Low-temperature co-pyrolysis behaviours and kinetics of oily sludge: effect of agricultural biomass.
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.
Pyrolysis process for the treatment of food waste.
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.
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.
Pyrolysis of tyre powder using microwave thermogravimetric analysis: Effect of microwave power.
Song, Zhanlong; Yang, Yaqing; Zhou, Long; Zhao, Xiqiang; Wang, Wenlong; Mao, Yanpeng; Ma, Chunyuan
2017-02-01
The pyrolytic characteristics of tyre powder treated under different microwave powers (300, 500, and 700 W) were studied via microwave thermogravimetric analysis. The product yields at different power levels were studied, along with comparative analysis of microwave pyrolysis and conventional pyrolysis. The feedstock underwent preheating, intense pyrolysis, and final pyrolysis in sequence. The main and secondary weight loss peaks observed during the intense pyrolysis stage were attributed to the decomposition of natural rubbers and synthetic rubbers, respectively. The total mass loss rates, bulk temperatures, and maximum temperatures were distinctively higher at higher powers. However, the maximum mass loss rate (0.005 s -1 ), the highest yields of liquid product (53%), and the minimum yields of residual solid samples (43.83%) were obtained at 500 W. Compared with conventional pyrolysis, microwave pyrolysis exhibited significantly different behaviour with faster reaction rates, which can decrease the decomposition temperatures of both natural and synthetic rubber by approximately 110 °C-140 °C.
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.
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.
Factors affecting the yield of bio-oil from the pyrolysis of coconut shell.
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.
Ma, Rui; Yuan, Nana; Sun, Shichang; Zhang, Peixin; Fang, Lin; Zhang, Xianghua; Zhao, Xuxin
2017-06-01
Under microwave irradiation, raw sludge was pyrolyzed mainly by evaporation of water, with a weight loss ratio of 84.8% and a maximum temperature not exceeding 200°C. High-temperature pyrolysis of SiC sludge could be realized, with a weight loss ratio of 93.4% and a final pyrolysis temperature of 1131.7°C. Variations between the electric field intensity distribution are the main reason for the differences of pyrolysis efficiencies. HFSS simulation showed that the electric field intensity of the raw sludge gradually decreased from 2.94×10 4 V/m to 0.88×10 4 V/m when pyrolysis ends, while that of SiC sludge decreased from 3.73×10 4 V/m at the beginning to 1.28×10 4 V/m, then increased to 4.03×10 4 V/m. The electromagnetic effect is the main factor (r≥0.91) influencing the temperature increase and weight loss of raw sludge. Both the electromagnetic effect and heat conduction effect influenced temperature rise and weight loss of SiC sludge, but the former's influence was comparatively larger. Copyright © 2017 Elsevier Ltd. All rights reserved.
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.
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
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
Influence of mineral matter on pyrolysis of palm oil wastes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yang, Haiping; Chen, Hanping; Zheng, Chuguang
2006-09-15
The influence of mineral matter on pyrolysis of biomass (including pure biomass components, synthesized biomