolysis in a moving bed reactor.

PubMed

Aylón, E; Fernández-Colino, A; Murillo, R; Navarro, M V; García, T; Mastral, A M

2010-07-01

The aim of this work is to assess the behaviour of a moving bed reactor, based on a screw transporter design, in waste tyre pyrolysis under several experimental conditions. Waste tyre represents a significant problem in developed countries and it is necessary to develop new technology that could easily process big amounts of this potentially raw material. In this work, the influence of the main pyrolysis process variables (temperature, solid residence time, mass flow rate and inert gas flow) has been studied by a thorough analysis of product yields and properties. It has been found that regardless the process operational parameters, a total waste tyre devolatilisation is achieved, producing a pyrolytic carbon black with a volatile matter content under 5 wt.%. In addition, it has been proven that, in the range studied, the most influencing process variables are temperature and solid mass flow rate, mainly because both variables modify the gas residence time inside the reactor. In addition, it has been found that the modification of these variables affects to the chemical properties of the products. This fact is mainly associated to the different cracking reaction of the primary pyrolysis products. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Valorisation of waste tyre by pyrolysis in a moving bed reactor

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

Aylon, E.; Fernandez-Colino, A.; Murillo, R., E-mail: ramonm@icb.csic.e

2010-07-15

The aim of this work is to assess the behaviour of a moving bed reactor, based on a screw transporter design, in waste tyre pyrolysis under several experimental conditions. Waste tyre represents a significant problem in developed countries and it is necessary to develop new technology that could easily process big amounts of this potentially raw material. In this work, the influence of the main pyrolysis process variables (temperature, solid residence time, mass flow rate and inert gas flow) has been studied by a thorough analysis of product yields and properties. It has been found that regardless the process operationalmore » parameters, a total waste tyre devolatilisation is achieved, producing a pyrolytic carbon black with a volatile matter content under 5 wt.%. In addition, it has been proven that, in the range studied, the most influencing process variables are temperature and solid mass flow rate, mainly because both variables modify the gas residence time inside the reactor. In addition, it has been found that the modification of these variables affects to the chemical properties of the products. This fact is mainly associated to the different cracking reaction of the primary pyrolysis products.« less

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Development of advanced technologies for biomass pyrolysis

NASA Astrophysics Data System (ADS)

Xu, Ran

The utilization of biomass resources as a renewable energy resource is of great importance in responding to concerns over the protection of the environment and the security of energy supply. This PhD research focuses on the investigation of the conversion of negative value biomass residues into value-added fuels through flash pyrolysis. Pyrolysis Process Study. A pilot plant bubbling fluidized bed pyrolyzer has been set up and extensively used to thermally crack various low or negative value agricultural, food and biofuel processing residues to investigate the yields and quality of the liquid [bio-oil] and solid (bio-char] products. Another novel aspect of this study is the establishment of an energy balance from which the thermal self-sustainability of the pyrolysis process can be assessed. Residues such as grape skins and mixture of grape skins and seeds, dried distiller's grains from bio-ethanol plants, sugarcane field residues (internal bagasse, external and whole plant) have been tested. The pyrolysis of each residue has been carried out at temperatures ranging from 300 to 600°C and at different vapor residence times, to determine its pyrolysis behavior including yields and the overall energy balance. The thermal sustainability of the pyrolysis process has been estimated by considering the energy contribution of the product gases and liquid bio-oll in relation to the pyrolysis heat requirements. The optimum pyrolysis conditions have been identified in terms of maximizing the liquid blo-oil yield, energy density and content of the product blo-oil, after ensuring a self-sustainable process by utilizing the product gases and part of char or bio-oil as heat sources. Adownflow pyrolyzer has also been set up. Preliminary tests have been conducted using much shorter residence times. Bio-oil Recovery. Bio-oil recovery from the pyrolysis unit includes condensation followed by demisting. A blo-oil cyclonic condensing system is designed A nearly tangential entry forces the entering vapors and gases to spin, providing good heat transfer and driving the condensed droplets to the wall through cyclonic action. This condenser design has been successfully demonstrated for the application on the pilot fluidized bed pyrolysis unit. After condensation, a stable aerosol is also typically formed which is difficult to be efficiently captured with conventional technologies. A pilot scale helicoidal rotary demister, a novel technology for removing persistent fine bio-oil droplets from gases using dynamic centrifugal forces, has been developed. The demister uses a helicoidal element, which consists of a metal sheet wound as a spiral, designed to rotate at high speeds within a cyclone body. Larger droplets are separated as they enter the cyclone housing, while the smaller droplets are carried by the gas into the helicoidal path of the rotating element, where they are centrifuged towards the outer collecting walls and, as a result of a specially designed baffle, may flow counter-currently to the gas and are drained out from the bottom of the rotating element. The mist-free gas leaves through a channel located at the center of the spiral. This unique demister design has demonstrated a high separation efficiency when tested offline with artificial submicron mist and tested online for demisting bio-oil aerosol on the pyrolysis unit. Bio-oil Upgrading: Very often, phase separation of bio-oil occurs naturally upon condensation of the bio-oil vapors, typically through the use of cyclonic condensers. The bio-oil is separated into an organic phase and an aqueous phase. Research has been conducted on the possibility to enhance the fuel properties and energy performance of the organic phase by reducing its water content, enhancing its heating value and improving its stability. Through the use of drying agents, a remarkable reduction of water content and an increase of heating value can be achieved. Moreover, the volumetric energy density can be greatly enhanced. Besides, the energy yield of the process has also been investigated. (Abstract shortened by UMI.)

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

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.

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

Chemistry of rubber processing and disposal.

PubMed Central

Bebb, R L

1976-01-01

The major chemical changes during the processing of rubber occur with the breakdown in mastication and during vulcanization of the molded tire. There is little chemical change during the compounding, calendering, extrusion, and molding steps. Reclaiming is the process of converting scrap rubber into an unsaturated, processible product that can be vulcanized with sulfur. Pyrolysis of scrap rubber yields a complex mixture of liquids, gas, and residue in varying ratios dependent on the nature of the scrap and the conditions of pyrolysis. PMID:799964

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

Pyrolysis of chromium rich tanning industrial wastes and utilization of carbonized wastes in metallurgical process.

PubMed

Tôrres Filho, Artur; Lange, Liséte Celina; de Melo, Gilberto Caldeira Bandeira; Praes, Gustavo Eduardo

2016-02-01

Pyrolysis is the thermal degradation of organic material in oxygen-free or very lean oxygen atmosphere. This study evaluates the use of pyrolysis for conversion of leather wastes from chromium tanning processes into Carbonized Leather Residues (CLR), and the utilization of CLR in metallurgical processes through the production of iron ore pellets. CLR was used to replace mineral coal in proportions of 10% and 25% on fixed carbon basis content in the mixtures for pellets preparation. Experimental conversions were performed on a pilot scale pyrolysis plant and a pelletizing reactor of the "pot grate" type. The results demonstrated the technical feasibility of using the charcoal product from animal origin as an energy source, with recovery of up to 76.47% of chromium contained in CLR in the final produced of iron ore pellets. Pellets with 25% replacement of fixed carbon in the coal showed an enhanced compressive strength, with an average value of 344kgfpellet(-1), compared to 300kgfpellet(-1) for standard produced pellets. Copyright © 2015. Published by Elsevier Ltd.

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% (

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

Oxygen production by pyrolysis of lunar regolith

NASA Technical Reports Server (NTRS)

Senior, Constance L.

1991-01-01

Oxygen was identified as the most important product of initial lunar materials processing efforts. A source of oxygen on the Moon provides an alternative to the costly transport of propellant to the Moon or to low earth orbit. Pyrolysis, or vapor-phase reduction, involves heating a feedstock to temperatures sufficient to decompose the constituent metal oxides and release oxygen. The process relies on the vaporization of metal oxides in the form of reduced suboxides or atomic species. The reduced species must then be condensed without re-oxidizing, yielding oxygen in the gas phase. The feasibility of obtaining oxygen from common lunar minerals was demonstrated using solar furnace experiments. These results are discussed together with chemical equilibrium models which were extended to include the multicomponent oxides used in experiments. For the first time, both experiments and theoretical models dealt with the complex oxides that make up potential lunar feedstocks. Two major conclusions are drawn from this preliminary work. First, unbeneficiated regolith is a suitable feedstock for pyrolysis. Second, the process can operate at moderate temperatures, circa 2000 K, which could be supplied by direct solar or electrical energy. In addition to these advantages in choice of feedstock and energy source, the pyrolysis process requires no chemicals or reagents, making it an attractive process for lunar oxygen production.

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.

Feedstock Interface Fy2017 Q3 Report

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

Carpenter, Danny; Howe, Daniel; Westover, Tyler

This report summarized the results obtained in FY2017 Q3 of a collaborative effort between researchers at NREL, PNNL, and INL to develop rapid screening methods and models to predict the fact pyrolysis conversion performance of a range of biomass materials.

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.

A case study of pyrolysis of oil palm wastes in Malaysia

NASA Astrophysics Data System (ADS)

Abdullah, Nurhayati; Sulaiman, Fauziah; Aliasak, Zalila

2013-05-01

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

The influence of composition and final pyrolysis temperature variations on global kinetics of combustion of segregated municipal solid waste

NASA Astrophysics Data System (ADS)

Pranoto; Himawanto, D. A.; Arifin, N. A.

2017-04-01

The combustion of segregated municipal solid waste (MSW) and the resulted char from the pyrolysis process were investigated in this research. The segregated MSW that was collected and used can be divided into organic and inorganic waste materials. The organic materials were bamboo and banana leaves and the inorganic materials were Styrofoam and snack wrappings. The composition ratio of the waste was based on the percentage of weight of each sample. The thermal behaviour of the segregated MSW was investigated by thermo gravimetric analysis. For the pyrolysis process the prepared samples of 200gram were heated from ambient temperature until a variance of final pyrolysis temperature of 550°C, 650°C and 750°C at a constant heating rate of 25°C/min. It was found that the highest activation energy of the raw materials is achieved from sample CC1 (Char with 100% inorganic materials). The activation energy of the raw materials is relatively lower than that of the char. The higher the final pyrolysis temperature, the lower the calorific value of char. The calorific value gradually increases with the amount of inorganic materials.

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.

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

DOEpatents

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

2015-11-04

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

Laboratory Reactor for Processing Carbon-Containing Sludge

NASA Astrophysics Data System (ADS)

Korovin, I. O.; Medvedev, A. V.

2016-10-01

The paper describes a reactor for high-temperature pyrolysis of carbon-containing sludge with the possibility of further development of environmentally safe technology of hydrocarbon waste disposal to produce secondary products. A solution of the urgent problem has been found: prevention of environmental pollution resulting from oil pollution of soils using the pyrolysis process as a method of disposal of hydrocarbon waste to produce secondary products.

Design criteria for Reedy Creek Demonstration Project

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

Felicione, F.S.; Logan, J.A.

1980-11-01

This document defines the basic criteria for the 100-ton/day pilot plant which will use the Andco-Torrax pyrolysis process at Walt Disney World in Orlando, Florida, to produce hot water. The waste will simulate transuranic wastes which are stored at INEL. The Andco-Torrax process is designed to convert mixed municipal refuse into energy and is called slagging pyrolysis solid waste conversion. (DLC)

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.

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

Mann, M.K.

Technoeconomic analyses have been conducted on two processes to produce hydrogen from biomass: indirectly-heated gasification of biomass followed by steam reforming of the syngas, and biomass pyrolysis followed by steam reforming of the pyrolysis oil. The analysis of the gasification-based process was highly detailed, including a process flowsheet, material and energy balances calculated with a process simulation program, equipment cost estimation, and the determination of the necessary selling price of hydrogen. The pyrolysis-based process analysis was of a less detailed nature, as all necessary experimental data have not been obtained; this analysis is a follow-up to the preliminary economic analysismore » presented at the 1994 Hydrogen Program Review. A coproduct option in which pyrolysis oil is used to produce hydrogen and a commercial adhesive was also studied for economic viability. Based on feedstock availability estimates, three plant sizes were studied: 907 T/day, 272 T/day, and 27 T/day. The necessary selling price of hydrogen produced by steam reforming syngas from the Battelle Columbus Laboratories indirectly heated biomass gasifier falls within current market values for the large and medium size plants within a wide range of feedstock costs. Results show that the small scale plant does not produce hydrogen at economically competitive prices, indicating that if gasification is used as the upstream process to produce hydrogen, local refueling stations similar to current gasoline stations, would probably not be feasible.« less

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.

Innovative Processing of Composites for Ultra-High Temperature Applications. Book 1

DTIC Science & Technology

1993-11-01

pyrolysis step (in which the polymer is converted at higher temperatures to a SiC -rich ceramic). However, curing in air also leads to the high oxygen...The fac’ that the ceramic the vinylic SiC precursor, i.e., a compound or polymer resulting from pyrolysis of the vinylic precursor re- having vinylic...12 %herein said atmosphere 1. A method of preparing preceramic SiC fibers hay- 65 utilized for pyrolysis ik a reactime atmosphere contain- ing a very

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

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.

Biological markers from Green River kerogen decomposition

NASA Astrophysics Data System (ADS)

Burnham, A. K.; Clarkson, J. E.; Singleton, M. F.; Wong, C. M.; Crawford, R. W.

1982-07-01

Isoprenoid and other carbon skeletons that are formed in living organisms and preserved essentially intact in ancient sediments are often called biological markers. The purpose of this paper is to develop improved methods of using isoprenoid hydrocarbons to relate petroleum or shale oil to its source rock. It is demonstrated that most, but not all, of the isoprenoid hydrocarbon structures are chemically bonded in kerogen (or to minerals) in Green River oil shale. The rate constant for thermally producing isoprenoid, cyclic, and aromatic hydrocarbons is substantially greater than for the bulk of shale oil. This may be related to the substantial quantity of CO 2 which is evolved coincident with the isoprenoid hydrocarbons but prior to substantial oil evolution. Although formation of isoprenoid alkenes is enhanced by rapid heating and high pyrolysis temperatures, the ratio of isoprenoid alkenes plus alkanes to normal alkenes plus alkanes is independent of heating rate. High-temperature laboratory pyrolysis experiments can thus be used to predict the distribution of aliphatic hydrocarbons in low temperature processes such as in situ shale oil production and perhaps petroleum formation. Finally, we demonstrate that significant variation in biological marker ratios occurs as a function of stratigraphy in the Green River formation. This information, combined with methods for measuring process yield from oil composition, enables one to relate time-dependent processing conditions to the corresponding time-dependent oil yield in a vertical modified- in situ retort even if there is a substantial and previously undetermined delay in drainage of shale oil from the retort.

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.

Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels

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

Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve

Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the non-catalytic process separates into a non-polar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon presentmore » in this stream. Our work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical micro-reactor coupled to a molecular beam mass spectrometer (MBMS). Furthermore, the MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction to fuels comprising small olefins and aromatic hydrocarbons. During processing the aqueous bio-oil fraction the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt% of the carbon in the feed stream is recovered as hydrocarbons.« less

Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels

DOE PAGES

Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve; ...

2017-01-07

Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the non-catalytic process separates into a non-polar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon presentmore » in this stream. Our work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical micro-reactor coupled to a molecular beam mass spectrometer (MBMS). Furthermore, the MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction to fuels comprising small olefins and aromatic hydrocarbons. During processing the aqueous bio-oil fraction the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt% of the carbon in the feed stream is recovered as hydrocarbons.« less

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.

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.

Development of SiC/SiC composites by PIP in combination with RS

NASA Astrophysics Data System (ADS)

Kotani, Masaki; Kohyama, Akira; Katoh, Yutai

2001-02-01

In order to improve the mechanical performances of SiC/SiC composite, process improvement and modification of polymer impregnation and pyrolysis (PIP) and reaction sintering (RS) process were investigated. The fibrous prepregs were prepared by a polymeric intra-bundle densification technique using Tyranno-SA™ fiber. For inter-bundle matrix, four kinds of process options utilizing polymer pyrolysis and reaction sintering were studied. The process conditions were systematically optimized through fabricating monoliths. Then, SiC/SiC composites were fabricated using optimized inter-bundle matrix slurries in each process for the first inspection of process requirements.

Bifunctional catalysts for upgrading of biomass-derived oxygenates: A review

DOE PAGES

Robinson, Allison M.; Hensley, Jesse E.; Medlin, J. Will

2016-06-21

Deoxygenation is an important reaction in the conversion of biomass-derived oxygenates to fuels and chemicals. A key route for biomass refining involves the production of pyrolysis oil through rapid heating of the raw biomass feedstock. Pyrolysis oil as produced is highly oxygenated, so the feasibility of this approach depends in large part on the ability to selectively deoxygenate pyrolysis oil components to create a stream of high-value finished products. Identification of catalytic materials that are active and selective for deoxygenation of pyrolysis oil components has therefore represented a major research area. One catalyst is rarely capable of performing the differentmore » types of elementary reaction steps required to deoxygenate biomass-derived compounds. For this reason, considerable attention has been placed on bifunctional catalysts, where two different active materials are used to provide catalytic sites for diverse reaction steps. Here, we review recent trends in the development of catalysts, with a focus on catalysts for which a bifunctional effect has been proposed. We summarize recent studies of hydrodeoxygenation (HDO) of pyrolysis oil and model compounds for a range of materials, including supported metal and bimetallic catalysts as well as transition-metal oxides, sulfides, carbides, nitrides, and phosphides. Particular emphasis is placed on how catalyst structure can be related to performance via molecular-level mechanisms. Finally, these studies demonstrate the importance of catalyst bifunctionality, with each class of materials requiring hydrogenation and C-O scission sites to perform HDO at reasonable rates.« less

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

Larson, Natalie M.; Zok, Frank W.

One route for producing fiber-reinforced ceramic-matrix composites entails repeated impregnation and pyrolysis of a preceramic polymer in a fiber preform. The process relies crucially on the development of networks of contiguous cracks during pyrolysis, thereby allowing further impregnation to attain nearly-full densification. The present study employs in-situ x-ray computed tomography (XCT) to reveal in three dimensions the evolution of matrix structure during pyrolysis of a SiC-based preceramic polymer to 1200 °C. Observations are used to guide the development of a taxonomy of crack geometries and crack structures and to identify the temporal sequence of their formation. A quantitative analysis ismore » employed to characterize effects of local microstructural dimensions on the conditions required to form cracks of various types. Complementary measurements of gas evolution and mass loss of the preceramic polymer during pyrolysis as well as changes in mass density and Young's modulus provide context for the physical changes revealed by XCT. Furthermore, the findings provide a foundation for future development of physics-based models to guide composite fabrication processes.« less

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

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

Czernik, S.; Wang, D.; Chornet, E.

1998-08-01

Hydrogen is the prototype of the environmentally cleanest fuel of interest for power generation using fuel cells and for transportation. The thermochemical conversion of biomass to hydrogen can be carried out through two distinct strategies: (a) gasification followed by water-gas shift conversion, and (b) catalytic steam reforming of specific fractions derived from fast pyrolysis and aqueous/steam processes of biomass. This paper presents the latter route that begins with fast pyrolysis of biomass to produce bio-oil. This oil (as a whole or its selected fractions) can be converted to hydrogen via catalytic steam reforming followed by a water-gas shift conversion step.more » Such a process has been demonstrated at the bench scale using model compounds, poplar oil aqueous fraction, and the whole pyrolysis oil with commercial Ni-based steam reforming catalysts. Hydrogen yields as high as 85% have been obtained. Catalyst initial activity can be recovered through regeneration cycles by steam or CO{sub 2} gasification of carbonaceous deposits.« less

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

Product Chemistry and Process Efficiency of Biomass Torrefaction, Pyrolysis and Gasification Studied by High-Throughput Techniques and Multivariate Analysis

NASA Astrophysics Data System (ADS)

Xiao, Li

Despite the great passion and endless efforts on development of renewable energy from biomass, the commercialization and scale up of biofuel production is still under pressure and facing challenges. New ideas and facilities are being tested around the world targeting at reducing cost and improving product value. Cutting edge technologies involving analytical chemistry, statistics analysis, industrial engineering, computer simulation, and mathematics modeling, etc. keep integrating modern elements into this classic research. One of those challenges of commercializing biofuel production is the complexity from chemical composition of biomass feedstock and the products. Because of this, feedstock selection and process optimization cannot be conducted efficiently. This dissertation attempts to further evaluate biomass thermal decomposition process using both traditional methods and advanced technique (Pyrolysis Molecular Beam Mass Spectrometry). Focus has been made on data base generation of thermal decomposition products from biomass at different temperatures, finding out the relationship between traditional methods and advanced techniques, evaluating process efficiency and optimizing reaction conditions, comparison of typically utilized biomass feedstock and new search on innovative species for economical viable feedstock preparation concepts, etc. Lab scale quartz tube reactors and 80il stainless steel sample cups coupled with auto-sampling system were utilized to simulate the complicated reactions happened in real fluidized or entrained flow reactors. Two main high throughput analytical techniques used are Near Infrared Spectroscopy (NIR) and Pyrolysis Molecular Beam Mass Spectrometry (Py-MBMS). Mass balance, carbon balance, and product distribution are presented in detail. Variations of thermal decomposition temperature range from 200°C to 950°C. Feedstocks used in the study involve typical hardwood and softwood (red oak, white oak, yellow poplar, loblolly pine), fast growing energy crops (switchgrass), and popular forage crop (alfalfa), as well as biochar derived from those materials and their mixtures. It demonstrated that Py-MBMS coupled with MVA could be used as fast analytical tools for the study of not only biomass composition but also its thermal decomposition behaviors. It found that the impact of biomass composition heavily depends on the thermal decomposition temperature because at different temperature, the composition of biomass decomposed and the impact of minerals on the decomposition reaction varies. At low temperature (200-500°C), organic compounds attribute to the majority of variation in thermal decomposition products. At higher temperature, inorganics dramatically changed the pyrolysis pathway of carbohydrates and possibly lignin. In gasification, gasification tar formation is also observed to be impacted by ash content in vapor and char. In real reactor, biochar structure also has interactions with other fractions to make the final pyrolysis and gasification product. Based on the evaluation of process efficiencies during torrefaction, temperature ranging from 275°C to 300°C with short residence time (<10min) are proposed to be optimal torrefaction conditions. 500°C is preferred to 700°C as primary pyrolysis temperature in two stage gasification because higher primary pyrolysis temperature resulted in more tar and less gasification char. Also, in terms of carbon yield, more carbon is lost in tar while less carbon is retained in gas product using 700°C as primary pyrolysis temperature. In addition, pyrolysis char is found to produce less tar and more gas during steam gasification compared with gasification of pyrolysis vapor. Thus it is suggested that torrefaction might be an efficient pretreatment for biomass gasification because it can largely improve the yield of pyrolysis char during the primary pyrolysis step of gasification thus reduce the total tar of the overall gasification products. Future work is suggested in the end.

Mechanistic study of the influence of pyrolysis conditions on potassium speciation in biochar "preparation-application" process.

PubMed

Tan, Zhongxin; Liu, Liyun; Zhang, Limei; Huang, Qiaoyun

2017-12-01

Biochar samples produced from rice straw by pyrolysis at different temperatures (400°C and 800°C) and under different atmospheres (N 2 and CO 2 ) were applied to lettuce growth in a 'preparation-application' system. The conversion of potassium in the prepared biochar and the effect of the temperature used for pyrolysis on the bioavailability of potassium in the biochar were investigated. Root samples from lettuce plants grown with and without application of biochar were assayed by X-ray photoelectron spectroscopy (XPS). The optimal conditions for preparation of biochar to achieve the maximum bioavailability of potassium (i.e. for returning biochar to soil) were thus determined. Complex-K, a stable speciation of potassium in rice straw, was transformed into potassium sulfate, potassium nitrate, potassium nitrite, and potassium chloride after oxygen-limited pyrolysis. The aforementioned ionic-state potassium species can be directly absorbed and used by plants. Decomposition of the stable speciation of potassium during the pyrolysis process was more effective at higher temperature, whereas the pyrolysis atmosphere (CO 2 and N 2 ) had little effect on the quality of the biochar. Based on the potassium speciation in the biochar, the preparation cost, and the plant growth and rigor after the application of returning biochar to soil, 400°C and CO 2 atmosphere were the most appropriate conditions for preparation of biochar. Copyright © 2017. Published by Elsevier B.V.

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.

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

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.

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.

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.

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

MERCURY MEASUREMENTS FOR SOLIDS MADE RAPIDLY, SIMPLY, AND INEXPENSIVELY

EPA Science Inventory

While traditional methods for determining mercury in solid samples involve the use of aggressive chemicals to dissolve the matrix and the use of other chemicals to properly reduce the mercury to the volatile elemental form, pyrolysis-based analyzers can be used by directly weighi...

DETERMINATION OF TOTAL MERCURY IN FISH TISSUES USING PYROLYSIS ATOMIC ABSORPTION SPECTROMETRY WITH GOLD AMALGAMATION

EPA Science Inventory

A simple and rapid procedure for measuring total mercury in fish tissues is evaluated and
compared with conventional techniques. Using an automated instrument incorporating combustion, preconcentration by amalgamation with gold, and atomic absorption spectrometry (AAS), mill...

Comparing corn stover and switchgrass biochar: characterization and sorption properties

USDA-ARS?s Scientific Manuscript database

A switchgrass biochar (SB) produced by fast pyrolysis and a corn stover biochar (CSB) from a slow pyrolysis process were mechanically milled and characterized. Both of these biochars are very cost-effective and originate as residues from bioenergy production and the corn industry, respectively. Thes...

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.

3D Material Response Analysis of PICA Pyrolysis Experiments

NASA Technical Reports Server (NTRS)

Oliver, Brandon A.

2017-01-01

Primarily interested in improving ablation modeling for use in inverse reconstruction of flight environments on ablative heat shields. Ablation model is essentially a component of the heat flux sensor, so model uncertainties lead to measurement uncertainties. Non-equilibrium processes have been known to be significant in low density ablators for a long time, but increased accuracy requirements of the reconstruction process necessitates incorporating this physical effect. Attempting to develop a pyrolysis model for implementation in material response based on the PICA data produced by Bessire and Minton. Pyrolysis gas species molar yields as a function of temperature and heating rate. Several problems encountered while trying to fit Arrhenius models to the data led to further investigation of the experimental setup.

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

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

Chum, Helena L.

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

Effect of chemical pretreatment on pyrolysis of non-metallic fraction recycled from waste printed circuit boards.

PubMed

Shen, Yafei

2018-06-01

The non-metallic fraction from waste printed circuit boards (NMF-WPCB) generally consists of plastics with high content of Br, glass fibers and metals (e.g. Cu), which are normally difficult to dispose. This work aims to study the chemical pretreatments by using alkalis, acids and alkali-earth-metal salts on pyrolysis of NMF-WPCB. Char (60-79%) and volatile matter (21-40%) can be produced via the pyrolysis process. In particular, the ash content can reach up to 42-56%, which was attributed to the high content of glass fibers and other minerals. Copper (Cu, 2.5%), calcium (Ca, 28.7%), and aluminum (Al, 6.9%) were the main metal constituents. Meanwhile, silicon (Si, 28.3%) and bromine (Br, 26.4%) were the predominant non-metallic constituents. The heavy metals such as Cu were significantly reduced by 92.4% with the acid (i.e. HCl) pretreatment. It has been proved that the organic Br in the plastics (e.g. BFR) can be transformed into HBr via the pyrolysis process at relatively high temperature. It was noteworthy that the alkali pretreatment was more benefit for the Br fixation in the solid char. Particularly, the Br fixation efficiency can reach up to 53.6% by the sodium hydroxide (NaOH) pretreatment with the pyrolysis process. The formed HBr can react with NaOH to generate NaBr. Copyright © 2018 Elsevier Ltd. All rights reserved.

Depolymerization of lignin via co-pyrolysis with 1,4-butanediol in a microwave reactor

USDA-ARS?s Scientific Manuscript database

The production of valuable compounds from low cost but abundant residual lignin has proven to be challenging. The lack of effective biochemical lignin depolymerization processes has led many to focus on thermochemical conversion methods. Bench scale microwave pyrolysis of lignin has been performed...

Dual fluidized bed design for the fast pyrolysis of biomass

USDA-ARS?s Scientific Manuscript database

A mechanism for the transport of solids between fluidised beds in dual fluidised bed systems for the fast pyrolysis of biomass process was selected. This mechanism makes use of an overflow standpipe to transport solids from the fluidised bed used for the combustion reactions to a second fluidised be...

Phosphorus distribution in soils amended with bioenergy co-product materials following corn growth

USDA-ARS?s Scientific Manuscript database

Biochar is a carbonaceous co-product that results from pyrolysis of organic material in the absence of oxygen produced for use as a soil amendment. Pyrolysis, gasification, and combustion are three processes being investigated and/or used to convert biomass into renewable energy and other products. ...

Co-processing of agricultural plastic waste and switchgrass via tail gas reactive pyrolysis

USDA-ARS?s Scientific Manuscript database

Mixtures of agricultural plastic waste in the form of polyethylene hay bale covers (PE) (4-37%) and switchgrass were investigated using the US Department of Agriculture’s tail gas reactive pyrolysis (TGRP) at different temperatures (400-570 deg C). TGRP of switchgrass and plastic mixtures significan...

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

USDA-ARS?s Scientific Manuscript database

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

Comparing Effects of Feedstock and Run Conditions on Pyrolysis Products Produced at Pilot-Scale

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

Dunning, Timothy C; Gaston, Katherine R; Wilcox, Esther

2018-01-19

Fast pyrolysis is a promising pathway for mass production of liquid transportable biofuels. The Thermochemical Process Development Unit (TCPDU) pilot plant at NREL is conducting research to support the Bioenergy Technologies Office's 2017 goal of a $3 per gallon biofuel. In preparation for down select of feedstock and run conditions, four different feedstocks were run at three different run conditions. The products produced were characterized extensively. Hot pyrolysis vapors and light gasses were analyzed on a slip stream, and oil and char samples were characterized post run.

Pyrolysis process and apparatus

DOEpatents

Lee, Chang-Kuei

1983-01-01

This invention discloses a process and apparatus for pyrolyzing particulate coal by heating with a particulate solid heating media in a transport reactor. The invention tends to dampen fluctuations in the flow of heating media upstream of the pyrolysis zone, and by so doing forms a substantially continuous and substantially uniform annular column of heating media flowing downwardly along the inside diameter of the reactor. The invention is particularly useful for bituminous or agglomerative type coals.

High liquid yield process for retorting various organic materials including oil shale

DOEpatents

Coburn, Thomas T.

1990-01-01

This invention is a continuous retorting process for various high molecular weight organic materials, including oil shale, that yields an enhanced output of liquid product. The organic material, mineral matter, and an acidic catalyst, that appreciably adsorbs alkenes on surface sites at prescribed temperatures, are mixed and introduced into a pyrolyzer. A circulating stream of olefin enriched pyrolysis gas is continuously swept through the organic material and catalyst, whereupon, as the result of pyrolysis, the enhanced liquid product output is provided. Mixed spent organic material, mineral matter, and cool catalyst are continuously withdrawn from the pyrolyzer. Combustion of the spent organic material and mineral matter serves to reheat the catalyst. Olefin depleted pyrolysis gas, from the pyrolyzer, is enriched in olefins and recycled into the pyrolyzer. The reheated acidic catalyst is separated from the mineral matter and again mixed with fresh organic material, to maintain the continuously cyclic process.

A high liquid yield process for retorting various organic materials including oil shale

DOEpatents

Coburn, T.T.

1988-07-26

This invention is a continuous retorting process for various high molecular weight organic materials, including oil shale, that yields an enhanced output of liquid product. The organic material, mineral matter, and an acidic catalyst, that appreciably adsorbs alkenes on surface sites at prescribed temperatures, are mixed and introduced into a pyrolyzer. A circulating stream of olefin enriched pyrolysis gas is continuously swept through the organic material and catalyst, whereupon, as the result of pyrolysis, the enhanced liquid product output is provided. Mixed spent organic material, mineral matter, and cool catalyst are continuously withdrawn from the pyrolyzer. Combustion of the spent organic material and mineral matter serves to reheat the catalyst. Olefin depleted pyrolysis gas, from the pyrolyzer, is enriched in olefins and recycled into the pyrolyzer. The reheated acidic catalyst is separated from the mineral matter and again mixed with fresh organic material, to maintain the continuously cyclic process. 2 figs.

Critical analysis of pyrolysis process with cellulosic based municipal waste as renewable source in energy and technical perspective.

PubMed

Agarwal, Manu; Tardio, James; Venkata Mohan, S

2013-11-01

To understand the potential of cellulosic based municipal waste as a renewable feed-stock, application of pyrolysis by biorefinery approach was comprehensively studied for its practicable application towards technical and environmental viability in Indian context. In India, where the energy requirements are high, the pyrolysis of the cellulosic waste shows numerous advantages for its applicability as a potential waste-to-energy technology. The multiple energy outputs of the process viz., bio-gas, bio-oil and bio-char can serve the two major energy sectors, viz., electricity and transportation. The process suits best for high bio-gas and electrical energy production when energy input is satisfied from bio-char in form of steam (scheme-1). The bio-gas generated through the process shows its direct utility as a transportation fuel while the bio-oil produced can serve as fuel or raw material to chemical synthesis. On a commercial scale the process is a potent technology towards sustainable development. The process is self-sustained when operated on a continuous mode. Copyright © 2013 Elsevier Ltd. All rights reserved.

TELEPHONIC PRESENTATION: MERCURY MEASUREMENTS FOR SOLIDS MADE RAPIDLY, SIMPLY, AND INEXPENSIVELY

EPA Science Inventory

While traditional methods for determining mercury in solid samples involve the use of aggressive chemicals to dissolve the matrix and the use of other chemicals to properly reduce the mercury to the volatile elemental form, pyrolysis-based analyzers can be used by directly weighi...

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

PubMed

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

2017-02-01

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

Biomass conversion processes for energy and fuels

NASA Astrophysics Data System (ADS)

Sofer, S. S.; Zaborsky, O. R.

The book treats biomass sources, promising processes for the conversion of biomass into energy and fuels, and the technical and economic considerations in biomass conversion. Sources of biomass examined include crop residues and municipal, animal and industrial wastes, agricultural and forestry residues, aquatic biomass, marine biomass and silvicultural energy farms. Processes for biomass energy and fuel conversion by direct combustion (the Andco-Torrax system), thermochemical conversion (flash pyrolysis, carboxylolysis, pyrolysis, Purox process, gasification and syngas recycling) and biochemical conversion (anaerobic digestion, methanogenesis and ethanol fermentation) are discussed, and mass and energy balances are presented for each system.

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.

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.

Magnesium Sulfate as a Key Mineral for the Detection of Organic Molecules on Mars Using Pyrolysis

NASA Technical Reports Server (NTRS)

Francois, P.; Szopa, C.; Buch, A.; Coll, P.; McAdam, A. C.; Mahaffy, P. R.; Freissinet, C.; Glavin, D. P.; Navarro-Gonzalez, R.; Cabane, M.

2016-01-01

Pyrolysis of soil or rock samples is the preferred preparation technique used on Mars to search for organic molecules up today. During pyrolysis, oxichlorines present in the soil of Mars release oxidant species that alter the organic molecules potentially contained in the samples collected by the space probes.This process can explain the difficulty experienced by in situ exploration probes to detect organic materials in Mars soil samples until recently. Within a few months, the Curiosity rover should reach and analyze for the first time soils rich in sulfates which could induce a different behavior of the organics during the pyrolysis compared with the types of soils analyzed up today. For this reason, we systematically studied the pyrolysis of organic molecules trapped in magnesium sulfate, in the presence or absence of calcium perchlorate. Our results show that organics trapped in magnesium sulfate can undergo some oxidation and sulfuration during the pyrolysis. But these sulfates are also shown to protect organics trapped inside the crystal lattice and/or present in fluid inclusions from the oxidation induced by the decomposition of calcium perchlorate and probably other oxychlorine phases currently detected on Mars. Trapped organics may also be protected from degradation processes induced by other minerals present in the sample, at least until these organics are released from the pyrolyzed sulfate mineral (700C in our experiment). Hence, we suggest magnesium sulfate as one of the minerals to target in priority for the search of organic molecules by the Curiosity and ExoMars 2018 rovers.

Development of manufacturing process for large-diameter composite monofilaments by pyrolysis of resin-impregnated carbon-fiber bundles

NASA Technical Reports Server (NTRS)

Bradshaw, W. G.; Pinoli, P. C.; Vidoz, A. E.

1972-01-01

Large diameter, carbon-carbon composite, monofilaments were produced from the pyrolysis of organic precursor resins reinforced with high-strenght carbon fibers. The mechanical properties were measured before and after pyrolysis and the results were correlated with the properties of the constituents. The composite resulting from the combination of Thornel 75 and GW-173 resin precursor produced the highest tensile strength. The importance of matching strain-to-failure of fibers and matrix to obtain all the potential reinforcement of fibers is discussed. Methods are described to reduce, within the carbonaceous matrix, pyrolysis flaws which tend to reduce the composite strength. Preliminary studies are described which demonstrated the feasibility of fiber-matrix copyrolysis to alleviate matrix cracking and provide an improved matrix-fiber interfacial bonding.

Study on pyrolysis characteristics of lignocellulosic biomass impregnated with ammonia source.

PubMed

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

2016-06-01

The current study presents the pyrolysis characteristics of rice husk impregnated with different kinds of ammonia source (ammonium acetate, urea, ammonium sulfate and ammonium dihydrogen phosphate) in a fixed bed reactor. The introduction of ammonia source in pyrolysis process achieved the conversation from carbonyl compounds to nitrogenous heterocyclic compounds. The liquid product of urea-impregnated biomass has higher content of nitrogenous heterocyclic compounds (8.35%) and phenols (30.4%). For ammonium sulfate and ammonium dihydrogen phosphate-impregnated biomass, the quantity of compounds in liquid products reduces remarkably, and the gas products are rich in CO and H2. All the solid products of pyrolysis have great potential application in biochar-based fertilizer and activated carbon for their high N content. Copyright © 2016 Elsevier Ltd. All rights reserved.

PRESENTED 04/05/2006: MERCURY MEASUREMENTS FOR SOLIDS MADE RAPIDLY, SIMPLY, AND INEXPENSIVELY

EPA Science Inventory

While traditional methods for determining mercury in solid samples involve the use of aggressive chemicals to dissolve the matrix and the use of other chemicals to properly reduce the mercury to the volatile elemental form, pyrolysis-based analyzers can be used by directly weighi...

PRESENTED MAY 10, 2005, MERCURY MEASUREMENTS FOR SOLIDS MADE RAPIDLY, SIMPLY, AND INEXPENSIVELY

EPA Science Inventory

While traditional methods for determining mercury in solid samples involve the use of aggressive chemicals to dissolve the matrix and the use of other chemicals to properly reduce the mercury to the volatile elemental form, pyrolysis-based analyzers can be used by directly weighi...

Comparison of biochar formation from various agricultural by-products using FTIR spectroscopy

USDA-ARS?s Scientific Manuscript database

Biochar is charred material produced by the pyrolysis of organic biomass. In this work, Fourier transform infrared (FTIR) spectra of different agricultural by-products feedstock and their derived biochars were collected to explore the potential of FTIR technique as a simple and rapid method for char...

Ex situ themo-catalytic upgrading of biomass pyrolysis vapors using a traveling wave microwave reactor

USDA-ARS?s Scientific Manuscript database

Microwave heating offers a number of advantages over conventional heating methods, such as, rapid and volumetric heating, precise temperature control, energy efficiency and lower temperature gradient. In this article we demonstrate the use of 2450 MHz microwave traveling wave reactor to heat the cat...

Influence of biochar pyrolysis temperature and post-treatment on the uptake of mercury from flue gas

USDA-ARS?s Scientific Manuscript database

Thermal processing, or pyrolysis, of plant and animal waste under oxygen limiting conditions results in a carbonized material called biochar. Most often, the proposed application for the biochar is soil applications as a conditioner or for the purpose of carbon sequestration. In this paper we demons...

Biochar as a soil amendment: Environmental friend or foe?

EPA Science Inventory

Pyrolysis to produce biofuels and biochar from biomass is not a new idea, but the use of pyrolysis to extract energy from biomass through a process that can be carbon neutral to carbon negative (i.e., reduces atmospheric CO2) is a novel application of an old technology to a curre...

Application of the distributed activation energy model to the kinetic study of pyrolysis of the fresh water algae Chlorococcum humicola.

PubMed

Kirtania, Kawnish; Bhattacharya, Sankar

2012-03-01

Apart from capturing carbon dioxide, fresh water algae can be used to produce biofuel. To assess the energy potential of Chlorococcum humicola, the alga's pyrolytic behavior was studied at heating rates of 5-20K/min in a thermobalance. To model the weight loss characteristics, an algorithm was developed based on the distributed activation energy model and applied to experimental data to extract the kinetics of the decomposition process. When the kinetic parameters estimated by this method were applied to another set of experimental data which were not used to estimate the parameters, the model was capable of predicting the pyrolysis behavior, in the new set of data with a R(2) value of 0.999479. The slow weight loss, that took place at the end of the pyrolysis process, was also accounted for by the proposed algorithm which is capable of predicting the pyrolysis kinetics of C. humicola at different heating rates. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

In-situ 3D visualization of composite microstructure during polymer-to-ceramic conversion

DOE PAGES

Larson, Natalie M.; Zok, Frank W.

2017-10-31

One route for producing fiber-reinforced ceramic-matrix composites entails repeated impregnation and pyrolysis of a preceramic polymer in a fiber preform. The process relies crucially on the development of networks of contiguous cracks during pyrolysis, thereby allowing further impregnation to attain nearly-full densification. The present study employs in-situ x-ray computed tomography (XCT) to reveal in three dimensions the evolution of matrix structure during pyrolysis of a SiC-based preceramic polymer to 1200 °C. Observations are used to guide the development of a taxonomy of crack geometries and crack structures and to identify the temporal sequence of their formation. A quantitative analysis ismore » employed to characterize effects of local microstructural dimensions on the conditions required to form cracks of various types. Complementary measurements of gas evolution and mass loss of the preceramic polymer during pyrolysis as well as changes in mass density and Young's modulus provide context for the physical changes revealed by XCT. Furthermore, the findings provide a foundation for future development of physics-based models to guide composite fabrication processes.« less

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

PubMed

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

2018-05-18

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

Study of combustion and emission characteristics of fuel derived from waste plastics by various waste to energy (W-t-E) conversion processes

NASA Astrophysics Data System (ADS)

Hazrat, M. A.; Rasul, M. G.; Khan, M. M. K.

2016-07-01

Reduction of plastic wastes by means of producing energy can be treated as a good investment in the waste management and recycling sectors. In this article, conversion of plastics into liquid fuel by two thermo-chemical processes, pyrolysis and gasification, are reviewed. The study showed that the catalytic pyrolysis of homogenous waste plastics produces better quality and higher quantity of liquefied fuel than that of non-catalytic pyrolysis process at a lower operating temperature. The syngas produced from gasification process, which occurs at higher temperature than the pyrolysis process, can be converted into diesel by the Fischer-Tropsch (FT) reaction process. Conducive bed material like Olivine in the gasification conversion process can remarkably reduce the production of tar. The waste plastics pyrolysis oil showed brake thermal efficiency (BTE) of about 27.75%, brake specific fuel consumption (BSFC) of 0.292 kg/kWh, unburned hydrocarbon emission (uHC) of 91 ppm and NOx emission of 904 ppm in comparison with the diesel for BTE of 28%, BSFC of 0.276 kg/kWh, uHC of 57 ppm and NOx of 855 ppm. Dissolution of Polystyrene (PS) into biodiesel also showed the potential of producing alternative transport fuel. It has been found from the literature that at higher engine speed, increased EPS (Expanded Polystyrene) quantity based biodiesel blends reduces CO, CO2, NOx and smoke emission. EPS-biodiesel fuel blend increases the brake thermal efficiency by 7.8%, specific fuel consumption (SFC) by 7.2% and reduces brake power (Pb) by 3.2%. More study using PS and EPS with other thermoplastics is needed to produce liquid fuel by dissolving them into biodiesel and to assess their suitability as a transport fuel. Furthermore, investigation to find out most suitable W-t-E process for effective recycling of the waste plastics as fuel for internal combustion engines is necessary to reduce environmental pollution and generate revenue which will be addressed in this article.

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.

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

Life cycle water footprint of hydrogenation-derived renewable diesel production from lignocellulosic biomass.

PubMed

Wong, Alain; Zhang, Hao; Kumar, Amit

2016-10-01

The conversion of lignocellulosic biomass to biofuel requires water. This study is focused on the production of hydrogenation-derived renewable diesel (HDRD) from lignocellulosic biomass. Although there has been considerable focus on the assessment of greenhouse gas (GHG) emissions, there is limited work on the assessment of the life cycle water footprint of HDRD production. This paper presents a life cycle water consumption study on lignocellulosic biomass to HDRD via pyrolysis and hydrothermal liquefaction (HTL) processes. The results of this study show that whole tree (i.e., tree chips) biomass has water requirements of 497.79 L/MJ HDRD and 376.16 L/MJ HDRD for production through fast pyrolysis and the HTL process, respectively. Forest residues (i.e., chips from branches and tops generated during logging operations) have water requirements of 338.58 L/MJ HDRD and 255.85 L/MJ HDRD for production through fast pyrolysis and the HTL process, respectively. Agricultural residues (i.e., straw from wheat, oats, and barley), which are more water efficient, have water requirements of 83.7 L/MJ HDRD and 59.1 L/MJ HDRD through fast pyrolysis and the HTL process, respectively. Differences in water use between feedstocks and conversion processes indicate that the choices of biomass feedstock and conversion pathway water efficiency are crucial factors affecting water use efficiency of HDRD production. Copyright © 2016 Elsevier Ltd. All rights reserved.

The effect of chars and their water extractable organic carbon (WEOC) fractions on atrazine adsorption-desorption processes

NASA Astrophysics Data System (ADS)

Cavoski, I.; Jablonowski, N.; Burauel, P.; Miano, T.

2012-04-01

Chars are carbonaceous material produced from different type of biomass by pyrolysis. They are known as highly effective adsorbents for atrazine therefore limiting its degradation and its diffusion into the aqueous phase. The aim of the present work is to study the effects of different chars and char's derived WEOC on atrazine sorption-desorption processes. The five chars been used in this study derived from: 1) fast pyrolysis from hard wood (FP1); 2) flash pyrolysis from soft wood (FP2); 3) slow pyrolysis from deciduous wood (CC); 4) gasification from deciduous wood (GC) and 5) the market, purchased as activated charcoal standard (AC). Short-term batch equilibration tests were conducted to assess the sorption-desorption behavior of 14C-labeled atrazine on the chars, with a special focus on the desorption behavior using successive dilution method with six consecutive desorption step. Chars and their WEOC were physically and chemically characterized. Results demonstrate that biomass and pyrolysis process used to produce chars affect their physical and chemical properties, and atrazine adsorption-desorption behavior. Atrazine desorption resulted from the positive and competitive interactions between WEOC and chars surfaces. WEOC pool play important role in atrazine adsorption-desorption behavior. FP1 and FP2 with higher concentration of WEOC showed higher desorption rates, whereas GC, CC and AC with insignificant WEOC concentration strongly adsorb atrazine with low desorption rates. According to our results, when high WEOC pools chars are concerned, an increase in atrazine desorption can be observed but further studies would help in confirming the present results.

Changes imposed by pyrolysis, thermal gasification and incineration on composition and phosphorus fertilizer quality of municipal sewage sludge.

PubMed

Thomsen, Tobias Pape; Sárossy, Zsuzsa; Ahrenfeldt, Jesper; Henriksen, Ulrik B; Frandsen, Flemming J; Müller-Stöver, Dorette Sophie

2017-08-01

Fertilizer quality of ash and char from incineration, gasification and pyrolysis of a single municipal sewage sludge sample were investigated by comparing composition and phosphorus (P) plant availability. A process for post oxidation of gasification ash and pyrolysis char was developed and the oxidized materials were investigated as well. Sequential extraction with full elemental balances of the extracted pools as well as scanning electron microscopy with energy dispersive X-ray spectroscopy were used to investigate the mechanisms driving the observed differences in composition and P plant availability in a short-term soil incubation study. The compositional changes related mainly to differences in the proximate composition as well as to the release of especially nitrogen, sulfur, cadmium and to some extent, phosphorus (P). The cadmium load per unit of P was reduced with 75-85% in gasification processes and 10-15% in pyrolysis whereas no reduction was observed in incineration processes. The influence on other heavy metals was less pronounced. The plant availability of P in the substrates varied from almost zero to almost 100% of the plant availability of P in the untreated sludge. Post-oxidized slow pyrolysis char was found to be the substrate with the highest P fertilizer value while ash from commercial fluid bed sludge incineration had the lowest P fertilizer quality. The high P fertilizer value in the best substrate is suggested to be a function of several different mechanisms including structural surface changes and improvements in the association of P to especially magnesium, calcium and aluminum. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gradient elution moving boundary electrophoresis enables rapid analysis of acids in complex biomass-derived streams

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

Munson, Matthew S.; Karp, Eric M.; Nimlos, Claire T.

Biomass conversion processes such as pretreatment, liquefaction, and pyrolysis often produce complex mixtures of intermediates that are a substantial challenge to analyze rapidly and reliably. To characterize these streams more comprehensively and efficiently, new techniques are needed to track species through biomass deconstruction and conversion processes. Here, we present the application of an emerging analytical method, gradient elution moving boundary electrophoresis (GEMBE), to quantify a suite of acids in a complex, biomass-derived streams from alkaline pretreatment of corn stover. GEMBE offers distinct advantages over common chromatography-spectrometry analytical approaches in terms of analysis time, sample preparation requirements, and cost of equipment.more » As demonstrated here, GEMBE is able to track 17 distinct compounds (oxalate, formate, succinate, malate, acetate, glycolate, protocatechuate, 3-hydroxypropanoate, lactate, glycerate, 2-hydroxybutanoate, 4-hydroxybenzoate, vanillate, p-coumarate, ferulate, sinapate, and acetovanillone). The lower limit of detection was compound dependent and ranged between 0.9 and 3.5 umol/L. Results from GEMBE were similar to recent results from an orthogonal method based on GCxGC-TOF/MS. Altogether, GEMBE offers a rapid, robust approach to analyze complex biomass-derived samples, and given the ease and convenience of deployment, may offer an analytical solution for online tracking of multiple types of biomass streams.« less

Gradient elution moving boundary electrophoresis enables rapid analysis of acids in complex biomass-derived streams

DOE PAGES

Munson, Matthew S.; Karp, Eric M.; Nimlos, Claire T.; ...

2016-09-27

Biomass conversion processes such as pretreatment, liquefaction, and pyrolysis often produce complex mixtures of intermediates that are a substantial challenge to analyze rapidly and reliably. To characterize these streams more comprehensively and efficiently, new techniques are needed to track species through biomass deconstruction and conversion processes. Here, we present the application of an emerging analytical method, gradient elution moving boundary electrophoresis (GEMBE), to quantify a suite of acids in a complex, biomass-derived streams from alkaline pretreatment of corn stover. GEMBE offers distinct advantages over common chromatography-spectrometry analytical approaches in terms of analysis time, sample preparation requirements, and cost of equipment.more » As demonstrated here, GEMBE is able to track 17 distinct compounds (oxalate, formate, succinate, malate, acetate, glycolate, protocatechuate, 3-hydroxypropanoate, lactate, glycerate, 2-hydroxybutanoate, 4-hydroxybenzoate, vanillate, p-coumarate, ferulate, sinapate, and acetovanillone). The lower limit of detection was compound dependent and ranged between 0.9 and 3.5 umol/L. Results from GEMBE were similar to recent results from an orthogonal method based on GCxGC-TOF/MS. Altogether, GEMBE offers a rapid, robust approach to analyze complex biomass-derived samples, and given the ease and convenience of deployment, may offer an analytical solution for online tracking of multiple types of biomass streams.« less

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.

Pyrolysis characteristics of integrated circuit boards at various particle sizes and temperatures.

PubMed

Chiang, Hung-Lung; Lin, Kuo-Hsiung; Lai, Mei-Hsiu; Chen, Ting-Chien; Ma, Sen-Yi

2007-10-01

A pyrolysis method was employed to recycle the metals and brominated compounds blended into printed circuit boards. This research investigated the effect of particle size and process temperature on the element composition of IC boards and pyrolytic residues, liquid products, and water-soluble ionic species in the exhaust, with the overall goal being to identify the pyrolysis conditions that will have the least impact on the environment. Integrated circuit (IC) boards were crushed into 5-40 mesh (0.71-4.4mm), and the crushed particles were pyrolyzed at temperatures ranging from 200 to 500 degrees C. The thermal decomposition kinetics were measured by a thermogravimetric (TG) analyzer. The composition of pyrolytic residues was analyzed by Energy Dispersive X-ray Spectrometer (EDS), Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). In addition, the element compositions of liquid products were analyzed by ICP-AES and ICP-MS. Pyrolytic exhaust was collected by a water-absorption system in an ice-bath cooler, and IC analysis showed that the absorbed solution comprised 11 ionic species. Based on the pyrolytic kinetic parameters of TG analysis and pyrolytic residues at various temperatures for 30 min, the effect of particle size was insignificant in this study, and temperature was the key factor for the IC board pyrolysis. Two stages of decomposition were found for IC board pyrolysis under nitrogen atmosphere. The activation energy was 38-47 kcal/mol for the first-stage reaction and 5.2-9.4 kcal/mol for the second-stage reaction. Metal content was low in the liquid by-product of the IC board pyrolysis process, which is an advantage in that the liquid product could be used as a fuel. Brominate and ammonium were the main water-soluble ionic species of the pyrolytic exhaust. A plan for their safe and effective disposal must be developed if the pyrolytic recycling process is to be applied to IC boards.

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.

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

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.

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.

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

Microwave pyrolysis of multilayer plastic waste (LDPE) using zeolite catalyst

NASA Astrophysics Data System (ADS)

Juliastuti, Sri Rachmania; Hendrianie, Nuniek; Ramadhan, Pandu Jati; Satria, Dama Husin

2017-05-01

To overcome the problem of garbage, especially plastic waste, environmental experts and scholars from various disciplines have conducted various studies and actions. One way to degrade the multilayer packaging plastic waste LDPE (Low Density Poliethylene) with microwave pyrolysis process by using natural zeolite catalysts. The purpose of this experiment was to determine the effect of temperature and time of microwave pyrolysis process by using natural zeolite catalyst to degrade the plastic waste LDPE and compare them. Pyrolysis process was done by using a closed glass reactor with a capacity of 500 ml, operated at a pressure of 1 atm and flowed nitrogen 0.5 1 / min. Plastic waste was LDPE, and natural zeolite was used as its catalyst. Sample was heated at temperature 300, 400, 500 or 550 °C and was kept during time variables of 45, 60, 75 and 90 minutes. Liquid product was analyzed by Gas Chromatography-Mass Spectrometry (GC-MS), raw material was analyzed by Fourier Transform Infrared (FTIR), and solid product was analyzed by X-Ray Fluorescene (XRF). From the experimental resulted in the best yield products of pyrolisis using natural zeolite at 550 °C and 90 minutes was 2.88 % of solid yield, 28.12 % of liquid yield and the highest hydrocarbon concentration of 19.02 %.

Processing real-world waste plastics by pyrolysis-reforming for hydrogen and high-value carbon nanotubes.

PubMed

Wu, Chunfei; Nahil, Mohamad A; Miskolczi, Norbert; Huang, Jun; Williams, Paul T

2014-01-01

Producing both hydrogen and high-value carbon nanotubes (CNTs) derived from waste plastics is reported here using a pyrolysis-reforming technology comprising a two-stage reaction system, in the presence of steam and a Ni-Mn-Al catalyst. The waste plastics consisted of plastics from a motor oil container (MOC), commercial waste high density polyethylene (HDPE) and regranulated HDPE waste containing polyvinyl chloride (PVC). The results show that hydrogen can be produced from the pyrolysis-reforming process, but also carbon nanotubes are formed on the catalyst. However, the content of 0.3 wt.% polyvinyl chloride in the waste HDPE (HDPE/PVC) has been shown to poison the catalyst and significantly reduce the quantity and purity of CNTs. The presence of sulfur has shown less influence on the production of CNTs in terms of quantity and CNT morphologies. Around 94.4 mmol H2 g(-1) plastic was obtained for the pyrolysis-reforming of HDPE waste in the presence of the Ni-Mn-Al catalyst and steam at a reforming temperature of 800 °C. The addition of steam in the process results in an increase of hydrogen production and reduction of carbon yield; in addition, the defects of CNTs, for example, edge dislocations were found to be increased with the introduction of steam (from Raman analysis).

Catalytic Pyrolysis of Waste Plastic Mixture

NASA Astrophysics Data System (ADS)

Sembiring, Ferdianta; Wahyu Purnomo, Chandra; Purwono, Suryo

2018-03-01

Inorganic waste especially plastics still become a major problem in many places. Low biodegradability of this materials causes the effort in recycling become very difficult. Most of the municipal solid waste (MSW) recycling facilities in developing country only use composting method to recover the organic fraction of the waste, while the inorganic fraction is still untreated. By pyrolysis, plastic waste can be treated to produce liquid fuels, flammable gas and chars. Reduction in volume and utilization of the liquid and gas as fuel are the major benefits of the process. By heat integration actually this process can become a self-sufficient system in terms of energy demand. However, the drawback of this process is usually due to the diverse type of plastic in the MSW creating low grade of liquid fuel and harmful gases. In this study, the mixture of plastics i.e. polypropylene (PP) and polyethylene terephthalate (PET) is treated using pyrolysis with catalyst in several operating temperature. PET is problematic to be treated using pyrolysis due to wax-like byproduct in liquid which may cause pipe clogging. The catalyst is the mixture of natural zeolite and bentonite which is able to handle PP and PET mixture feed to produce high grade liquid fuels in terms of calorific value and other fuel properties.

Sonochemical and photosonochemical degradation of 4-chlorophenol in aqueous media.

PubMed

Hamdaoui, Oualid; Naffrechoux, Emmanuel

2008-09-01

The degradation of 4-chlorophenol (4-CP) in aqueous media by 516 kHz ultrasonic irradiation was investigated in order to clarify the degradation mechanism. The degradation of concentrated 4-CP solution by means of ultrasound, UV irradiation and their combined application was also studied. The obtained results indicate that *OH radical are the primary reactive species responsible for 4-CP ultrasonic degradation. Very little 4-CP degradation occurs if the sonolysis is carried out in the presence of the *OH radical scavenger tert-butyl alcohol, also indicating that little or no pyrolysis of the compound occurs. The dominant degradation mechanism is the reaction of substrate with *OH radicals at the gas bubble-liquid interface rather than high temperature direct pyrolysis in ultrasonic cavities. This mechanism can explain the lower degradation rate of the ionic form of 4-CP that is partly due to the rapid dissociation of *OH radicals in alkaline solutions. The sonochemical destruction of concentrated 4-CP aqueous solution is obtained with low rate. Coupling photolysis with ultrasound irradiation results in increased efficiency compared to the individual processes operating at common conditions. Interestingly, the photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. This may be the result of three different oxidative processes direct photochemical action, high frequency sonochemistry and reaction with ozone produced by UV irradiation of air, dissolved in liquid phase because of the geyser effect of ultrasound streaming. Additionally, the photodecomposition, at 254 nm, of hydrogen peroxide produced by ultrasound generating *OH radical can partly explain the destruction enhancement.

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

DOEpatents

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

2014-12-02

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

Upgraded bio-oil production via catalytic fast co-pyrolysis of waste cooking oil and tea residual.

PubMed

Wang, Jia; Zhong, Zhaoping; Zhang, Bo; Ding, Kuan; Xue, Zeyu; Deng, Aidong; Ruan, Roger

2017-02-01

Catalytic fast co-pyrolysis (co-CFP) offers a concise and effective process to achieve an upgraded bio-oil production. In this paper, co-CFP experiments of waste cooking oil (WCO) and tea residual (TR) with HZSM-5 zeolites were carried out. The influences of pyrolysis reaction temperature and H/C ratio on pyrolytic products distribution and selectivities of aromatics were performed. Furthermore, the prevailing synergetic effect of target products during co-CFP process was investigated. Experimental results indicated that H/C ratio played a pivotal role in carbon yields of aromatics and olefins, and with H/C ratio increasing, the synergetic coefficient tended to increase, thus led to a dramatic growth of aromatics and olefins yields. Besides, the pyrolysis temperature made a significant contribution to carbon yields, and the yields of aromatics and olefins increased at first and then decreased at the researched temperature region. Note that 600°C was an optimum temperature as the maximum yields of aromatics and olefins could be achieved. Concerning the transportation fuel dependence and security on fossil fuels, co-CFP of WCO and TR provides a novel way to improve the quality and quantity of pyrolysis bio-oil, and thus contributes bioenergy accepted as a cost-competitive and promising alternative energy. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Effect of pre-pyrolysis mode on simultaneous introduction of nitrogen/oxygen-containing functional groups into the structure of bagasse-based mesoporous carbon and its influence on Cu(II) adsorption.

PubMed

Wan, Zeqing; Li, Kunquan

2018-03-01

A convenient effective microwave pre-pyrolysis treatment to synthesize biomass-based mesoporous carbon with higher nitrogen/oxygen-chelating adsorption for Cu(II) is reported here, in which phosphoric acid impregnated bagasse was used as a microwave absorber and porogen. For comparison, conventional electric-heating pyrolyzed carbon was prepared and doped with nitrogen/oxygen groups. Nitrogen adsorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS) and batch adsorption were employed to investigate the effects of the two pre-pyrolysis modes on the sample physicochemical and Cu(II) adsorptive properties. The 22-min-microwave-pyrolyzed bagasse mesoporous activated carbon (MBAC, 85.32% mesoporosity) contained 10.52% O, which is 3.94% more than electric-heating pyrolyzed mesoporous activated carbon (89.52% mesoporosity). After electrophilic aromatic substitutions of N/O doping, the former possessed more N (5.83%) and more O (21.40%), confirming that time-saving energy-efficient microwave pyrolysis favors the formation of defective C/O atoms in or at the edges of the graphite layer of MBAC, which are highly active and tend to act as preferred reactive positions for the doping of N/O-containing groups simultaneously compared with conventional electric-heating pyrolysis. These N and O species existed mainly as COOH, OH, NH and NH 2 functional groups, and were confirmed by XPS to be active sites for metal binding via electrostatic attraction, hydrogen bonding, a chelate effect and complexation, resulting in the great enhancement of Cu(II) adsorption. Langmuir isotherm and pseudo-second-order kinetic fitting further proved that Cu(II) adsorption by N/O-doped MBAC is ascribed mainly to chemisorption. Therefore, rapid microwave pre-pyrolysis provides a promising route to prepare excellent-performance N/O-doped carbon adsorbents. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermochemical Process Integration, Scale-Up, and Piloting Publications |

Science.gov Websites

-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility, Topics in Catalysis Image of a schematic of hot gas filter and ex situ Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors, NREL Technical Report Image

Method for Biochar Passivation Using Low Percent Oxygen

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

Smith, Kristin; Dupuis, Dan; Wilcox, Esther

2016-06-06

The thermochemical process development unit may be configured for pyrolysis or gasification. The pyrolysis unit operations include: feed transport system; entrained flow reactor; solids removal and collection; and liquid scrubbing, collection, and filtration. Char accumulates in the collection drums at a rate of ~1.5 kg/hr and must be passivated before it is stored or transported.

Utilization of eucalyptus for bioelectricity production in brazil via fast pyrolysis: a techno-economic analysis

USDA-ARS?s Scientific Manuscript database

In this study, a process model of a 2000 metric ton per day (MTPD) eucalyptus Tail Gas Reactive Pyrolysis (TGRP) and electricity generation plant was developed and simulated in SimSci Pro/II software for the purpose of evaluating its techno-economic viability in Brazil. Two scenarios were compared b...

Speculations on the nature of cellulose pyrolysis

Treesearch

F.J. Kilzer; A. Broido

1965-01-01

Consideration of the available data on cellulose pyrolysis suggests that, with relative importance depending upon heating rate in the temperature range 200-400°C, very pure cellulose decomposes by two competitive endothermic processes. lt is postulated that an unzipping reaction produces 1,4-anhydro-α-D-glucopyranose which rearranges to give levoglucosan. The other...

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

Treesearch

Qiangu Yan; Hossein Toghiani; Zhiyong Cai; Jilei Zhang

2014-01-01

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

Density functional theory study of the concerted pyrolysis mechanism for lignin models

Treesearch

Thomas Elder; Ariana Beste

2014-01-01

ABSTRACT: Studies on the pyrolysis mechanisms of lignin model compounds have largely focused on initial homolytic cleavage reactions. It has been noted, however, that concerted mechanisms may also account for observed product formation. In the current work, the latter processes are examined and compared to the former, by the application of density functional theory...

Natural Catalysts for Molten Cellulose Pyrolysis to Targeted Bio-Oils

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

Dauenhauer, Paul J.

2017-06-02

Catalysis of biomass biopolymer cellulose by alkaline earth metals is a fundamental chemistry relevant to energy processes including combustion, pyrolysis and gasification. In this work, the catalytic decomposition of cellulose by calcium ions was evaluated at high temperature (400-500°C) to elucidate the chemical mechanisms leading to the formation of volatile organic compounds.

Lifecycle Assessment of Biofuel Production from Wood Pyrolysis Technology

ERIC Educational Resources Information Center

Manyele, S. V.

2007-01-01

Due to a stronger dependency on biomass for energy, there is a need for improved technologies in biomass-to-energy conversion in Tanzania. This paper presents a life cycle assessment (LCA) of pyrolysis technology used for conversion of wood and wood waste to liquid biofuel. In particular, a survey of environmental impacts of the process is…

THE USE OF PYROLYSIS/GC/MS TO CHARACTERIZE THE ORGANIC QUALITY OF SURFACE WATERS; SPECIAL APPLICATION TO DRINKING WATER TREATMENT AND THE FORMATION OF DISINFECTION BYPRODUCTS

EPA Science Inventory

Natural Organ Material (NOM) in aquatic systems controls the effectiveness of engineered treatment processes and the fate of metals and pollutants in natural systems. At present less than 20% of NOM components can be identified. Pyrolysis-Gas Chromatography-Mass Spectrometry (P...

Organic emissions from coal pyrolysis: mutagenic effects.

PubMed Central

Braun, A G; Wornat, M J; Mitra, A; Sarofim, A F

1987-01-01

Four different types of coal have been pyrolyzed in a laminar flow, drop tube furnace in order to establish a relationship between polycyclic aromatic compound (PAC) evolution and mutagenicity. Temperatures of 900K to 1700K and particle residence times up to 0.3 sec were chosen to best simulate conditions of rapid rate pyrolysis in pulverized (44-53 microns) coal combustion. The specific mutagenic activity (i.e., the activity per unit sample weight) of extracts from particulates and volatiles captured on XAD-2 resin varied with coal type according to the order: subbituminous greater than high volatile bituminous greater than lignite greater than anthracite. Total mutagenic activity (the activity per gram of coal pyrolyzed), however, varied with coal type according to the order: high volatile bituminous much greater than subbituminous = lignite much greater than anthracite, due primarily to high organic yield during high volatile bituminous coal pyrolysis. Specific mutagenic activity peaked in a temperature range of 1300K to 1500K and generally appeared at higher temperatures and longer residence times than peak PAC production. PMID:3311724

Pyrolysis of polyolefins for increasing the yield of monomers' recovery

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

Donaj, Pawel J., E-mail: pawel@mse.kth.se; Kaminsky, W.; Buzeto, F.

2012-05-15

Highlights: Black-Right-Pointing-Pointer Thermal and catalytic pyrolysis of mixed polyolefins in fluidized bed has been studied. Black-Right-Pointing-Pointer We tested applicability of a commercial Ziegler-Natta catalyst (Z-N: TiCl{sub 4}/MgCl{sub 2}). Black-Right-Pointing-Pointer The catalyst has a strong influence on product distribution, increasing gas fraction. Black-Right-Pointing-Pointer At 650 Degree-Sign C the monomer generation increased by 55% when the catalyst was used. Black-Right-Pointing-Pointer We showed the concept of treatment of mixed polyolefins without a need of separation. - Abstract: Pyrolysis of plastic waste is an alternative way of plastic recovery and could be a potential solution for the increasing stream of solid waste. The objectivemore » of this work was to increase the yield the gaseous olefins (monomers) as feedstock for polymerization process and to test the applicability of a commercial Ziegler-Natta (Z-N): TiCl{sub 4}/MgCl{sub 2} for cracking a mixture of polyolefins consisted of 46% wt. of low density polyethylene (LDPE), 30% wt. of high density polyethylene (HDPE) and 24% wt. of polypropylene (PP). Two sets of experiments have been carried out at 500 and 650 Degree-Sign C via catalytic pyrolysis (1% of Z-N catalyst) and at 650 and 730 Degree-Sign C via only-thermal pyrolysis. These experiments have been conducted in a lab-scale, fluidized quartz-bed reactor of a capacity of 1-3 kg/h at Hamburg University. The results revealed a strong influence of temperature and presence of catalyst on the product distribution. The ratios of gas/liquid/solid mass fractions via thermal pyrolysis were: 36.9/48.4/15.7% wt. and 42.4/44.7/13.9% wt. at 650 and 730 Degree-Sign C while via catalytic pyrolysis were: 6.5/89.0/4.5% wt. and 54.3/41.9/3.8% wt. at 500 and 650 Degree-Sign C, respectively. At 650 Degree-Sign C the monomer generation increased by 55% up to 23.6% wt. of total pyrolysis products distribution while the catalyst was added. Obtained yields of olefins were compared with the naphtha steam cracking process and other potentially attractive processes for feedstock generation. The concept of closed cycle material flow for polyolefins has been discussed, showing the potential benefits of feedstock recycling in a plastic waste management.« less

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.

Pyrolysis of forest residues: An approach to techno-economics for bio-fuel production

DOE PAGES

Carrasco, Jose L.; Gunukula, Sampath; Boateng, Akwasi A.; ...

2017-04-01

Here, the techno-economics for producing liquid fuels from Maine forest residues were determined from a combination of: (1) laboratory experiments at USDA-ARS’s Eastern Regional Research Center using hog fuel (a secondary woody residue produced from mill byproducts such as sawdust, bark and shavings) as a feedstock for pyrolysis to establish product yields and composition, and (2) Aspen Plus® process simulation for a feed rate of 2000 dry metric tons per day to estimate energy requirements and equipment sizes. The simulated plant includes feedstock sizing and drying, pyrolysis, hydrogen production and hydrotreatment of pyrolysis oils. The biomass is converted into bio-oilmore » (61% yield), char (24%) and gases (15%) in the pyrolysis reactor, with an energy demand of 17%. The bio-oil is then hydrotreated to remove oxygen, thereby producing hydrocarbon fuels. The final mass yield of gasoline/diesel hydrocarbons is 16% with a 40% energy yield based on the dry biomass fed, this yield represents a fuel production of 51.9 gallons per dry metric ton of feedstock. A unique aspect of the process simulated herein is that pyrolysis char and gases are used as sources for both thermal energy and hydrogen, greatly decreasing the need to input fossil energy. The total capital investment for a grass-roots plant was estimated to be US$427 million with an annual operational cost of US$154 million. With a 30 year project life, a minimum fuel selling price was determined to be US$6.25 per gallon. The economic concerns are related to high capital costs, high feedstock costs and short hydrotreating catalyst lifetimes.« less

Pyrolysis of forest residues: An approach to techno-economics for bio-fuel production

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

Carrasco, Jose L.; Gunukula, Sampath; Boateng, Akwasi A.

Here, the techno-economics for producing liquid fuels from Maine forest residues were determined from a combination of: (1) laboratory experiments at USDA-ARS’s Eastern Regional Research Center using hog fuel (a secondary woody residue produced from mill byproducts such as sawdust, bark and shavings) as a feedstock for pyrolysis to establish product yields and composition, and (2) Aspen Plus® process simulation for a feed rate of 2000 dry metric tons per day to estimate energy requirements and equipment sizes. The simulated plant includes feedstock sizing and drying, pyrolysis, hydrogen production and hydrotreatment of pyrolysis oils. The biomass is converted into bio-oilmore » (61% yield), char (24%) and gases (15%) in the pyrolysis reactor, with an energy demand of 17%. The bio-oil is then hydrotreated to remove oxygen, thereby producing hydrocarbon fuels. The final mass yield of gasoline/diesel hydrocarbons is 16% with a 40% energy yield based on the dry biomass fed, this yield represents a fuel production of 51.9 gallons per dry metric ton of feedstock. A unique aspect of the process simulated herein is that pyrolysis char and gases are used as sources for both thermal energy and hydrogen, greatly decreasing the need to input fossil energy. The total capital investment for a grass-roots plant was estimated to be US$427 million with an annual operational cost of US$154 million. With a 30 year project life, a minimum fuel selling price was determined to be US$6.25 per gallon. The economic concerns are related to high capital costs, high feedstock costs and short hydrotreating catalyst lifetimes.« less

Incineration, pyrolysis and gasification of electronic waste

NASA Astrophysics Data System (ADS)

Gurgul, Agnieszka; Szczepaniak, Włodzimierz; Zabłocka-Malicka, Monika

2017-11-01

Three high temperature processes of the electronic waste processing: smelting/incineration, pyrolysis and gasification were shortly discussed. The most distinctive feature of electronic waste is complexity of components and their integration. This type of waste consists of polymeric materials and has high content of valuable metals that could be recovered. The purpose of thermal treatment of electronic waste is elimination of plastic components (especially epoxy resins) while leaving non-volatile mineral and metallic phases in more or less original forms. Additionally, the gaseous product of the process after cleaning may be used for energy recovery or as syngas.

A life cycle assessment of options for producing synthetic fuel via pyrolysis.

PubMed

Vienescu, D N; Wang, J; Le Gresley, A; Nixon, J D

2018-02-01

The aim of this study was to investigate the sustainability of producing synthetic fuels from biomass using thermochemical processing and different upgrading pathways. Life cycle assessment (LCA) models consisting of biomass collection, transportation, pre-treatment, pyrolysis and upgrading stages were developed. To reveal the environmental impacts associated with greater post-processing to achieve higher quality fuels, six different bio-oil upgrading scenarios were analysed and included esterification, ketonisation, hydrotreating and hydrocracking. Furthermore, to take into account the possible ranges in LCA inventory data, expected, optimistic and pessimistic values for producing and upgrading pyrolysis oils were evaluated. We found that the expected carbon dioxide equivalent emissions could be as high as 6000 gCO 2e /kg of upgraded fuel, which is greater than the emissions arising from the use of diesel fuel. Other environmental impacts occurring from the fuel production process are outlined, such as resource depletion, acidification and eutrophication. Copyright © 2017 Elsevier Ltd. All rights reserved.

Technological process and optimum design of organic materials vacuum pyrolysis and indium chlorinated separation from waste liquid crystal display panels.

PubMed

Ma, En; Xu, Zhenming

2013-12-15

In this study, a technology process including vacuum pyrolysis and vacuum chlorinated separation was proposed to convert waste liquid crystal display (LCD) panels into useful resources using self-design apparatuses. The suitable pyrolysis temperature and pressure are determined as 300°C and 50 Pa at first. The organic parts of the panels were converted to oil (79.10 wt%) and gas (2.93 wt%). Then the technology of separating indium was optimized by central composite design (CCD) under response surface methodology (RSM). The results indicated the indium recovery ratio was 99.97% when the particle size is less than 0.16 mm, the weight percentage of NH4Cl to glass powder is 50 wt% and temperature is 450°C. The research results show that the organic materials, indium and glass of LCD panel can be recovered during the recovery process efficiently and eco-friendly. Copyright © 2013 Elsevier B.V. All rights reserved.

Intoxication by cyanide in fires: a study in monkeys using polyacrylonitrile

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

Purser, D.A.; Grimshaw, P.; Berrill, K.R.

It is suspected that hydrogen cyanide (HCN) may be an important factor in incapacitating fire victims, but the effects of sublethal exposures are not well characterized. Also, the incapacitating effects of fire atmospheres result from exposure to a mixture of toxic products so that the contribution from each component is difficult to determine. The mechanisms of incapacitation in monkeys exposed to the pyrolysis products of polyacrylonitrile (PAN) were compared to those resulting from low level HCN gas exposures. The physiological effects of the PAN atmospheres were almost identical to those of HCN gas alone. They consisted of hyperventilation, followed bymore » loss of consciousness after 1-5 min, bradycardia with arrhythmias and T-wave abnormalities, and were followed by a rapid recovery after exposure. Hydrogen cyanide is considered to be the major toxic product formed by the pyrolysis of PAN. It is suggested that HCN may produce rapid incapacitation at low blood levels of cyanide in fires, while death may occur later due to carbon monoxide poisoning or other factors.« less

Incorporation of 13C labeled Pinus ponderosa needle and fine root litter into soil organic matter measured by Py-GC/MS-C-IRMS

NASA Astrophysics Data System (ADS)

Mambelli, S.; Gleixner, G.; Dawson, T. E.; Bird, J. A.; Torn, M. S.

2006-12-01

Developing effective strategies for enhancing C storage in soils requires understanding the influence of plant C quality. In turn, plant C quality impacts the decay continuum between plant residue and humified, stable SOM. This remains one of the least understood aspects of soil biogeochemistry. We investigated the initial phase of incorporation of 13C labeled Pinus ponderosa needle and fine root litter into SOM. The two litter types were placed in separate microcosms in the A horizon in a temperate conifer soil. Curie-point pyrolysis-gas chromatography coupled with on-line mass spectrometry and isotope ratio mass spectrometry (Py-GC/MS-C- IRMS) were used to determine the identity and the 13C enrichment of pyrolysis products (fragments of carbohydrates, lignin, proteins and lipids). We compared the two initial litter types, needles and fine roots, to samples of the bulk soil (A horizon, < 2mm) and soil humin fraction (from chemical solubility) obtained from each microcosm 1.5y after litter addition. Pyrolysis of plant material and SOM produced 56 suitable products for isotopic analysis; of them, 15 occurred in both the litter and bulk soil, 7 in both the litter and the humin fraction and 9 in both bulk soil and the humin fraction. The pyrolysis products found in common in the plant and soil were related either to polysaccharides or were non-specific and could have originated from various precursors. The data suggest that the majority of plant inputs, both from needles or fine roots, were degraded very rapidly. In the humin fraction, the most recalcitrant pool of C in soil, with a measured turnover time of 260y (this soil), only products from the fragmentation of polysaccharides and alkyl-benzene compounds were found. Comparisons of the enrichment normalized by input level suggest little difference between the incorporation of C from needles versus fine roots into SOM. The most enriched fragments in the humin fraction were products from polysaccharides degradation, indicating a very important role of microbial processing in the stabilization of C in SOM.

Cleavage and crosslinking of polymeric coal structures during pyrolysis. Final report

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

McMillen, D.F.; Malhotra, R.

1992-02-01

The ultimate objective of this project was to develop a better understanding of volatiles production to help optimize the yield and character of condensable coproducts during coal pyrolysis or mild gasification. The specific objectives were to (1) Develop pyrolysis procedures that minimize secondary reactions; and (2) Develop coal pretreatments that current knowledge suggests will prorate bond scission or prevent retrograde reactions. Our approach was to study the pyrolysis of coals and tar-loaded coals by using several techniques that span a range of heating rates and pressures. Slow-heating pyrolyses were performed at low pressures in the inlet of a field ionizationmore » mass spectrometer and at atmospheric pressures in a thermogravimetric analyzer. Moderately rapid-heating pyrolyses were performed in a vacuum TGA apparatus and in sealed silica ampules heated in a molten-salt bath. The fastest heating rates were achieved with laser pyrolysis at about 30,000 X/s. The high tar yield seen in this work where the entire volume of the coal particle becomes hot and fluid at very nearly the same time, taken together with the evident non-vapor transport of the tar under these conditions, emphasizes the importance of better understanding the development of fluidity during coal heating. This specifically includes the profound effects--long-recognized but poorly understood that mild oxidation has in suppressing coal fluidity. It also includes the more recently recognized fact that heating in the presence of an inert gas produced substantially greater fluidity than does heating in the presence of combustion gases, even if the conditions are very fuel rich and all the oxygen itself has already been consumed when the coal particles are encountered.« less

Cleavage and crosslinking of polymeric coal structures during pyrolysis

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

McMillen, D.F.; Malhotra, R.

1992-02-01

The ultimate objective of this project was to develop a better understanding of volatiles production to help optimize the yield and character of condensable coproducts during coal pyrolysis or mild gasification. The specific objectives were to (1) Develop pyrolysis procedures that minimize secondary reactions; and (2) Develop coal pretreatments that current knowledge suggests will prorate bond scission or prevent retrograde reactions. Our approach was to study the pyrolysis of coals and tar-loaded coals by using several techniques that span a range of heating rates and pressures. Slow-heating pyrolyses were performed at low pressures in the inlet of a field ionizationmore » mass spectrometer and at atmospheric pressures in a thermogravimetric analyzer. Moderately rapid-heating pyrolyses were performed in a vacuum TGA apparatus and in sealed silica ampules heated in a molten-salt bath. The fastest heating rates were achieved with laser pyrolysis at about 30,000 X/s. The high tar yield seen in this work where the entire volume of the coal particle becomes hot and fluid at very nearly the same time, taken together with the evident non-vapor transport of the tar under these conditions, emphasizes the importance of better understanding the development of fluidity during coal heating. This specifically includes the profound effects--long-recognized but poorly understood that mild oxidation has in suppressing coal fluidity. It also includes the more recently recognized fact that heating in the presence of an inert gas produced substantially greater fluidity than does heating in the presence of combustion gases, even if the conditions are very fuel rich and all the oxygen itself has already been consumed when the coal particles are encountered.« less

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.

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.

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.

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.

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.

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.

In Depth Analysis of AVCOAT TPS Response to a Reentry Flow

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

Titov, E. V.; Kumar, Rakesh; Levin, D. A.

2011-05-20

Modeling of the high altitude portion of reentry vehicle trajectories with DSMC or statistical BGK solvers requires accurate evaluation of the boundary conditions at the ablating TPS surface. Presented in this article is a model which takes into account the complex ablation physics including the production of pyrolysis gases, and chemistry at the TPS surface. Since the ablation process is time dependent the modeling of the material response to the high energy reentry flow starts with the solution of the rarefied flow over the vehicle and then loosely couples with the material response. The objective of the present work ismore » to carry out conjugate thermal analysis by weakly coupling a flow solver to a material thermal response model. The latter model solves the one dimensional heat conduction equation accounting for the pyrolysis process that takes place in the reaction zone of an ablative thermal protection system (TPS) material. An estimate of the temperature range within which the pyrolysis reaction (decomposition and volatilization) takes place is obtained from Ref. [1]. The pyrolysis reaction results in the formation of char and the release of gases through the porous charred material. These gases remove additional amount of heat as they pass through the material, thus cooling the material (the process known as transpiration cooling). In the present work, we incorporate the transpiration cooling model in the material thermal response code in addition to the pyrolysis model. The flow in the boundary layer and in the vicinity of the TPS material is in the transitional flow regime. Therefore, we use a previously validated statistical BGK method to model the flow physics in the vicinity of the micro-cracks, since the BGK method allows simulations of flow at pressures higher than can be computed using DSMC.« less

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

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.

Thermogravimetric analysis, kinetic study, and pyrolysis-GC/MS analysis of 1,1'-azobis-1,2,3-triazole and 4,4'-azobis-1,2,4-triazole.

PubMed

Jia, Chenhui; Li, Yuchuan; Zhang, Shujuan; Fei, Teng; Pang, Siping

2018-03-01

In general, the greater the number of directly linked nitrogen atoms in a molecule, the better its energetic performance, while the stability will be accordingly lower. But 1,1'-azobis-1,2,3-triazole (1) and 4,4'-azobis-1,2,4-triazole (2) show remarkable properties, such as high enthalpies of formation, high melting points, and relatively high stabilities. In order to rationalize this unexpected behavior of the two compounds, it is necessary to study their thermal decompositions and pyrolyses. Although a great deal of research has been focused on the synthesis and characterization of energetic materials with 1 and 2 as the backbone, a complete report on their fundamental thermodynamic parameters and thermal decomposition properties has not been published. Thermogravimetric-differential scanning calorimetry were used to obtain the thermal decomposition data of the title compounds. Kissinger and Ozawa-Doyle methods, the two selected non-isothermal methods, are presented for analysis of the solid-state kinetic data. Pyrolysis-gas chromatography/mass spectrometry was used to study the pyrolysis process of the title compounds. The DSC curves show that the thermal decompositions of 1 and 2 are at different heating rates involved a single exothermic process. The TG curves provide insight into the total weight losses from the compounds associated with this process. At different pyrolysis temperatures, the compositions and types of the pyrolysis products differ greatly and the pyrolysis reaction at 500 °C is more thorough than 400 °C. Apparent activation energies (E) and pre-exponential factors (lnA/s -1 ) are 291.4 kJ mol -1 and 75.53 for 1; 396.2 kJ mol -1 and 80.98 for 2 (Kissinger). The values of E are 284.5 kJ mol -1 for 1 and 386.1 kJ mol -1 for 2 (Ozawa-Doyle). The critical temperature of thermal explosion (T b ) is evaluated as 187.01 °C for 1 and 282.78 °C for 2. The title compounds were broken into small fragment ions under the pyrolysis conditions, which then might undergo a multitude of collisions and numerous other reactions, resulting in the formation of C 2 N 2 (m/z 52), etc., before being analyzed by the GC/MS system.

Past, Present, and Future Production of Bio-oil

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

Steele, Philip; Yu, Fei; Gajjela, Sanjeev

Bio-oil is a liquid product produced by fast pyrol-ysis of biomass. The fast pyrolysis is performed by heating the biomass rapidly (2 sec) at temperatures ranging from 350 to 650 oC. The vapors produced by this rapid heating are then condensed to produce a dark brown water-based emulsion composed of frag-ments of the original hemicellulose, cellulose and lignin molecules contained in the biomass. Yields range from 60 to 75% based on the feedstock type and the pyrolysis reactor employed. The bio-oil pro-duced by this process has a number of negative prop-erties that are produced mainly by the high oxygen contentmore » (40 to 50%) contributed by that contained in water (25 to 30% of total mass) and oxygenated compounds. Each bio-oil contains hundreds of chemi-cal compounds. The chemical composition of bio-oil renders it a very recalcitrant chemical compound. To date, the difficulties in utilizing bio-oil have limited its commercial development to the production of liq-uid smoke as food flavoring. Practitioners have at-tempted to utilize raw bio-oil as a fuel; they have also applied many techniques to upgrade bio-oil to a fuel. Attempts to utilize raw bio-oil as a combustion engine fuel have resulted in engine or turbine dam-age; however, Stirling engines have been shown to successfully combust raw bio-oil without damage. Utilization of raw bio-oil as a boiler fuel has met with more success and an ASTM standard has recently been released describing bio-oil characteristics in relation to assigned fuel grades. However, commercialization has been slow to follow and no reports of distribution of these bio-oil boiler fuels have been reported. Co-feeding raw bio-oil with coal has been successfully performed but no current power generation facilities are following this practice. Upgrading of bio-oils to hydrocarbons via hydroprocessing is being performed by several organizations. Currently, limited catalyst life is the obstacle to commercialization of this tech-nology. Researchers have developed means to increase the anhydrosugars content of bio-oil above the usual 3% produced during normal pyrolysis by mild acid pretreatment of the biomass feedstock. Mississippi State University has developed a proprietary method to produce an aqueous fraction containing more than 50% of anhydrosugars content. These anhydrosugars can be catalyzed to hydrogen or hydrocarbons; alter-nately, the aqueous fraction can be hydrolyzed to pro-duce a high-glucose content. The hydrolyzed product can then be filtered to remove microbial inhibitor compounds followed by production of alcohols by fer-mentation. Production of bio-oil is now considered a major candidate as a technology promising production of drop-in transportation and boiler fuels.« less

Biochar from Biosolids Pyrolysis: A Review.

PubMed

Paz-Ferreiro, Jorge; Nieto, Aurora; Méndez, Ana; Askeland, Matthew Peter James; Gascó, Gabriel

2018-05-10

Ever increasing volumes of biosolids (treated sewage sludge) are being produced by municipal wastewater facilities. This is a consequence of the continued expansion of urban areas, which in turn require the commissioning of new treatment plants or upgrades to existing facilities. Biosolids contain nutrients and energy which can be used in agriculture or waste-to-energy processes. Biosolids have been disposed of in landfills, but there is an increasing pressure from regulators to phase out landfilling. This article performs a critical review on options for the management of biosolids with a focus on pyrolysis and the application of the solid fraction of pyrolysis (biochar) into soil.

Experimental study on the liquefaction of cellulose in supercritical ethanol

NASA Astrophysics Data System (ADS)

Peng, Jinxing; Liu, Xinyuan; Bao, Zhenbo

2018-03-01

Cellulose is the major composition of solid waste for producing biofuel; cellulose liquefaction is helpful for realizing biomass supercritical liquefaction process. This paper is taking supercritical ethanol as the medium, liquefied cellulose with the intermittence installation of high press cauldron. Experiments have studied technical condition and the technology parameter of cellulose liquefaction in supercritical ethanol, and the pyrolysis mechanism was analysed based on the pyrolysis product. Results show that cellulose can be liquefied, can get good effect through appropriate technology condition. Under not catalyst, highest liquefaction rate of cellulose can reach 73.5%. The composition of the pyrolysis product was determined by GC-MS.

Biochar from Biosolids Pyrolysis: A Review

PubMed Central

Nieto, Aurora; Méndez, Ana; Askeland, Matthew Peter James; Gascó, Gabriel

2018-01-01

Ever increasing volumes of biosolids (treated sewage sludge) are being produced by municipal wastewater facilities. This is a consequence of the continued expansion of urban areas, which in turn require the commissioning of new treatment plants or upgrades to existing facilities. Biosolids contain nutrients and energy which can be used in agriculture or waste-to-energy processes. Biosolids have been disposed of in landfills, but there is an increasing pressure from regulators to phase out landfilling. This article performs a critical review on options for the management of biosolids with a focus on pyrolysis and the application of the solid fraction of pyrolysis (biochar) into soil. PMID:29748488

Syngas obtained by microwave pyrolysis of household wastes as feedstock for polyhydroxyalkanoate production in Rhodospirillum rubrum.

PubMed

Revelles, Olga; Beneroso, Daniel; Menéndez, J Angel; Arenillas, Ana; García, J Luis; Prieto, M Auxiliadora

2017-11-01

The massive production of urban and agricultural wastes has promoted a clear need for alternative processes of disposal and waste management. The potential use of municipal solid wastes (MSW) as feedstock for the production of polyhydroxyalkanoates (PHA) by a process known as syngas fermentation is considered herein as an attractive bio-economic strategy to reduce these wastes. In this work, we have evaluated the potential of Rhodospirillum rubrum as microbial cell factory for the synthesis of PHA from syngas produced by microwave pyrolysis of the MSW organic fraction from a European city (Seville). Growth rate, uptake rate, biomass yield and PHA production from syngas in R. rubrum have been analysed. The results revealed the strong robustness of this syngas fermentation where the purity of the syngas is not a critical constraint for PHA production. Microwave-induced pyrolysis is a tangible alternative to standard pyrolysis, because it can reduce cost in terms of energy and time as well as increase syngas production, providing a satisfactory PHA yield. © 2016 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Chemical looping combustion: A new low-dioxin energy conversion technology.

PubMed

Hua, Xiuning; Wang, Wei

2015-06-01

Dioxin production is a worldwide concern because of its persistence and carcinogenic, teratogenic, and mutagenic effects. The pyrolysis-chemical looping combustion process of disposing solid waste is an alternative to traditional solid waste incineration developed to reduce the dioxin production. Based on the equilibrium composition of the Deacon reaction, pyrolysis gas oxidized by seven common oxygen carriers, namely, CuO, NiO, CaSO4, CoO, Fe2O3, Mn3O4, and FeTiO3, is studied and compared with the pyrolysis gas directly combusted by air. The result shows that the activity of the Deacon reaction for oxygen carriers is lower than that for air. For four typical oxygen carriers (CuO, NiO, Fe2O3, and FeTiO3), the influences of temperature, pressure, gas composition, and tar on the Deacon reaction are discussed in detail. According to these simulation results, the dioxin production in China, Europe, the United States, and Japan is predicted for solid waste disposal by the pyrolysis-chemical looping combustion process. Thermodynamic analysis results in this paper show that chemical looping combustion can reduce dioxin production in the disposal of solid waste. Copyright © 2015. Published by Elsevier B.V.

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.

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.

Concepts of risk assesment of complex chemical mixtures in laser pyrolysis fumes

NASA Astrophysics Data System (ADS)

Weber, Lothar W.; Meier, Thomas H.

1996-01-01

Laser-tissue interaction may generate by energy absorption a complex mixture of gaseous, volatile, semi-volatile and particular substances. At the time about 150 different components are known from IR-laser interaction with different organ tissues like liver, fat, muscle and skin. The laser-tissue interaction process thereby is dominated by heating processes, which is confirmed by the similarity of formed chemical products in comparison with conventional cooking processes for food preparation. With the identified chemical substances and relative amounts in backmind a walk along the think path of risk assessment with special reference to pyrolysis products is given. The main way of intake of pyrolysis products is the inhalative one, which results from the fine aerosols formed and the high spreading energy out of the irradiated source. The liberated amounts of irritative chemicals as (unsaturated) aldehydes, heterocycles of bad odor and possibly cancerogenic acting substances relates to some (mu) g/g of laser vaporized tissue. With regard to this exposure level in a hypothetic one cubic meter volume the occupational limit settings are far away. Even indoor air exposure levels are in nearly all cases underwent, for the content of bad smelling substances forces an effective ventilation. Up to now no laser typical chemical substance could be identified, which was not elsewhere known by frying or baking processes of meat, food or familiar. Starting with the GRAS concept of 1957 the process of risk assessment by modified food products and new ingredients is still improofing. The same process of risk assessment is governing the laser pyrolysis products of mammalian tissues. By use of sufficient suction around the laser tissue source the odor problems as well as the toxicological problems could be solved.

Using vacuum pyrolysis and mechanical processing for recycling waste printed circuit boards.

PubMed

Long, Laishou; Sun, Shuiyu; Zhong, Sheng; Dai, Wencan; Liu, Jingyong; Song, Weifeng

2010-05-15

The constant growth in generation of waste printed circuit boards (WPCB) poses a huge disposal problem because they consist of a heterogeneous mixture of organic and metallic chemicals as well as glass fiber. Also the presence of heavy metals, such as Pb and Cd turns this scrap into hazardous waste. Therefore, recycling of WPCB is an important subject not only from the recovery of valuable materials but also from the treatment of waste. The aim of this study was to present a recycling process without negative impact to the environment as an alternative for recycling WPCB. In this work, a process technology containing vacuum pyrolysis and mechanical processing was employed to recycle WPCB. At the first stage of this work, the WPCB was pyrolyzed under vacuum in a self-made batch pilot-scale fixed bed reactor to recycle organic resins contained in the WPCB. By vacuum pyrolysis the organic matter was decomposed to gases and liquids which could be used as fuels or chemical material resources, however, the inorganic WPCB matter was left unaltered as solid residues. At the second stage, the residues obtained at the first stage were investigated to separate and recover the copper through mechanical processing such as crushing, screening, and gravity separation. The copper grade of 99.50% with recovery of 99.86% based on the whole WPCB was obtained. And the glass fiber could be obtained by calcinations in a muffle furnace at 600 degrees C for 10 min. This study had demonstrated the feasibility of vacuum pyrolysis and mechanical processing for recycling WPCB. Copyright (c) 2009 Elsevier B.V. All rights reserved.

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

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

Gangwal, Santosh; Meng, Jiajia; McCabe, Kevin

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

High density Polyethylene plastic waste treatment with microwave heating pyrolysis method using coconut-shell activated carbon to produce alternative fuels

NASA Astrophysics Data System (ADS)

Juliastuti, S. R.; Hisbullah, M. I.; Abdillah, M.

2018-03-01

Pyrolysis is a technology that could crack polimer such as plastic waste into alternative fuels. This research uses microwave heating methode, which more efficient than conventional heating methode. The plastic waste used is 200 grams of HDPE, with feed to catalyst weight ratio are 1:1, 0.6:1, 0.4:1. Pyrolysis was run at temperatures of 250, 300, 350, & 400 °C for 15, 30 and 45 min. From the experimental result, the best variable of pyrolysis process with microwave method is at 45 minutes, at 400°C, and 1:1 feed to catalyst weight ratio. Result shows that yield of liquid and gas product is 99.22%; yield of residue is 0.78%; value of liquid product’s composition (cycloparaffin and n-paraffin) is 54.09% and concentration of methane gas is 10.2%.

Pyrolysis of a waste from the grinding of scrap tyres.

PubMed

Fernández, A M; Barriocanal, C; Alvarez, R

2012-02-15

The fibres that are used to reinforce tyres can be recovered as a waste in the process of grinding of scrap tyres. In this paper beneficiation through pyrolysis is studied since the fibres are made up of polymers with a small amount of rubber because the latter is difficult to separate. The experiments were performed at three temperatures (400, 550 and 900°C) in a horizontal oven. The three products - gas, oil and char - obtained from the pyrolysis were investigated. The composition of the gas was analyzed by means of gas chromatography. The oil was studied by gas chromatography and infrared spectroscopy. The char porous structure was determined by N(2) adsorption. In addition, the topography of the chars was studied by means of scanning electron microscopy (SEM). The products resulting from the pyrolysis of the fibres were compared with those obtained from scrap rubber. Copyright © 2011 Elsevier B.V. All rights reserved.

Lunar oxygen production by pyrolysis of regolith

NASA Technical Reports Server (NTRS)

Senior, Constance L.

1991-01-01

Oxygen represents one of the most desirable products of lunar mining and manufacturing. Among the many processes which have been proposed for oxygen production, pyrolysis stands out as one which is uncomplicated and easy to bootstrap. Pyrolysis or vapor-phase reduction involves heating regolith to temperatures sufficient to allow partial decomposition and vaporization. Some metal oxides give up oxygen upon heating, either in the gas phase to form reduced gaseous species or in the condensed phase to form a metallic phase. Based on preliminary experiments and equilibrium calculations, the temperatures needed for pyrolysis are expected to be in the range of 2000 to 2200 K, giving total gas pressures of 0.001 to 0.1 torr. Bulk regolith can be used as a feedstock without beneficiation with concentrated solar radiation supplying most of energy needed. Further, selective condensation of metal-containing species from the gas phase may yield metallic iron and silicon as byproducts.

Specialists' workshop on fast pyrolysis of biomass

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

Not Available

1980-01-01

This workshop brought together most of those who are currently working in or have published significant findings in the area of fast pyrolysis of biomass or biomass-derived materials, with the goal of attaining a better understanding of the dominant mechanisms which produce olefins, oxygenated liquids, char, and tars. In addition, background papers were given in hydrocarbon pyrolysis, slow pyrolysis of biomass, and techniques for powdered-feedstock preparation in order that the other papers did not need to introduce in depth these concepts in their presentations for continuity. In general, the authors were requested to present summaries of experimental data with asmore » much interpretation of that data as possible with regard to mechanisms and process variables such as heat flux, temperatures, partial pressure, feedstock, particle size, heating rates, residence time, etc. Separate abstracts have been prepared of each presentation for inclusion in the Energy Data Base. (DMC)« less

Fabrication of ZnO nanorod using spray-pyrolysis and chemical bath deposition method

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

Ramadhani, Muhammad F., E-mail: brian@tf.itb.ac.id; Pasaribu, Maruli A. H., E-mail: brian@tf.itb.ac.id; Yuliarto, Brian, E-mail: brian@tf.itb.ac.id

2014-02-24

ZnO thin films with nanorod structure were deposited using Ultrasonic Spray Pyrolysis method for seed growth, and Chemical Bath Deposition (CBD) for nanorod growth. High purity Zn-hydrate and Urea are used to control Ph were dissolved in ethanol and aqua bidest in Ultrasonic Spray Pyrolysis process. Glass substrate was placed above the heater plate of reaction chamber, and subsequently sprayed with the range duration of 5, 10 and 20 minutes at the temperatures of 3500 C. As for the Chemical Bath Deposition, the glass substrate with ZnO seed on the surface was immerse to Zn-hydrate, HMTA (Hexa Methylene Tetra Amine)more » and deionized water solution for duration of 3, 5 and 7 hour and temperatures of 600 C, washed in distilled water, dried, and annealed at 3500 C for an hour. The characterization of samples was carried out to reveal the surface morphology using Scanning Electron Microscopy (SEM). From the data, the combination of 5 minutes of Ultrasonic Spray Pyrolysis process and 3 hour of CBD has showed the best structure of nanorod. Meanwhile the longer Spraying process and CBD yield the bigger nanorod structure that have been made, and it makes the films more dense which make the nanorod collide each other and as a result produce unsymetric nanorod structure.« less

Prediction of biochar yield from cattle manure pyrolysis via least squares support vector machine intelligent approach.

PubMed

Cao, Hongliang; Xin, Ya; Yuan, Qiaoxia

2016-02-01

To predict conveniently the biochar yield from cattle manure pyrolysis, intelligent modeling approach was introduced in this research. A traditional artificial neural networks (ANN) model and a novel least squares support vector machine (LS-SVM) model were developed. For the identification and prediction evaluation of the models, a data set with 33 experimental data was used, which were obtained using a laboratory-scale fixed bed reaction system. The results demonstrated that the intelligent modeling approach is greatly convenient and effective for the prediction of the biochar yield. In particular, the novel LS-SVM model has a more satisfying predicting performance and its robustness is better than the traditional ANN model. The introduction and application of the LS-SVM modeling method gives a successful example, which is a good reference for the modeling study of cattle manure pyrolysis process, even other similar processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

In Situ Infrared Spectroscopic Studies of Molecular Layer Deposition and Atomic Layer Etching Processes

NASA Astrophysics Data System (ADS)

DuMont, Jaime Willadean

In this thesis, in situ Fourier transform infrared (FTIR) spectroscopy was used to study: i) the growth and pyrolysis of molecular layer deposition (MLD) films. ii) the surface chemistry of atomic layer etching (ALE) processes. Atomic layer processes such as molecular layer deposition (MLD) and atomic layer etching (ALE) are techniques that can add or remove material with atomic level precision using sequential, self-limiting surface reactions. Deposition and removal processes at the atomic scale are powerful tools for many industrial and research applications such as energy storage and semiconductor nanofabrication. The first section of this thesis describes the chemistry of reactions leading to the MLD of aluminum and tin alkoxide polymer films known as "alucone" and "tincone", respectively. The subsequent pyrolysis of these films to produce metal oxide/carbon composites was also investigated. In situ FTIR spectroscopy was conducted to monitor surface species during MLD film growth and to monitor the films background infrared absorbance versus pyrolysis temperature. Ex situ techniques such as transmission electron microscopy (TEM), four-point probe and X-ray diffraction (XRD) were utilized to study the properties of the films post-pyrolysis. TEM confirmed that the pyrolyzed films maintained conformality during post-processing. Four-point probe monitored film resistivity versus pyrolysis temperature and XRD determined the film crystallinity. The second section of this thesis focuses on the surface chemistry of Al2O3 and SiO2 ALE processes, respectively. Thermal ALE processes have been recently developed which utilize sequential fluorination and ligand exchange reactions. An intimate knowledge of the surface chemistry is important in understanding the ALE process. In this section, the competition between the Al2O3 etching and AlF 3 growth that occur during sequential HF (fluorinating agent) and TMA (ligand exchange) exposures is investigated using in situ FTIR spectroscopy. Also included in this section is the first demonstration of thermal ALE for SiO2. In situ FTIR spectroscopy was conducted to monitor the loss of bulk Si-O vibrational modes corresponding to the removal of SiO2. FTIR was also used to monitor surface species during each ALE half cycle and to verify self-limiting behavior. X-ray reflectivity experiments were conducted to establish etch rates on thermal oxide silicon wafers.

Thermochemical conversion of microalgal biomass into biofuels: a review.

PubMed

Chen, Wei-Hsin; Lin, Bo-Jhih; Huang, Ming-Yueh; Chang, Jo-Shu

2015-05-01

Following first-generation and second-generation biofuels produced from food and non-food crops, respectively, algal biomass has become an important feedstock for the production of third-generation biofuels. Microalgal biomass is characterized by rapid growth and high carbon fixing efficiency when they grow. On account of potential of mass production and greenhouse gas uptake, microalgae are promising feedstocks for biofuels development. Thermochemical conversion is an effective process for biofuel production from biomass. The technology mainly includes torrefaction, liquefaction, pyrolysis, and gasification. Through these conversion technologies, solid, liquid, and gaseous biofuels are produced from microalgae for heat and power generation. The liquid bio-oils can further be upgraded for chemicals, while the synthesis gas can be synthesized into liquid fuels. This paper aims to provide a state-of-the-art review of the thermochemical conversion technologies of microalgal biomass into fuels. Detailed conversion processes and their outcome are also addressed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Process for producing phenolic compounds from lignins

DOEpatents

Agblevor, Foster A.

1998-01-01

A process for the production of low molecular weight phenolic compounds from lignins through the pyrolysis of the lignins in the presence of a strong base. In a preferred embodiment, potassium hydroxide is present in an amount of from about 0.1% to about 5% by weight, the pyrolysis temperature is from about 400.degree. C. to about 600.degree. C. at atmospheric pressure, and the time period for substantial completion of the reaction is from about 1-3 minutes. Examples of low molecular weight phenolic compounds produced include methoxyphenols, non-methoxylated phenols, and mixtures thereof.

Literature survey of properties of synfuels derived from coal

NASA Technical Reports Server (NTRS)

Flores, F.

1982-01-01

A literature survey of the properties of synfuels for ground-based turbine applications is presented. The four major concepts for converting coal into liquid fuels (solvent extraction, catalytic liquefaction, pyrolysis, and indirect liquefaction), and the most important concepts for coal gasification (fixed bed, fluidized bed, entrained flow, and underground gasification) are described. Upgrading processes for coal derived liquid fuels are also described. Data presented for liquid fuels derived from various processes, including H-coal, synthoil, solvent refined coal, COED, donor solvent, zinc chloride hydrocracking, co-steam, and flash pyrolysis. Typical composition, and property data is also presented for low and medium-BTU gases derived from the various coal gasification processes.

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

Organosilicon Polymers as Precursors for Silicon Containing Ceramics: Recent Developments.

DTIC Science & Technology

1987-08-14

the polymer to a ceramic material, hopefully of the desired composition . In the latter alternative, shrinkage during pyrolysis should not be great...carbon-carbon composite materials. In order to have a useful preceramic polymer . considerations of structure and reactivitv are of paramount importance...process so that on pyrolysis non-volatile, three-dimensional networks (which lead to maximum weight retention) are formed. Thus. preceramic polymer

Laboratory for the Processing and Evaluation of Inorganic Matrix Composites

DTIC Science & Technology

1989-06-01

preceramic polymers .’ Ceramic data (yield and elemental composition ) for the pyrolysis ... polymer matrix composites can feature apparent fracture energies as high as those of unreinforced metals (Ashby and Jones 1980). I I Fig. 1 SiC VLS...materials has pyrolysis of shaped bodies of such " preceramic " polymers . received much attention in recent years.’ This procedure The issues that are

The role of moisture on combustion of pyrolysis gases in wildland fires

Treesearch

Selina C. Ferguson; Ambarish Dahale; Babak Shotorban; S. Mahalingam; David R. Weise

2013-01-01

The role of water vapor, originated from the moisture content in vegetation, on the combustion process was investigated via simulating an opposed diffusion flame and a laminar premixed flame with pyrolysis gases as the fuel and air as the oxidizer. The fuel was mixed with water vapor, and the simulation was repeated for various water mole fractions. In both of the...

Influence of vegetation moisture on combustion of pyrolysis gases in wildland fires

Treesearch

S.C. Dover; A.R. Dahale; B. Shotorban; S. Mahalingam; D.R. Weise

2011-01-01

Since wildland fires occur in living vegetation, the fuel moisture content must be considered in order to correctly predict the behavior of the fire. One facet of combustion of pyrolysis gases that has not been considered in previous research is the effect of moisture on the combustion process. This effect is investigated by using CHEMKIN software to study an opposed...

A Review on Biomass Torrefaction Process and Product Properties

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

Jaya Shankar Tumuluru; Shahab Sokhansanj; Christopher T. Wright

2011-08-01

Biomass Torrefaction is gaining attention as an important preprocessing step to improve the quality of biomass in terms of physical properties and chemical composition. Torrefaction is a slow heating of biomass in an inert or reduced environment to a maximum temperature of approximately 300 C. Torrefaction can also be defined as a group of products resulting from the partially controlled and isothermal pyrolysis of biomass occurring in a temperature range of 200-280 C. Thus, the process can be called a mild pyrolysis as it occurs at the lower temperature range of the pyrolysis process. At the end of the torrefactionmore » process, a solid uniform product with lower moisture content and higher energy content than raw biomass is produced. Most of the smoke-producing compounds and other volatiles are removed during torrefaction, which produces a final product that will have a lower mass but a higher heating value. The present review work looks into (a) torrefaction process and different products produced during the process and (b) solid torrefied material properties which include: (i) physical properties like moisture content, density, grindability, particle size distribution and particle surface area and pelletability; (ii) chemical properties like proximate and ultimate composition; and (iii) storage properties like off-gassing and spontaneous combustion.« less

Strategy for Passivating Char Efficiently at the Pilot Scale

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

Dunning, Timothy C

Fast pyrolysis is a promising pathway for the commercialization of liquid transportation fuels from biomass. Fast pyrolysis is performed at moderate heat (450-600 degrees Celcius) in an oxygen-deficient environment. One of the products of fast pyrolysis is biochar, which is often used as a heat source or as a soil amendment. Biochar is a partially reacted solid that is created in the production of bio-oil during fast pyrolysis. Biochar produced at these conditions contains significant quantities of carbon that adsorb oxygen when exposed to air. Biochar adsorption of oxygen is an exothermic process that may generate sufficient heat for combustionmore » in ambient air. Biochar is also a self-insulating material which compounds the effects of heat generated internally. These factors lead to safety concerns and material handling difficulties. The Thermochemical Process Development Unit at the National Renewable Energy Laboratory operates a pilot plant that may be configured for fast pyrolysis, gasification, and will be introducing catalytic fast pyrolysis capabilities in 2018. The TCPDU designed and installed a system to introduce oxygen to collected biochar systematically for a controlled passivation. Biochar is collected and cooled in an oxygen deficient environment during fast pyrolysis. Oxygen is then introduced to the biochar on a mass flow basis. A sparger imbedded within the biochar sample near the bottom of the bed flows air diluted with nitrogen into the char bed, and excess gasses are removed from the top of the collection drum, above the char bed. Pressure within the collection drum is measured indicating adequate flow through filters. Sample weight is recorded before and after passivation. During passivation, temperature is measured at 18 points within the char bed. Oxygen content and temperature are measured leaving the char bed. Maximum temperature parameters were established to ensure operator safety during biochar passivation. Extensive passivation data was collected on pine and blended feedstocks and has been analyzed to characterize the exotherm of char samples. Observations and data collected while passivating char will be discussed.« less

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.

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.

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

Pyrolysis of tyres. Influence of the final temperature of the process on emissions and the calorific value of the products recovered.

PubMed

Díez, C; Martínez, O; Calvo, L F; Cara, J; Morán, A

2004-01-01

A study was made of the pyrolysis of tyre particles, with the aim of determining the possibilities of using the products resulting from the process as fuel. Three final temperatures were used, determined from thermogravimetric data. The design of the experiment was a horizontal oven containing a reactor into which particles of the original tyre were placed. After the process, a solid fraction (char) remained in the reactor, while the gases generated went through a set of scrubbers where most of the condensable fraction (oils) was retained. Finally, once free of this fraction, the gases were collected in glass ampoules. Solid and liquids fractions were subjected to thermogravimetric analyses in order to study their combustibility. The gas fraction was analysed by means of gas chromatography to establish the content of CO, CO2, H2 and hydrocarbons present in the samples (mainly components of gases produced in the pyrolysis process). A special study was made of the sulphur and chlorine content of all the fractions, as the presence of these elements could be problematic if the products are used as fuel. Tyre pyrolysis engenders a solid carbon residue that concentrates sulphur and chorine, with a relatively high calorific value, although not so high as that of the original tyre. The liquid fraction produced by the process has a high calorific value, which rises with the final temperature, up to 40 MJ/kg. The chlorine content of this fraction is negligible. Over 95% of the gas fraction, regardless of the final temperature, is composed of hydrocarbons of a low molecular weight and hydrogen, this fraction also appearing to be free of chlorine.

Life cycle assessment of microalgae to biofuel: Thermochemical processing through hydrothermal liquefaction or pyrolysis

NASA Astrophysics Data System (ADS)

Bennion, Edward P.

Microalgae are currently being investigated as a renewable transportation fuel feedstock based on various advantages that include high annual yields, utilization of poor quality land, does not compete with food, and can be integrated with various waste streams. This study focuses on directly assessing the impact of two different thermochemical conversion technologies on the microalgae-to-biofuel process through life cycle assessment. A system boundary of a "well to pump" (WTP) is defined and includes sub-process models of the growth, dewatering, thermochemical bio-oil recovery, bio-oil stabilization, conversion to renewable diesel, and transport to the pump. Models were validated with experimental and literature data and are representative of an industrial-scale microalgae-to-biofuel process. Two different thermochemical bio-oil conversion systems are modeled and compared on a systems level, hydrothermal liquefaction (HTL) and pyrolysis. The environmental impact of the two pathways were quantified on the metrics of net energy ratio (NER), defined here as energy consumed over energy produced, and greenhouse gas (GHG) emissions. Results for WTP biofuel production through the HTL pathway were determined to be 1.23 for the NER and GHG emissions of -11.4 g CO2 eq (MJ renewable diesel)-1. WTP biofuel production through the pyrolysis pathway results in a NER of 2.27 and GHG emissions of 210 g CO2 eq (MJ renewable diesel)-1. The large environmental impact associated with the pyrolysis pathway is attributed to feedstock drying requirements and combustion of co-products to improve system energetics. Discussion focuses on a detailed breakdown of the overall process energetics and GHGs, impact of modeling at laboratory-scale compared to industrial-scale, environmental impact sensitivity to engineering systems input parameters for future focused research and development, and a comparison of results to literature.

Pyrolysis of corn stalk biomass briquettes in a scaled-up microwave technology.

PubMed

Salema, Arshad Adam; Afzal, Muhammad T; Bennamoun, Lyes

2017-06-01

Pyrolysis of corn stalk biomass briquettes was carried out in a developed microwave (MW) reactor supplied with 2.45GHz frequency using 3kW power generator. MW power and biomass loading were the key parameters investigated in this study. Highest bio-oil, biochar, and gas yield of 19.6%, 41.1%, and 54.0% was achieved at different process condition. In terms of quality, biochar exhibited good heating value (32MJ/kg) than bio-oil (2.47MJ/kg). Bio-oil was also characterised chemically using FTIR and GC-MS method. This work may open new dimension towards development of large-scale MW pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Process for fixed bed coal gasification

DOEpatents

Sadowski, Richard S.

1992-01-01

The combustion of gas produced from the combination of coal pyrolysis and gasification involves combining a combustible gas coal and an oxidant in a pyrolysis chamber and heating the components to a temperature of at least 1600.degree. F. The products of coal pyrolysis are dispersed from the pyrolyzer directly into the high temperature gasification region of a pressure vessel. Steam and air needed for gasification are introduced in the pressure vessel and the materials exiting the pyrolyzer flow down through the pressure vessel by gravity with sufficient residence time to allow any carbon to form carbon monoxide. Gas produced from these reactions are then released from the pressure vessel and ash is disposed of.

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

PubMed

Wang, Huamin; Elliott, Douglas C; French, Richard J; Deutch, Steve; Iisa, Kristiina

2016-12-25

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. The protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.

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

PubMed Central

Wang, Huamin; Elliott, Douglas C.; French, Richard J.; Deutch, Steve; Iisa, Kristiina

2016-01-01

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. The protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research. PMID:28060311

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

NASA Astrophysics Data System (ADS)

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

2017-03-01

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

Inhibitory effects of CaO/Fe2O3 on arsenic emission during sewage sludge pyrolysis.

PubMed

Han, Hengda; Hu, Song; Lu, Chaofeng; Wang, Yi; Jiang, Long; Xiang, Jun; Su, Sheng

2016-10-01

This work aimed to investigate effects and reaction mechanisms of CaO/Fe2O3 on emission behaviors of arsenic during sewage sludge pyrolysis. The results showed that 24.8-54.2%, 26.4-60.4% and 27.7-63.1% of arsenic escaped from three samples when pyrolysis process happened at 723, 923 and 1123K respectively. And the sludge which contained higher calcium and iron contents released less arsenic than others. External CaO and Fe2O3 were added into the sewage sludge to study their effects on arsenic emissions during pyrolysis, where both of them inhibited arsenic emission effectively, especially at high temperatures. With the help of thermogravimetry analysis and X-ray fluorescence, inhibitory mechanisms of CaO/Fe2O3 on arsenic emission during sewage sludge pyrolysis were studied. CaO could react with As2O3, As2S3 and NaAsO2 to form nonvolatile substances, such as Ca(AsO2)2; while Fe2O3 could react with NaAsO2 to generate certain substances which was stable below 1123K. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pyrolysis of plastic waste for liquid fuel production as prospective energy resource

NASA Astrophysics Data System (ADS)

Sharuddin, S. D. A.; Abnisa, F.; Daud, W. M. A. W.; Aroua, M. K.

2018-03-01

The worldwide plastic generation expanded over years because of the variety applications of plastics in numerous sectors that caused the accumulation of plastic waste in the landfill. The growing of plastics demand definitely affected the petroleum resources availability as non-renewable fossil fuel since plastics were the petroleum-based material. A few options that have been considered for plastic waste management were recycling and energy recovery technique. Nevertheless, several obstacles of recycling technique such as the needs of sorting process that was labour intensive and water pollution that lessened the process sustainability. As a result, the plastic waste conversion into energy was developed through innovation advancement and extensive research. Since plastics were part of petroleum, the oil produced through the pyrolysis process was said to have high calorific value that could be used as an alternative fuel. This paper reviewed the thermal and catalytic degradation of plastics through pyrolysis process and the key factors that affected the final end product, for instance, oil, gaseous and char. Additionally, the liquid fuel properties and a discussion on several perspectives regarding the optimization of the liquid oil yield for every plastic were also included in this paper.

Hydropyrolysis process

DOEpatents

Ullman, Alan Z.; Silverman, Jacob; Friedman, Joseph

1986-01-01

An improved process for producing a methane-enriched gas wherein a hydrogen-deficient carbonaceous material is treated with a hydrogen-containing pyrolysis gas at an elevated temperature and pressure to produce a product gas mixture including methane, carbon monoxide and hydrogen. The improvement comprises passing the product gas mixture sequentially through a water-gas shift reaction zone and a gas separation zone to provide separate gas streams of methane and of a recycle gas comprising hydrogen, carbon monoxide and methane for recycle to the process. A controlled amount of steam also is provided which when combined with the recycle gas provides a pyrolysis gas for treatment of additional hydrogen-deficient carbonaceous material. The amount of steam used and the conditions within the water-gas shift reaction zone and gas separation zone are controlled to obtain a steady-state composition of pyrolysis gas which will comprise hydrogen as the principal constituent and a minor amount of carbon monoxide, steam and methane so that no external source of hydrogen is needed to supply the hydrogen requirements of the process. In accordance with a particularly preferred embodiment, conditions are controlled such that there also is produced a significant quantity of benzene as a valuable coproduct.

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

PubMed

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

2018-03-01

Thermochemical processes can convert the biomass into fuels, such as bio-oil. The biomass submitted to pyrolysis process, such as fibers, are generally rich in silicon, an element that can lead to damages in an engine when there is high concentration in a fuel. High-resolution continuum source atomic absorption spectrometry (HR-CS AAS) is an interesting alternative for Si determination in the products and byproducts of the pyrolysis process because, besides the flame (F) and graphite furnace (GF) atomizers, it has enhanced the application of direct analysis of solid samples (SS) within GF. This study aimed the development of methods to determine Si in biomass samples, their products and byproducts using HR-CS AAS. A high-resolution continuum source atomic absorption spectrometer contrAA 700 equipped with F and GF atomizers was used throughout the study. HR-CS F AAS (λ = 251.611nm, 1 detection pixel, N 2 O/C 2 H 2 flame) was used to evaluate Si content in biomass and ash, after a microwave-assisted acid digestion with HNO 3 and HF. HR-CS GF AAS (T pyr = 1400°C, T atom = 2650°C) has evaluated Si in pyrolysis water and bio-oil at 251.611nm, and in peach pit biomass and ash at 221.174nm using SS, both wavelengths with 1 detection pixel. Rhodium (300μg) was applied as permanent modifier and 10μgPd + 6μg Mg were pipetted onto the standards/samples at each analysis. Three different biomass samples were studied: palm tree fiber, coconut fiber and peach pit, and three certified reference materials (CRM) were used to verify the accuracy of the methods. The figures of merit were LOD 0.09-20mgkg -1 , and LOQ 0.3-20mgkg -1 , considering all the methods. There were no significant differences between the CRM certified values and the determined ones, using a Student t-test with a confidence interval of 95% (n = 5). Si concentration ranged from 0.11-0.92% mm -1 , 1.1-1.7mgkg -1 , 3.3-13mgkg -1 , and 0.41-1.4%mm -1 , in biomass, bio-oil, pyrolysis water and ash, respectively. Si remained mostly in the ash, leading to a mass fraction of up to 103%, even when the Si loss is not considered. Silicon concentration in bio-oil was below 1.7mgkg -1 , which is suitable for its application as a fuel. The developed methods using HR-CS AAS are suitable for Si determination in biomass, bio-oil, pyrolysis water, and ash. The application of bio-oil as an alternative fuel would be possible evaluating its Si content due to its low levels. The mass balance for Si has proved to be an important tool in order to evaluate the correct disposal of pyrolysis process byproducts. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of Thermophysical Hydrocarbon Wastes Pyrolysis Model (in the Case of Wood)

NASA Astrophysics Data System (ADS)

Shantarin, V. D.; Zemenkova, M. Yu; Zemenkov, Yu D.

2016-10-01

The article is devoted to solving environmental problems in the operation in oil and gas industry objects. Reduction of environmental damage by pollution with hydrocarbons can be achieved by disposing oil-contaminated hydrocarbon wastes, using high-temperature pyrolysis process. Authors proposed a recycling method by which in the output there generates the maximum amount of syngas, which, in its turn, is an expensive resource

Research and development plan for the Slagging Pyrolysis Incinerator. [For TRU waste

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

Hedahl, T.G.; McCormack, M.D.

1979-01-01

Objective is to develop an incinerator for processing disposed transuranium waste. This R and D plan describes the R and D efforts required to begin conceptual design of the Slagging Pyrolysis Incinerator (Andco-Torrax). The program includes: incinerator, off-gas treatment, waste handling, instrumentation, immobilization analyses, migration studies, regulations, Belgium R and D test plan, Disney World test plan, and remote operation and maintenance. (DLC)

Resole resin products derived from fractionated organic and aqueous condensates made by fast-pyrolysis of biomass materials

DOEpatents

Chum, Helena L.; Black, Stuart K.; Diebold, James P.; Kreibich, Roland E.

1993-01-01

A process for preparing phenol-formaldehyde resole resins by fractionating organic and aqueous condensates made by fast-pyrolysis of biomass materials while using a carrier gas to move feed into a reactor to produce phenolic-containing/neutrals in which portions of the phenol normally contained in said resins are replaced by a phenolic/neutral fractions extract obtained by fractionation.

Resole resin products derived from fractionated organic and aqueous condensates made by fast-pyrolysis of biomass materials

DOEpatents

Chum, H.L.; Black, S.K.; Diebold, J.P.; Kreibich, R.E.

1993-08-10

A process for preparing phenol-formaldehyde resole resins by fractionating organic and aqueous condensates made by fast-pyrolysis of biomass materials while using a carrier gas to move feed into a reactor to produce phenolic-containing/neutrals in which portions of the phenol normally contained in said resins are replaced by a phenolic/neutral fractions extract obtained by fractionation.

Process for the conversion of carbonaceous feedstocks to particulate carbon and methanol

DOEpatents

Steinberg, Meyer; Grohse, Edward W.

1995-01-01

A process for the production of a pollutant-free particulate carbon (i.e., a substantially ash-, sulfur- and nitrogen-free carbon) from carbonaceous feedstocks. The basic process involves de-oxygenating one of the gas streams formed in a cyclic hydropyrolysis-methane pyrolysis process in order to improve conversion of the initial carbonaceous feedstock. De-oxygenation is effected by catalytically converting carbon monoxide, carbon dioxide, and hydrogen contained in one of the pyrolysis gas streams, preferably the latter, to a methanol co-product. There are thus produced two products whose use is known per se, viz., a substantially pollutant-free particulate carbon black and methanol. These products may be admixed in the form of a liquid slurry of carbon black in methanol.

Thermochemical conversion of waste tyres-a review.

PubMed

Labaki, Madona; Jeguirim, Mejdi

2017-04-01

A review of the energy recovery from waste tyres is presented and focuses on the three thermochemical processes used to valorise waste tyres: pyrolysis, gasification, and combustion/incineration. After recalling the chemical composition of tyres, the thermogravimetric behaviours of tyres or their components under different atmospheres are described. Different kinetic studies on the thermochemical processes are treated. Then, the three processes were investigated, with a particular attention given to the gasification, due to the information unavailability on this process. Pyrolysis is a thermochemical conversion to produce a hydrocarbon rich gas mixture, condensable liquids or tars, and a carbon-rich solid residue. Gasification is a form of pyrolysis, carried out at higher temperatures and under given atmosphere (air, steam, oxygen, carbon dioxide, etc.) in order to yield mainly low molecular weight gaseous products. Combustion is a process that needs a fuel and an oxidizer with an ignition system to produce heat and/or steam. The effects of various process parameters such as temperature, heating rate, residence time, catalyst addition, etc. on the energy efficiency and the products yields and characteristics are mainly reviewed. These thermochemical processes are considered to be the more attractive and practicable methods for recovering energy and material from waste tyres. For the future, they are the main promising issue to treat and valorise used tyres. However, efforts should be done in developing more efficient technical systems.

Morphological characteristics of polyvinyl chloride (PVC) dechlorination during pyrolysis process: Influence of PVC content and heating rate.

PubMed

Cao, Qiongmin; Yuan, Guoan; Yin, Lijie; Chen, Dezhen; He, Pinjing; Wang, Hai

2016-12-01

In this research morphological techniques were used to characterize dechlorination process of PVC when it is in the mixed waste plastics and the two important factors influencing this process, namely, the proportion of PVC in the mixed plastics and heating rate adopted in the pyrolysis process were investigated. During the pyrolysis process for the mixed plastics containing PVC, the morphologic characteristics describing PVC dechlorination behaviors were obtained with help of a high-speed infrared camera and image processing tools. At the same time emission of hydrogen chloride (HCl) was detected to find out the start and termination of HCl release. The PVC contents in the mixed plastics varied from 0% to 12% in mass and the heating rate for PVC was changed from 10 to 60°C/min. The morphologic parameters including "bubble ratio" (BR) and "pixel area" (PA) were found to have obvious features matching with PVC dechlorination process therefore can be used to characterize dechlorination of PVC alone and in the mixed plastics. It has been also found that shape of HCl emission curve is independent of PVC proportions in the mixed plastics, but shifts to right side with elevated heating rate; and all of which can be quantitatively reflected in morphologic parameters vs. temperature curves. Copyright © 2016 Elsevier Ltd. All rights reserved.

Process for producing phenolic compounds from lignins

DOEpatents

Agblevor, F.A.

1998-09-15

A process is described for the production of low molecular weight phenolic compounds from lignins through the pyrolysis of the lignins in the presence of a strong base. In a preferred embodiment, potassium hydroxide is present in an amount of from about 0.1% to about 5% by weight, the pyrolysis temperature is from about 400 C to about 600 C at atmospheric pressure, and the time period for substantial completion of the reaction is from about 1--3 minutes. Examples of low molecular weight phenolic compounds produced include methoxyphenols, non-methoxylated phenols, and mixtures thereof. 16 figs.

Electrical Characteristics and Preparation of (Ba0.5Sr0.5)TiO3 Films by Spray Pyrolysis and Rapid Thermal Annealing

NASA Astrophysics Data System (ADS)

Koo, Horng-Show; Chen, Mi; Ku, Hong-Kou; Kawai, Tomoji

2007-04-01

Functional films of (Ba0.5Sr0.5)TiO3 on Pt (1000 Å)/Ti (100 Å)/SiO2 (2000 Å)/Si substrates are prepared by spray pyrolysis and subsequently rapid thermal annealing. Barium nitrate, strontium nitrate and titanium isopropoxide are used as starting materials with ethylene glycol as solvent. For (Ba0.5Sr0.5)TiO3 functional thin film, thermal characteristics of the precursor powder scratched from as-sprayed films show a remarkable peak around 300-400 °C and 57.7% weight loss up to 1000 °C. The as-sprayed precursor film with coffee-like color and amorphous-like phase is transformed into the resultant film with white, crystalline perovskite phase and characteristic peaks (110) and (100). The resultant films show correspondent increases of dielectric constant, leakage current and dissipation factor with increasing annealing temperatures. The dielectric constant is 264 and tangent loss is 0.21 in the resultant films annealed at 750 °C for 5 min while leakage current density is 1.5× 10-6 A/cm2 in the film annealed at 550 °C for 5 min.

Synthesis of carbon nanomaterials from different pyrolysis techniques: a review

NASA Astrophysics Data System (ADS)

Umer Zahid, Muhammad; Pervaiz, Erum; Hussain, Arshad; Shahzad, Muhammad Imran; Niazi, Muhammad Bilal Khan

2018-05-01

In the current age, the significance of carbon-based nanomaterials for many applications has made the efforts for the facile synthesis methods from abundantly available wastes in a cost-effective way. Pyrolysis in a broad spectrum is commonly employed for the synthesis of carbon nanostructures by thermally treating the organic waste. The mechanism of growth of the nanoparticles determines the functional distribution of nanoparticles based on the growing size, medium, and physio-chemical properties. Carbon nanomaterial’s growth is a complicated process which is profoundly influenced by temperature, catalyst, and type of precursor. Nowadays, significant progress has been made in improving nanomaterial’s growth techniques, opening new paths for commercial production of carbon-based nanomaterials. The most promising are the methods involving hydrocarbon-rich organic waste as the feed source. In this review, synthesis of carbon-based nanomaterials, specifically carbon nanotubes (CNTs), Carbon nanofibers (CNFs) and Graphene (G) are discussed by different pyrolysis techniques. Furthermore, the review explores recent advancements made in the context of pyrolysis.

Evaluation of on-line pyrolysis coupled to isotope ratio mass spectrometry for the determination of position-specific (13)C isotope composition of short chain n-alkanes (C6-C12).

PubMed

Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro

2016-06-01

We measured (13)C intramolecular isotopic composition of commercially available short-chain hydrocarbons (n-C6-n-C12) using (13)C-NMR. Results show that the main variation is between the terminal and the sub-terminal C-atom positions. Site-preference (difference in δ(13)C values between terminal and sub-terminal C-atom positions) among all the samples varies between -12.2‰ and +8.4‰. Comparison of these results with those obtained using on-line pyrolysis coupled with GC-C-IRMS show that the thermal cracking of hydrocarbons occurs with a good isotopic fidelity between terminal and sub-terminal C-atom positions of the starting material and the related pyrolysis products (methane and ethylene). On-line pyrolysis coupled with GC-C-IRMS can thus be used for tracing hydrocarbons biogeochemical processes. Copyright © 2016 Elsevier B.V. All rights reserved.

Selective production of chemicals from biomass pyrolysis over metal chlorides supported on zeolite.

PubMed

Leng, Shuai; Wang, Xinde; Cai, Qiuxia; Ma, Fengyun; Liu, Yue'e; Wang, Jianguo

2013-12-01

Direct biomass conversion into chemicals remains a great challenge because of the complexity of the compounds; hence, this process has attracted less attention than conversion into fuel. In this study, we propose a simple one-step method for converting bagasse into furfural (FF) and acetic acid (AC). In this method, bagasse pyrolysis over ZnCl2/HZSM-5 achieved a high FF and AC yield (58.10%) and a 1.01 FF/AC ratio, but a very low yield of medium-boiling point components. However, bagasse pyrolysis using HZSM-5 alone or ZnCl2 alone still remained large amounts of medium-boiling point components or high-boiling point components. The synergistic effect of HZSM-5 and ZnCl2, which combines pyrolysis, zeolite cracking, and Lewis acid-selective catalysis results in highly efficient bagasse conversion into FF and AC. Therefore, our study provides a novel, simple method for directly converting biomass into high-yield useful chemical. Copyright © 2013 Elsevier Ltd. All rights reserved.

Experimental study of trimethyl aluminum decomposition

NASA Astrophysics Data System (ADS)

Zhang, Zhi; Pan, Yang; Yang, Jiuzhong; Jiang, Zhiming; Fang, Haisheng

2017-09-01

Trimethyl aluminum (TMA) is an important precursor used for metal-organic chemical vapor deposition (MOCVD) of most Al-containing structures, in particular of nitride structures. The reaction mechanism of TMA with ammonia is neither clear nor certain due to its complexity. Pyrolysis of trimethyl metal is the start of series of reactions, thus significantly affecting the growth. Experimental study of TMA pyrolysis, however, has not yet been conducted in detail. In this paper, a reflectron time-of-flight mass spectrometer is adopted to measure the TMA decomposition from room temperature to 800 °C in a special pyrolysis furnace, activated by soft X-ray from the synchrotron radiation. The results show that generation of methyl, ethane and monomethyl aluminum (MMA) indicates the start of the pyrolysis process. In the low temperature range from 25 °C to 700 °C, the main product is dimethyl aluminum (DMA) from decomposition of TMA. For temperatures larger than 700 °C, the main products are MMA, DMA, methyl and ethane.

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

Effects of water washing and torrefaction pretreatments on rice husk pyrolysis by microwave heating.

PubMed

Zhang, Shuping; Dong, Qing; Zhang, Li; Xiong, Yuanquan; Liu, Xinzhi; Zhu, Shuguang

2015-10-01

The influences of water washing, torrefaction and combined water washing-torrefaction pretreatments on microwave pyrolysis of rice husk samples were investigated. The results indicated that the process of combined water washing-torrefaction pretreatment could effectively remove a large portion of inorganics and improve the fuel characteristics to a certain extent. The gas products were rich in combustible compositions and the syngas quality was improved by pretreatment process. The liquid products contained less moisture content, acids and furans, while more concentrated phenols and sugars from microwave pyrolysis of rice husk after pretreatments, especially after the combined water washing-torrefaction pretreatment. Biochar, produced in high yield, has the alkaline pH (pH 8.2-10.0) and high surface area (S(BET) 157.81-267.84 m(2)/g), they have the potential to be used as soil amendments. It is noteworthy that water washing increased the pore surface area of biochar, but torrefaction reduced the pore surface area. Copyright © 2015 Elsevier Ltd. All rights reserved.

Two stages catalytic pyrolysis of refuse derived fuel: production of biofuel via syncrude.

PubMed

Miskolczi, N; Buyong, F; Angyal, A; Williams, P T; Bartha, L

2010-11-01

Thermo-catalytic pyrolysis of refuse derived fuels with different catalysts had been conducted in a two stages process due to its important potential value as fuel. The first stage was a pure thermal pyrolysis in a horizontal tubular reactor with feed rate of 0.5kg hourly. The second stage was a semi-batch process in the presence of catalysts. Results showed that the tested catalysts significantly have affected the quantity of products. E.g. gas yield could be increased with 350% related to the catalyst free case using ZSM-5, while that of pyrolytic oil was 115% over Y-zeolite. Gases consisted of mainly CO and CO(2) obtained from the tubular reactor, while dominantly hydrocarbons from the second stage. Ni-Mo-catalyst and Co-Mo-catalyst had shown activity in pyrolytic oil upgrading via in-situ hydrogenation-dehydrogenation reactions. Sulphur, nitrogen and chlorine level in pyrolytic oils could be significantly declined by using of catalysts.

Biomass-based pyrolytic polygeneration system on cotton stalk pyrolysis: influence of temperature.

PubMed

Chen, Yingquan; Yang, Haiping; Wang, Xianhua; Zhang, Shihong; Chen, Hanping

2012-03-01

To study the process of biomass-based pyrolytic polygeneration and its mechanism in depth, the pyrolysis of cotton stalk was investigated in a packed bed, with focus on the evolution of the chemical and physical structures of the solid, liquid and gaseous products. The evolution of product characteristics could be good explaining the process mechanism of biomass pyrolysis. A relationship between the pore distribution of solid products and the fused aromatic rings system revealed by Raman analysis might be exist and need to quantify in further study. Regarding the optimum conditions for obtaining high-quality pyrolytic products from the polygeneration system, the optimum temperature is 550-750°C, with a higher calorific value of the obtained charcoal (≈ 28 MJ/kg) and a higher surface area (>200 m(2)/g). Meanwhile, the calorific value of the gas reaches 8-9 MJ/m(3) and the liquid oil would be used as a platform product in biorefinery. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

Intrinsic activation: the relationship between biomass inorganic content and porosity formation during pyrolysis.

PubMed

Stratford, James P; Hutchings, Tony R; de Leij, Frans A A M

2014-05-01

The utility of pyrolytic carbons is closely related to their porosity and surface area, there is a clear benefit to the development of biomass pyrolysis processes which produce highly porous carbons. The results presented in this work demonstrate that by using biomass precursors with high inorganic content along with specified process conditions, carbons can be consistently produced with specific surface areas between 900 and 1600 m(2)/g. Results from 12 different source materials show that the formation of increased porosity in pyrolytic carbons is strongly associated with the presence of inorganic elements in the precursors including: magnesium, potassium and sulfur. It was found that pyrolysis of macro-algae can produce especially high specific surface area carbons (mean: 1500 m(2)/g), without externally applied activating agents. Using cheap readily available agricultural residues such as oilseed rape straw, pyrolytic carbons can be produced with specific surface areas of around 950 m(2)/g. Copyright © 2014 Elsevier Ltd. All rights reserved.

Pyrolysis and Matrix-Isolation FTIR of Acetoin

NASA Astrophysics Data System (ADS)

Cole, Sarah; Ellis, Martha; Sowards, John; McCunn, Laura R.

2017-06-01

Acetoin, CH_3C(O)CH(OH)CH_3, is an additive used in foods and cigarettes as well as a common component of biomass pyrolysate during the production of biofuels, yet little is known about its thermal decomposition mechanism. In order to identify thermal decomposition products of acetoin, a gas-phase mixture of approximately 0.3% acetoin in argon was subject to pyrolysis in a resistively heated SiC microtubular reactor at 1100-1500 K. Matrix-isolation FTIR spectroscopy was used to identify pyrolysis products. Many products were observed in analysis of the spectra, including acetylene, propyne, ethylene, and vinyl alcohol. These results provide clues to the overall mechanism of thermal decomposition and are important for predicting emissions from many industrial and residential processes.

Global investigation of potential energy surfaces for the pyrolysis of C(1)-C(3) hydrocarbons: toward the development of detailed kinetic models from first principles.

PubMed

Ryazantsev, Mikhail N; Jamal, Adeel; Maeda, Satoshi; Morokuma, Keiji

2015-11-07

Detailed kinetic models (DKMs) are the most fundamental "bottom-up" approaches to computational investigation of the pyrolysis and oxidation of fuels. The weakest points of existing DKMs are incomplete information about the reaction types that can be involved in the potential energy surfaces (PESs) in pyrolysis and oxidation processes. Also, the computational thermodynamic parameters available in the literature vary widely with the level of theory employed. More sophisticated models require improvement both in our knowledge of the type of the reactions involved and the consistency of thermodynamic and kinetic parameters. In this paper, we aim to address these issues by developing ab initio models that can be used to describe early stages of pyrolysis of C1-C3 hydrocarbons. We applied a recently developed global reaction route mapping (GRRM) strategy to systematically investigate the PES of the pyrolysis of C1-C3 hydrocarbons at a consistent level of theory. The reactions are classified into 14 reaction types. The critical points on the PES for all reactions in the network are calculated at the highly accurate UCCSD(T)-F12b/cc-pVTZ//UM06-2X/cc-pVTZ level of theory. The data reported in this paper can be used for first principle calculations of kinetic constants and for a subsequent study on modeling the evolution of the species from the reaction network of the pyrolysis and oxidation of C1-C3 hydrocarbons.

Pyrolysis of polystyrene waste in the presence of activated carbon in conventional and microwave heating using modified thermocouple.

PubMed

Prathiba, R; Shruthi, M; Miranda, Lima Rose

2018-06-01

Pyrolysis process was experimented using two types of heating source, namely conventional and microwave. Polystyrene (PS) plastic waste was used as feedstock in a batch reactor for both the conventional (slow pyrolysis) and microwave pyrolysis. The effect of activated carbon to polystyrene ratio on (i) yield of oil, gas and residues (ii) reaction temperature (iii) reaction time were studied. Quality of oil from pyrolysis of polystyrene were assessed for the possible applicability in fuel production. Microwave power of 450 W and polymer to activated carbon ratio of 10:1, resulted in the highest oil yield of 93.04 wt.% with a higher heating value of 45 MJ kg -1 and a kinematic viscosity of 2.7 cSt. Microwave heating when compared to conventional heating method, exhibits a reaction temperature and time of 330 °C in 5.5 min, whereas in conventional heating system it was 418 °C in 60 min. The gas chromatography-mass spectrometry analysis of liquid oil from microwave pyrolysis predominantly yields alkenes of 8.44 wt.%, α-methyl styrene 0.96 wt.%, condensed ring aromatics 23.21 wt.% and benzene derivatives 26.77 wt.% when the polystyrene to activated carbon ratio was 10:1. Significant factor of using microwave heating is the amount of energy converted (kWh) is lesser than conventional heating. Copyright © 2018 Elsevier Ltd. All rights reserved.

Benefit of the Use of GCxGC/MS Profiles for 1D GC/MS Data Treatment Illustrated by the Analysis of Pyrolysis Products from East Asian Handmade Papers

NASA Astrophysics Data System (ADS)

Han, Bin; Lob, Silvia; Sablier, Michel

2018-06-01

In this study, we report the use of pyrolysis-GCxGC/MS profiles for an optimized treatment of data issued from pyrolysis-GC/MS combined with the automatic deconvolution software Automated Mass Spectral Deconvolution and Identification System (AMDIS). The method was illustrated by the characterization of marker compounds of East Asian handmade papers through the examination of pyrolysis-GCxGC/MS data to get information which was used for manually identifying low concentrated and co-eluting compounds in 1D GC/MS data. The results showed that the merits of a higher separation power for co-eluting compounds and a better sensitivity for low concentration compounds offered by a GCxGC system can be used effectively for AMDIS 1D GC/MS data treatment: (i) the compound distribution in pyrolysis-GCxGC/MS profiles can be used as "peak finder" for manual check of low concentration and co-eluting compound identification in 1D GC/MS data, and (ii) pyrolysis-GCxGC/MS profiles can provide better quality mass spectra with observed higher match factors in the AMDIS automatic match process. The combination of 2D profile with AMDIS was shown to contribute efficiently to a better characterization of compound profiles in the chromatograms obtained by 1D analysis in focusing on the mass spectral identification. [Figure not available: see fulltext.

New criteria for the characterization of traditional East Asian papers.

PubMed

Avataneo, Chiara; Sablier, Michel

2017-01-01

We report a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) method capable of analyzing traditional East Asian papers. The method proposed is based on rapid and easy single step Py-GC/MS analysis that can be carried out with a minimum amount of matter, in the few microgram range. Three reference papers manufactured from kozo (Broussonetia kazinoki Siebold & Zucc.), mitsumata (Edgeworthia chrysantha Lindl.), and gampi (Wikstroemia sikokiana Franch. & Sav.) with the traditional hand paper making processes were examined. The method allows discrimination between terpenic and steroid compounds, which were revealed as chemical markers of origin of the plant fibers. Each paper investigated was found to have characteristic pyrolysis fingerprints that were unique to the traditional handmade paper, demonstrating the potential for differentiation of these biochemical components of fiber plants on East Asian papers towards identification and conservation of cultural heritage. The investigation on Py-GC/MS was extended to liquid extraction followed by GC/MS analysis to characterize the biochemical components of fiber plants. The main contribution of this study is to provide molecular criteria for discriminating plant species used for traditional East Asian hand papermaking. Py-GC/MS complements efficiently microscope identification especially for adverse cases. A case study of archaeological Chinese paper painting artefacts was thereafter successfully investigated to address informative potential and efficiency of the criteria of identification on ancient and degraded East Asian paperworks.

Apparatus for entrained coal pyrolysis

DOEpatents

Durai-Swamy, Kandaswamy

1982-11-16

This invention discloses a process and apparatus for pyrolyzing particulate coal by heating with a particulate solid heating media in a transport reactor. The invention tends to dampen fluctuations in the flow of heating media upstream of the pyrolysis zone, and by so doing forms a substantially continuous and substantially uniform annular column of heating media flowing downwardly along the inside diameter of the reactor. The invention is particularly useful for bituminous or agglomerative type coals.

Portable in-woods pyrolysis: Using forest biomass to reduce forest fuels, increase soil productivity, and sequester carbon

Treesearch

Deborah Page-Dumroese; Mark Coleman; Greg Jones; Tyron Venn; R. Kasten Dumroese; Nathanial Anderson; Woodam Chung; Dan Loeffler; Jim Archuleta; Mark Kimsey; Phil Badger; Terry Shaw; Kristin McElligott

2009-01-01

We describe the use of an in-woods portable pyrolysis unit that converts forest biomass to bio-oil and the application of the byproduct bio-char in a field trial. We also discuss how in-woods processing may reduce the need for long haul distances of lowvalue woody biomass and eliminate open, currently wasteful burning of forest biomass. If transportation costs can be...

Silane-Pyrolysis Reactor With Nonuniform Heating

NASA Technical Reports Server (NTRS)

Iya, Sridhar K.

1991-01-01

Improved reactor serves as last stage in system processing metallurgical-grade silicon feedstock into silicon powder of ultrahigh purity. Silane pyrolized to silicon powder and hydrogen gas via homogeneous decomposition reaction in free space. Features set of individually adjustable electrical heaters and purge flow of hydrogen to improve control of pyrolysis conditions. Power supplied to each heater set in conjunction with flow in reactor to obtain desired distribution of temperature as function of position along reactor.

Thermal processing of paper sludge and characterisation of its pyrolysis products.

PubMed

Strezov, Vladimir; Evans, Tim J

2009-05-01

Paper sludge is a waste product from the paper and pulp manufacturing industry that is generally disposed of in landfills. Pyrolysis of paper sludge can potentially provide an option for managing this waste by thermal conversion to higher calorific value fuels, bio-gas, bio-oils and charcoal. This work investigates the properties of paper sludge during pyrolysis and energy required to perform thermal conversion. The products of paper sludge pyrolysis were also investigated to determine their properties and potential energy value. The dominant volatile species of paper sludge pyrolysis at 10 degrees C/min were found to be CO and CO(2), contributing to almost 25% of the paper sludge dry weight loss at 500 degrees C. The hydrocarbons (CH(4), C(2)H(4), C(2)H(6)) and hydrogen contributed to only 1% of the total weight loss. The bio-oils collected at 500 degrees C were primarily comprised of organic acids with the major contribution being linoleic acid, 2,4-decadienal acid and oleic acid. The high acidic content indicates that in order to convert the paper sludge bio-oil to bio-diesel or petrochemicals, further upgrading would be necessary. The charcoal produced at 500 degrees C had a calorific value of 13.3MJ/kg.

Studies of a peatified angiosperm log cross section from Indonesia by nuclear magnetic resonance spectroscopy and analytical pyrolysis

USGS Publications Warehouse

Bates, A.L.; Hatcher, P.G.; Lerch, H. E.; Cecil, C.B.; Neuzil, S.G.; ,

1991-01-01

Samples from a 10 cm cross-sectional radius of a peatified angiosperm log from Sumatra, Indonesia, were examined by 13C nuclear magnetic resonance and pyrolysis-gas chromatography in order to understand chemical changes due to the peatification process. NMR results show degradation by selective loss of carbohydrates in all parts of the log section compared with fresh wood; however, the degree of degradation is less near the center of the log section. The degree of ring substitution of aromatic lignin monomeric units, as measured by dipolar dephasing NMR methods, appears to be less at the center of the log section than at the periphery. The methoxyl carbon content of lignin in the log is lower than in unaltered angiospermous lignin but does not appear to change as a function of either radial position or the degree of aromatic ring substitution. Pyrolysis-gas chromatography indicates higher yields of catechols in the outer areas relative to the heartwood. Other than the variations in catechol contents and in the yields of carbohydrate-derived pyrolysis products (e.g. levoglucosan, angelicalactones), the pyrolysis results do not show significant changes related to radial position, indicating that the lignin is not significantly altered across the log section. ?? 1991.

Biomass conversion to produce hydrocarbon liquid fuel via hot-vapor filtered fast pyrolysis and catalytic hydrotreating

DOE PAGES

Wang, Huamin; Elliott, Douglas C.; French, Richard J.; ...

2016-12-25

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and themore » processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. As a result, the protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.« less

Analysis of good practices, barriers and drivers for ELTs pyrolysis industrial application.

PubMed

Zabaniotou, A; Antoniou, N; Bruton, G

2014-11-01

Boosting of eco-innovative solutions for End of Life Tyres (ELTs) management, under the principles of the EU Resource Efficiency Roadmap and the Waste Framework Directive, can not only diminish the environmental hazards and the consequent societal cost, but also result to the establishment of a novel perception regarding ELTs; thus, a valuable stock of resources that can be exploited. Despite the extensive scientific research of the previous years on ELTs depolymerisation via pyrolysis highlighting its eco-innovative characteristics, the use of pyrolysis to process scrap tyres has not yet achieved a broad commercial success, with economic viability and product standardization to constitute the primary impediments. More specifically, pyrolysis was not applied to an extensive industrial scale so far, due to deficient market analysis, legislative barriers, economic instability and sometimes public acceptance. All the above issues are addressed by the present study. Modifications on current EU legislation can prevent or reduce delays or derailment of efforts on pyrolysis, through its differentiation from incineration. The attainment of economic viability could be realized through the valorization of the pyrolytic char towards activated carbon production for environmental depollution applications; needless to say, the penetration on niche and well-organised markets is more than essential. Copyright © 2014 Elsevier Ltd. All rights reserved.

Biomass conversion to produce hydrocarbon liquid fuel via hot-vapor filtered fast pyrolysis and catalytic hydrotreating

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

Wang, Huamin; Elliott, Douglas C.; French, Richard J.

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and themore » processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. As a result, the protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.« less

A review on thermal and catalytic pyrolysis of plastic solid waste (PSW).

PubMed

Al-Salem, S M; Antelava, A; Constantinou, A; Manos, G; Dutta, A

2017-07-15

Plastic plays an important role in our daily lives due to its versatility, light weight and low production cost. Plastics became essential in many sectors such as construction, medical, engineering applications, automotive, aerospace, etc. In addition, economic growth and development also increased our demand and dependency on plastics which leads to its accumulation in landfills imposing risk on human health, animals and cause environmental pollution problems such as ground water contamination, sanitary related issues, etc. Hence, a sustainable and an efficient plastic waste treatment is essential to avoid such issues. Pyrolysis is a thermo-chemical plastic waste treatment technique which can solve such pollution problems, as well as, recover valuable energy and products such as oil and gas. Pyrolysis of plastic solid waste (PSW) has gained importance due to having better advantages towards environmental pollution and reduction of carbon footprint of plastic products by minimizing the emissions of carbon monoxide and carbon dioxide compared to combustion and gasification. This paper presents the existing techniques of pyrolysis, the parameters which affect the products yield and selectivity and identify major research gaps in this technology. The influence of different catalysts on the process as well as review and comparative assessment of pyrolysis with other thermal and catalytic plastic treatment methods, is also presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Process for the conversion of carbonaceous feedstocks to particulate carbon and methanol

DOEpatents

Steinberg, M.; Grohse, E.W.

1995-06-27

A process is described for the production of a pollutant-free particulate carbon (i.e., a substantially ash-, sulfur- and nitrogen-free carbon) from carbonaceous feedstocks. The basic process involves de-oxygenating one of the gas streams formed in a cyclic hydropyrolysis-methane pyrolysis process in order to improve conversion of the initial carbonaceous feedstock. De-oxygenation is effected by catalytically converting carbon monoxide, carbon dioxide, and hydrogen contained in one of the pyrolysis gas streams, preferably the latter, to a methanol co-product. There are thus produced two products whose use is known per se, viz., a substantially pollutant-free particulate carbon black and methanol. These products may be admixed in the form of a liquid slurry of carbon black in methanol. 3 figs.

Simultaneous biosorption of selenium, arsenic and molybdenum with modified algal-based biochars.

PubMed

Johansson, Charlotte L; Paul, Nicholas A; de Nys, Rocky; Roberts, David A

2016-01-01

Ash disposal waters from coal-fired power stations present a challenging water treatment scenario as they contain high concentrations of the oxyanions Se, As and Mo which are difficult to remove through conventional techniques. In an innovative process, macroalgae can be treated with Fe and processed through slow pyrolysis into Fe-biochar which has a high affinity for oxyanions. However, the effect of production conditions on the efficacy of Fe-biochar is poorly understood. We produced Fe-biochar from two algal sources; "Gracilaria waste" (organic remnants after agar is extracted from cultivated Gracilaria) and the freshwater macroalgae Oedogonium. Pyrolysis experiments tested the effects of the concentration of Fe(3+) in pre-treatment, and pyrolysis temperatures, on the efficacy of the Fe-biochar. The efficacy of Fe-biochar increased with increasing concentrations of Fe(3+) in the pre-treatment solutions, and decreased with increasing pyrolysis temperatures. The optimized Fe-biochar for each biomass was produced by treatment with a 12.5% w/v Fe(3+) solution, followed by slow pyrolysis at 300 °C. The Fe-biochar produced in this way had higher a biosorption capacity for As and Mo (62.5-80.7 and 67.4-78.5 mg g(-1) respectively) than Se (14.9-38.8 mg g(-1)) in single-element mock effluents, and the Fe-biochar produced from Oedogonium had a higher capacity for all elements than the Fe-biochar produced from Gracilaria waste. Regardless, the optimal Fe-biochars from both biomass sources were able to effectively treat Se, As and Mo simultaneously in an ash disposal effluent from a power station. The production of Fe-biochar from macroalgae is a promising technique for treatment of complex effluents containing oxyanions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fabrication of 3D Carbon Microelectromechanical Systems (C-MEMS).

PubMed

Pramanick, Bidhan; Martinez-Chapa, Sergio O; Madou, Marc; Hwang, Hyundoo

2017-06-17

A wide range of carbon sources are available in nature, with a variety of micro-/nanostructure configurations. Here, a novel technique to fabricate long and hollow glassy carbon microfibers derived from human hairs is introduced. The long and hollow carbon structures were made by the pyrolysis of human hair at 900 °C in a N2 atmosphere. The morphology and chemical composition of natural and pyrolyzed human hairs were investigated using scanning electron microscopy (SEM) and electron-dispersive X-ray spectroscopy (EDX), respectively, to estimate the physical and chemical changes due to pyrolysis. Raman spectroscopy was used to confirm the glassy nature of the carbon microstructures. Pyrolyzed hair carbon was introduced to modify screen-printed carbon electrodes ; the modified electrodes were then applied to the electrochemical sensing of dopamine and ascorbic acid. Sensing performance of the modified sensors was improved as compared to the unmodified sensors. To obtain the desired carbon structure design, carbon micro-/nanoelectromechanical system (C-MEMS/C-NEMS) technology was developed. The most common C-MEMS/C-NEMS fabrication process consists of two steps: (i) the patterning of a carbon-rich base material, such as a photosensitive polymer, using photolithography; and (ii) carbonization through the pyrolysis of the patterned polymer in an oxygen-free environment. The C-MEMS/NEMS process has been widely used to develop microelectronic devices for various applications, including in micro-batteries, supercapacitors, glucose sensors, gas sensors, fuel cells, and triboelectric nanogenerators. Here, recent developments of a high-aspect ratio solid and hollow carbon microstructures with SU8 photoresists are discussed. The structural shrinkage during pyrolysis was investigated using confocal microscopy and SEM. Raman spectroscopy was used to confirm the crystallinity of the structure, and the atomic percentage of the elements present in the material before and after pyrolysis was measured using EDX.

Comparative study on the pyrolysis behaviour and kinetics of two macroalgae biomass (Gracilaria changii and Gelidium pusillum) by thermogravimetric analysis

NASA Astrophysics Data System (ADS)

Roslee, A. N.; Munajat, N. F.

2017-10-01

Macroalgae are often referred as seaweed and could be significant biomass resource for the production of numerous energy carriers including biofuels. In this study, the chemical composition of Gracilaria changii (G. changii) and Gelidium pusillum (G. pusillum) were determined through proximate and ultimate analysis and the thermal degradation behaviour of G. changii and G. pusillum were investigated via thermogravimetric analysis (TGA) in determining the important main composition to be considered as biomass fuels. It has found the pyrolysis of G. changii and G. pusillum consists of three stages and stage II is the main decomposition stage with major mass loss of around 52.16% and 44.42%, respectively. The TGA data were then used for determination of kinetic parameters of the pyrolysis process using three model-free methods: Kissinger, Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO). The apparent activation energy calculated by using Kissinger method for G. changii was lower than G. Pusillum, i.e.173.12 kJ/mol and 193.22 kJ/mol, respectively. The activation energies calculated from KAS and FWO methods were increased with increasing the pyrolysis conversion with average activation energies of 172.32 kJ/mol and 181.19 kJ/mol for G. changii while for G. pusillum (177.42 kJ/mol and 187.4 kJ/mol). G. pusillum has lower and wider distribution of activation energy and revealed that the pyrolysis process for G. changii was easier than G. pusillum. These data provide information for further application for designing and modelling in thermochemical conversion system of macroalgae biomass.

Biomass Catalytic Pyrolysis on Ni/ZSM-5: Effects of Nickel Pretreatment and Loading

DOE PAGES

Yung, Matthew M.; Starace, Anne K.; Mukarakate, Calvin; ...

2016-04-25

Here in this work, Ni/ZSM-5 catalysts with varied nickel loadings were evaluated for their ability to produce aromatic hydrocarbons by upgrading of pine pyrolysis vapors. The effect of catalyst pretreatment by hydrogen reduction was also investigated. Results indicate that the addition of nickel increases the yield of aromatic hydrocarbons while simultaneously increasing the conversion of oxygenates, relative to ZSM-5, and these effects are more pronounced with increasing nickel loading. Additionally, while initial activity differences were observed between the oxidized and reduced forms of nickel on ZSM-5 (i.e., NiO/ZSM-5 versus Ni/ZSM-5), the activity of both catalysts converges with increasing time onmore » stream. These reaction results coupled with characterization of pristine and spent catalysts suggest that the catalysts reach similar active states during catalytic pyrolysis, regardless of pretreatment, as NiO undergoes in situ reduction to Ni by biomass pyrolysis vapors. This reduction of NiO to Ni was confirmed by reaction results and characterization by NH 3 temperature-programmed desorption, temperature-programmed reduction, and X-ray diffraction. This finding is significant in that the ability to reduce or eliminate the need for a pre-reaction H 2 reduction of Ni-modified zeolite catalysts could reduce process complexity and operating costs in a biorefinery-based vapor-phase upgrading process to produce biomass-derived fuels and chemicals. The ability to monitor catalyst activity in real time with a molecular beam mass spectrometer used to measure uncondensed, hot pyrolysis vapors allows for an improved understanding of the mechanism for improved activity with Ni addition to ZSM-5, which is attributed to the ability to prevent deactivation by deposition of coke and capping of zeolite micropores.« less

Methods and apparatuses for preparing upgraded pyrolysis oil

DOEpatents

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

2013-10-01

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

Abhijit Dutta | NREL

Science.gov Websites

Techno-economic analysis Process model development for existing and conceptual processes Detailed heat integration Economic analysis of integrated processes Integration of process simulation learnings into control ;Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A

Laboratory simulated hydrothermal alteration of sedimentary organic matter from Guaymas Basin, Gulf of California. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Leif, Roald N.

1993-01-01

High temperature alteration of sedimentary organic matter associated with marine hydrothermal systems involves complex physical and chemical processes that are not easily measured in most natural systems. Many of these processes can be evaluated indirectly by examining the geochemistry of the hydrothermal system in the laboratory. In this investigation, an experimental organic geochemical approach to studying pyrolysis of sedimentary organic matter is applied to the hydrothermal system in the Guaymas Basin, Gulf of California. A general survey of hydrothermal oils and extractable organic matter (bitumen) in hydrothermally altered sediments identified several homologous series of alkanones associated with a high temperature hydrothermal origin. The alkanones range in carbon number from C11 to C30 with no carbon number preference. Alkan-2-ones are in highest concentrations, with lower amounts of 3-, 4-, 5- (and higher) homologs. The alkanones appear to be pyrolysis products synthesized under extreme hydrothermal conditions. Hydrous pyrolysis and confinement pyrolysis experiments were performed to simulate thermally enhanced diagenetic and catagenetic changes in the immature sedimentary organic matter. The extent of alteration was measured by monitoring the n-alkanes, acyclic isoprenoids, steroid and triterpenoid biomarkers, polycyclic aromatic hydrocarbons and alkanones. The results were compared to bitumen extracts from sediments which have been naturally altered by a sill intrusion and accompanied hydrothermal fluid flow. These pyrolysis experiments duplicated many of the organic matter transformations observed in the natural system. Full hopane and sterane maturation occurred after 48 hr in experiments at 330 deg C with low water/rock mass ratios (0.29). A variety of radical and ionic reactions are responsible for the organic compound conversions which occur under extreme hydrothermal conditions. Short duration pyrolysis experiments revealed that a portion of the hydrocarbons generated from kerogen was observed to go through alkene intermediates, and the rate of alkene isomerization was influenced by the ionic strength and catalytic mineral phases. Confinement of the organic pyrolysate to the bulk sediment accelerated the rates of the biomarker epimerization reactions, suggesting that these reactions are influenced strongly by the association of the inorganic matrix, and that the relative rates of some ionic and radical reactions can be influenced by the water/rock ratio during the pyrolysis experiments.

Theoretical Study of the Thermal Decomposition of Carboxylic Acids at Pyrolysis Temperature

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

Clark, J. M.; Robichaud, D. J.; Nimlos, M. R.

2013-01-01

Carboxylic acids are important in the processing of biomass into renewable fuels and chemicals. They are formed from the pretreatment and pyrolysis of hemicellulose biopolymers and are released from the decomposition of sugars. They result from the deconstruction of polyhydroxyalkanoates (bacterial carbon storage polymers) from fatty acids derived from algae, bacteria, and oil crops. The thermal deoxygenation of carboxylic acids is an important step in the conversion of biomass into aliphatic hydrocarbons suitable for use in renewable biofuels and as petrochemical replacements. Decarboxylation, a primary decomposition pathway under pyrolysis conditions, represents an ideal conversion process, because it eliminates two atomsmore » of oxygen for every carbon atom removed. Problematically, additional deoxygenation processes exist (e.g. dehydration) that are in direct competition with decarboxylation and result in the formation of reactive and more fragmented end products. To better understand the competition between decarboxylation and other deoxygenation processes and to gain insight into possible catalysts that would favor decarboxylation, we have investigated the mechanisms and thermochemistry of the various unimolecular and bimolecular deoxygenation pathways for a family of C1-C4 organic acids using electronic structure calculations at the M06-2X/6-311++G(2df,p) level of theory.« less

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

NASA Astrophysics Data System (ADS)

Maulina, S.; Iriansyah, M.

2018-02-01

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

Recycling of Zinc- and Lead-Bearing Residues with Pyrolysis Gas

NASA Astrophysics Data System (ADS)

Pichler, C.; Antrekowitsch, J.

2015-09-01

Efforts in the metallurgical industry for an approximation to the zero waste concept has led to many different investigations. Together with the greenhouse effect, CO2 emissions have caused additional costs for different process steps in the industry. For this reason, alternative carbon carriers have been sought, and charcoal was found to be an ideal substitute, due to its CO2 neutrality. In order to use it in the metallurgical industry, an optimization of the charcoal production through a carbonization process must be carried out. Beside the charcoal, pyrolysis gas also occurs during the heating of wood or agricultural wastes under the exclusion of air. Because of combustible compounds in this gas, it is possible to use it as a reduction agent instead of fossil carbon carriers. Together with the idea of preventing landfilling of metallurgical by-products, an investigation was carried out to treat zinc- and lead-containing materials. For this issue a special process concept was designed and developed. The main aspect was to recycle the zinc- and lead-containing Waelz slag, which results from the processing of steel mill dusts, in a vertical retort. Two different sizes of facilities were constructed to perform the reaction system of the solid Waelz slag with the gaseous reduction agent of pyrolysis gas.

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

NASA Astrophysics Data System (ADS)

Li, Qi

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

Generation of ethylene tracer by noncatalytic pyrolysis of natural gas at elevated pressure

USGS Publications Warehouse

Lu, Y.; Chen, S.; Rostam-Abadi, M.; Ruch, R.; Coleman, D.; Benson, L.J.

2005-01-01

There is a critical need within the pipeline gas industry for an inexpensive and reliable technology to generate an identification tag or tracer that can be added to pipeline gas to identify gas that may escape and improve the deliverability and management of gas in underground storage fields. Ethylene is an ideal tracer, because it does not exist naturally in the pipeline gas, and because its physical properties are similar to the pipeline gas components. A pyrolysis process, known as the Tragen process, has been developed to continuously convert the ???2%-4% ethane component present in pipeline gas into ethylene at common pipeline pressures of 800 psi. In our studies of the Tragen process, pyrolysis without steam addition achieved a maximum ethylene yield of 28%-35% at a temperature range of 700-775 ??C, corresponding to an ethylene concentration of 4600-5800 ppm in the product gas. Coke deposition was determined to occur at a significant rate in the pyrolysis reactor without steam addition. The ?? 13C isotopic analysis of gas components showed a ?? 13C value of ethylene similar to ethane in the pipeline gas, indicating that most of the ethylene was generated from decomposition of the ethane in the raw gas. However, ?? 13C isotopic analysis of the deposited coke showed that coke was primarily produced from methane, rather than from ethane or other heavier hydrocarbons. No coke deposition was observed with the addition of steam at concentrations of > 20% by volume. The dilution with steam also improved the ethylene yield. ?? 2005 American Chemical Society.

Aspen Plus Model for In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors for the Conversion of Biomass to Hydrocarbon Fuels

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

This is an Aspen Plus process model for in situ and ex situ upgrading of fast pyrolysis vapors for the conversion of biomass to hydrocarbon fuels. It is based on conceptual designs that allow projections of future commercial implementations of the technologies based on a combination of research and existing commercial technologies. The process model was developed from the ground up at NREL. Results from the model are documented in a detailed design report NREL/TP-5100-62455 (available at http://www.nrel.gov/docs/fy15osti/62455.pdf).

Steam thermolysis of tire shreds: modernization in afterburning of accompanying gas with waste steam

NASA Astrophysics Data System (ADS)

Kalitko, V. A.

2010-03-01

On the basis of experience in the commercial operation of tire-shred steam thermolysis in EnresTec Inc. (Taiwan) producing high-grade commercial carbon, liquid pyrolysis fuel, and accompanying fuel gas by this method, we have proposed a number of engineering solutions and calculated-analytical substantiations for modernization and intensification of the process by afterburning the accompanying gas with waste steam condensable in the scrubber of water gas cleaning of afterburning products. The condensate is completely freed of the organic pyrolysis impurities and the necessity of separating it from the liquid fuel, as is the case with the active process, is excluded.

Inclined fluidized bed system for drying fine coal

DOEpatents

Cha, Chang Y.; Merriam, Norman W.; Boysen, John E.

1992-02-11

Coal is processed in an inclined fluidized bed dryer operated in a plug-flow manner with zonal temperature and composition control, and an inert fluidizing gas, such as carbon dioxide or combustion gas. Recycled carbon dioxide, which is used for drying, pyrolysis, quenching, and cooling, is produced by partial decarboxylation of the coal. The coal is heated sufficiently to mobilize coal tar by further pyrolysis, which seals micropores upon quenching. Further cooling with carbon dioxide enhances stabilization.

Pyrolysis as a way to close a CFRC life cycle: Carbon fibers recovery and their use as feedstock for a new composite production

NASA Astrophysics Data System (ADS)

Giorgini, Loris; Benelli, Tiziana; Mazzocchetti, Laura; Leonardi, Chiara; Zattini, Giorgio; Minak, Giangiacomo; Dolcini, Enrico; Tosi, Cristian; Montanari, Ivan

2014-05-01

Pyrolysis is shown to be an efficient method for recycling carbon fiber composites in the form of both uncured prepregs scraps or as cured end-of-life objects. The pyrolytic process leads to different products in three physical states of matter. The gaseous fraction, called syngas, can be used as energy feedstock in the process itself. The oil fraction can be used as fuel or chemical feedstock. The solid residue contains substantially unharmed carbon fibers that can be isolated and recovered for the production of new composite materials, thus closing the life cycle of the composite in a "cradle to cradle" approach. All the pyrolysis outputs were thoroughly analyzed and characterized in terms of composition for oil and gas fraction and surface characteristics of the fibers. In particular, it is of paramount importance to correlate the aspect and properties of the fibers obtained with different composite feedstock and operational conditions, that can be significantly different, with the reinforcing performance in the newly produced Recycled Carbon Fibers Reinforced Polymers. Present results have been obtained on a pyrolysis pilot plant that offers the possibility of treating up to 70kg of materials, thus leading to a significant amount of products to be tested in the further composites production, focused mainly on chopped carbon fiber reinforcement.

Molecular-Level Processing of Si-(B)-C Materials with Tailored Nano/Microstructures.

PubMed

Schmidt, Marion; Durif, Charlotte; Acosta, Emanoelle Diz; Salameh, Chrystelle; Plaisantin, Hervé; Miele, Philippe; Backov, Rénal; Machado, Ricardo; Gervais, Christel; Alauzun, Johan G; Chollon, Georges; Bernard, Samuel

2017-12-01

The design of Si-(B)-C materials is investigated, with detailed insight into the precursor chemistry and processing, the precursor-to-ceramic transformation, and the ceramic microstructural evolution at high temperatures. In the early stage of the process, the reaction between allylhydridopolycarbosilane (AHPCS) and borane dimethyl sulfide is achieved. This is investigated in detail through solid-state NMR and FTIR spectroscopy and elemental analyses for Si/B ratios ranging from 200 to 30. Boron-based bridges linking AHPCS monomeric fragments act as crosslinking units, extending the processability range of AHPCS and suppressing the distillation of oligomeric fragments during the low-temperature pyrolysis regime. Polymers with low boron contents display appropriate requirements for facile processing in solution, leading to the design of monoliths with hierarchical porosity, significant pore volume, and high specific surface area after pyrolysis. Polymers with high boron contents are more appropriate for the preparation of dense ceramics through direct solid shaping and pyrolysis. We provide a comprehensive study of the thermal decomposition mechanisms, and a subsequent detailed study of the high-temperature behavior of the ceramics produced at 1000 °C. The nanostructure and microstructure of the final SiC-based ceramics are intimately linked to the boron content of the polymers. B 4 C/C/SiC nanocomposites can be obtained from the polymer with the highest boron content. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular Chemistry and Engineering of Boron-Modified Polyorganosilazanes as New Processable and Functional SiBCN Precursors.

PubMed

Viard, Antoine; Fonblanc, Diane; Schmidt, Marion; Lale, Abhijeet; Salameh, Chrystelle; Soleilhavoup, Anne; Wynn, Mélanie; Champagne, Philippe; Cerneaux, Sophie; Babonneau, Florence; Chollon, Georges; Rossignol, Fabrice; Gervais, Christel; Bernard, Samuel

2017-07-06

A series of boron-modified polyorganosilazanes was synthesized from a poly(vinylmethyl-co-methyl)silazane and controlled amounts of borane dimethyl sulfide. The role of the chemistry behind their synthesis has been studied in detail by using solid-state NMR spectroscopy, FTIR spectroscopy, and elemental analysis. The intimate relationship between the chemistry and the processability of these polymers is discussed. Polymers with low boron contents displayed appropriate requirements for facile processing in solution, such as impregnation of host carbon materials, which resulted in the design of mesoporous monoliths with a high specific surface area after pyrolysis. Polymers with high boron content are more appropriate for solid-state processing to design mechanically robust monolith-type macroporous and dense structures after pyrolysis. Boron acts as a crosslinking element, which offers the possibility to extend the processability of polyorganosilazanes and suppress the distillation of oligomeric fragments in the low-temperature region of their thermal decomposition (i.e., pyrolysis) at 1000 °C under nitrogen. Polymers with controlled and high ceramic yields were generated. We provide a comprehensive mechanistic study of the two-step thermal decomposition based on a combination of thermogravimetric experiments coupled with elemental analysis, solid-state NMR spectroscopy, and FTIR spectroscopy. Selected characterization tools allowed the investigation of specific properties of the monolith-type SiBCN materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Estimation of terpene content in loblolly pine biomass using a hybrid fast-GC and pyrolysis-molecular beam mass spectrometry method

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

Harman-Ware, Anne E.; Davis, Mark F.; Peter, Gary F.

Terpenes can be used as renewable fuels and chemicals and quantifying their presence in biomass is becoming increasingly important. A novel method was developed to rapidly quantify total diterpenoid resin acids using pyrolysis-molecular beam mass spectrometry (py-MBMS). Pine sapling monoterpenes and diterpenoids were extracted from wood using a 1:1 (v/v) mixture of hexane and acetone and analyses were performed before and after extraction to determine the extraction efficiency of the solvent system. The resulting extract was analyzed for total diterpenoid content using py-MBMS and was combined with total monoterpene content that was determined using a low thermal mass modular acceleratedmore » column heater (LTM MACH) fast-GC/FID to measure the terpene content present in pine saplings. Oleoresin extruded from larger pine trees was used to validate mass balance closure of the terpene content in the extract solvent.« less

Estimation of terpene content in loblolly pine biomass using a hybrid fast-GC and pyrolysis-molecular beam mass spectrometry method

DOE PAGES

Harman-Ware, Anne E.; Davis, Mark F.; Peter, Gary F.; ...

2017-01-16

Terpenes can be used as renewable fuels and chemicals and quantifying their presence in biomass is becoming increasingly important. A novel method was developed to rapidly quantify total diterpenoid resin acids using pyrolysis-molecular beam mass spectrometry (py-MBMS). Pine sapling monoterpenes and diterpenoids were extracted from wood using a 1:1 (v/v) mixture of hexane and acetone and analyses were performed before and after extraction to determine the extraction efficiency of the solvent system. The resulting extract was analyzed for total diterpenoid content using py-MBMS and was combined with total monoterpene content that was determined using a low thermal mass modular acceleratedmore » column heater (LTM MACH) fast-GC/FID to measure the terpene content present in pine saplings. Oleoresin extruded from larger pine trees was used to validate mass balance closure of the terpene content in the extract solvent.« less

Taxonomic discrimination of higher plants by pyrolysis mass spectrometry.

PubMed

Kim, S W; Ban, S H; Chung, H J; Choi, D W; Choi, P S; Yoo, O J; Liu, J R

2004-02-01

Pyrolysis mass spectrometry (PyMS) is a rapid, simple, high-resolution analytical method based on thermal degradation of complex material in a vacuum and has been widely applied to the discrimination of closely related microbial strains. Leaf samples of six species and one variety of higher plants (Rosa multiflora, R. multiflora var. platyphylla, Sedum kamtschaticum, S. takesimense, S. sarmentosum, Hepatica insularis, and H. asiatica) were subjected to PyMS for spectral fingerprinting. Principal component analysis of PyMS data was not able to discriminate these plants in discrete clusters. However, canonical variate analysis of PyMS data separated these plants from one another. A hierarchical dendrogram based on canonical variate analysis was in agreement with the known taxonomy of the plants at the variety level. These results indicate that PyMS is able to discriminate higher plants based on taxonomic classification at the family, genus, species, and variety level.

Novel technologies to improve the performance of biomass pyrolsis systems

NASA Astrophysics Data System (ADS)

Liaw, Shi-Shen

Biomass pyrolysis is a thermochemical conversion process to convert lignocellosic materials into bio-oil, gas, and char. The bio-oil can be further refined to produce transportation fuels, high-value chemicals and heat. Although fast pyrolysis is a very promising technology for high bio-oil production yield, the reactors used have several technological problems that limit their future techno-economic viability. Current fast pyrolysis reactors use large quantities of carrier gas that reduce their thermal efficiency. The use of sand to accelerate heating rates results in serious attrition problems responsible for sand contamination of the bio-char produced. Most of the fast pyrolysis reactors currently used need to process very small particles which consume large quantities of energy in grinding. The bio-oil produced is also highly acidic and corrosive mainly due to the presence of acetic acid. The lack of a viable technology to use the acetic acid contained in these oils is a major challenge for the development of viable bio-oil refineries. The objective of this dissertation is to evaluate several technologies to improve the techno-economic viability of biomass pyrolysis systems. The main hypotheses of this dissertation are: (1) high yields of bio-oils could also be obtained by using auger pyrolysis reactors using very low volumes of carried gas and no sand as a heat carrier if the system is fed with very small particles (2) The grinding energy can be reduced if the biomass is torrefied. There are torrefaction conditions that will not affect the overall yield of pyrolysis products (3) Acetic acid produced during pyrolysis can be removed with the use of a fractional condensation system (4) The acids produced during the torrefaction and pyrolysis with the use of the fractional condensation system can be anaerobically digested to produce methane. In this dissertation, it was proved through Py-GC/MS studies that yield of most of the pyrolytic products can be explained by grouping them in five groups or families. The C1 family is formed by products of cellulose fragmentation reactions (glycoaldehyde, acetol, 1,2-ethanediol, monoacetate, butanedial). The products grouped in the C2 family (levoglucosan, levoglucosenone, 1,4:3,6-dianhydro-alpha-D-glucopyranose) are derived from cellulose depolymerization reactions. The molecules derived from hemicellulose (Acetic acid, furfural, 2-furanmethanol) were grouped in the H family. The products derived from lignin were grouped in two families L1 (derived from p-hydroxyl phenol (H) and guaiacyl (G) structures) and L2 (derived from syringyl (S) structures). The yield and properties of bio-oil obtained from an auger pyrolysis reactor is comparable with other existing fluidized bed reactors in the similar pyrolysis condition. The system proposed required much lower volumes of carrier gas and result in the production of a sand-free bio-char. It was also found that the reactions leadings to the formation of bio-char products and the yield of bio-oil are not affected if the pretreatment (torrefaction) temperature is maintained below 290 °C. Torrefaction at higher temperatures results in a dramatic reduction of the bio-oil yield and an increase in the bio-char yield. A condensation system coupled with the auger pyrolysis reactor was constructed and studied for the separation of crude bio-oil produced from Douglas Fir wood. As the first condenser temperature increases up to 80 °C, the content of light oxygenated organic compounds (chiefly the acetic acid and water) in the first condenser decreased significantly. For the first time, this dissertation reports the anaerobic digestion of the aqueous phase obtained in the thermal pretreatment (torrefaction) step and in the second condenser during biomass pyrolysis to produce bio-methane. Acid washing was studied to minimize the inhibitors (hydroxyacetaldehyde and monophenols) in aqueous phase for higher bio-methane production. The results of this dissertation confirm that with the implementation of the new technologies studied it is possible to improve the performance of existing fast pyrolysis systems.

Studies on pyrolysis and gasification of automobile shredder residue in China.

PubMed

Ni, Feijian; Chen, Ming

2014-10-01

With increasing automobile ownerships in China, the number of end-of-life vehicles has also rapidly increased. However, the automobile shredder residue generated during the dismantling of end-of-life vehicles in China is not treated properly and has caused great resource waste and environmental problems. In this work, automobile shredder residue from a domestic end-of-life vehicles dismantling company was comprehensively studied through element analysis, combustion heat experiment, proximate analysis, and thermogravimetric analysis. The feasibility of using pyrolysis combined with gasification to treat and recycle automobile shredder residue was investigated. The produced gas, oil, and residue yield was measured and the correlation between their yield and the experimental temperature and ratio of air to automobile shredder residue feed was studied. It is found that when ratio of air and experimental temperature are 1.5 mol kg(-1) and 900 °C, respectively, the heat energy of the gas produced per kilogram treated automobile shredder residue reaches a maximum value of 11.28 MJ. The characteristics of pyrolysis oil and solid residue were studied. The solid residue takes up 4.65%~5.57% of the original end-of-life vehicles weight. This greatly helps to reach the target of a 95% recycling rate. © The Author(s) 2014.

Development of Amplified 16S Ribosomal DNA Restriction Analysis for Identification of Actinomyces Species and Comparison with Pyrolysis-Mass Spectrometry and Conventional Biochemical Tests

PubMed Central

Hall, Val; O’Neill, G. L.; Magee, J. T.; Duerden, B. I.

1999-01-01

Identification of Actinomyces spp. by conventional phenotypic methods is notoriously difficult and unreliable. Recently, the application of chemotaxonomic and molecular methods has clarified the taxonomy of the group and has led to the recognition of several new species. A practical and discriminatory identification method is now needed for routine identification of clinical isolates. Amplified 16S ribosomal DNA restriction analysis (ARDRA) was applied to reference strains (n = 27) and clinical isolates (n = 36) of Actinomyces spp. and other gram-positive rods. Clinical strains were identified initially to the species level by conventional biochemical tests. However, given the low degree of confidence in conventional methods, the findings obtained by ARDRA were also compared with those obtained by pyrolysis-mass spectrometry. The ARDRA profiles generated by the combination of HaeIII and HpaII endonuclease digestion differentiated all reference strains to the species or subspecies level. The profiles correlated well with the findings obtained by pyrolysis-mass spectrometry and by conventional tests and enabled the identification of 31 of 36 clinical isolates to the species level. ARDRA was shown to be a simple, rapid, cost-effective, and highly discriminatory method for routine identification of Actinomyces spp. of clinical origin. PMID:10364594

Tertiary recycling of PVC-containing plastic waste by copyrolysis with cattle manure.

PubMed

Duangchan, Apinya; Samart, Chanatip

2008-11-01

The corrosion from pyrolysis of PVC in plastic waste was reduced by copyrolysis of PVC with cattle manure. The optimization of pyrolysis conditions between PVC and cattle manure was studied via a statistical method, the Box-Behnken model. The pyrolysis reaction was operated in a tubular reactor. Heating rate, reaction temperature and the PVC:cattle manure ratio were optimized in the range of 1-5 degrees C/min, 250-450 degrees C and the ratio of 1:1-1:5, respectively. The suitable conditions which provided the highest HCl reduction efficiency were the lowest heating rate of 1 degrees C/min, the highest reaction temperature of 450 degrees C, and the PVC:cattle manure ratio of 1:5, with reliability of more than 90%. The copyrolysis of the mixture of PVC-containing plastic and cattle manure was operated at optimized conditions and the synergistic effect was studied on product yields. The presence of manure decreased the oil yield by about 17%. The distillation fractions of oil at various boiling points from both the presence and absence of manure were comparable. The BTX concentration decreased rapidly when manure was present and the chlorinated hydrocarbon was reduced by 45%. However, the octane number of the gasoline fraction was not affected by manure and was in the range of 99-100.

Time value of emission and technology discounting rate for off-grid electricity generation in India using intermediate pyrolysis

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

Patel, Amit, E-mail: amitrp@iitrpr.ac.in; Faculty of Technology and Engineering, The Maharaja Sayajirao University of Baroda, Vadodara 390001, Gujarat; Sarkar, Prabir

The environmental impact assessment of a process over its entire operational lifespan is an important issue. Estimation of life cycle emission helps in predicting the contribution of a given process to abate (or to pollute) the environmental emission scenario. Considering diminishing and time-dependent effect of emission, assessment of the overall effect of emissions is very complex. The paper presents a generalized methodology for arriving at a single emission discounting number for a process option, using the concept of time value of carbon emission flow. This number incorporates the effect of the emission resulting from the process over the entire operationalmore » lifespan. The advantage of this method is its quantitative aspect as well as its flexible nature. It can be applied to any process. The method is demonstrated with the help of an Intermediate Pyrolysis process when used to generate off-grid electricity and opting biochar route for disposing straw residue. The scenarios of very high net emission to very high net carbon sequestration is generated using process by careful selection of process parameters for different scenarios. For these different scenarios, the process discounting rate was determined and its outcome is discussed. The paper also proposes a process specific eco-label that mentions the discounting rates. - Highlight: • Methodology to obtain emission discounting rate for a process is proposed. • The method includes all components of life cycle emission converts into a time dependent discounting number. • A case study of Intermediate Pyrolysis is used to obtain such number for a range of processes. • The method is useful to determine if the effect from the operation of a process will lead to a net absorption of emission or net accumulation of emission in the environment.« less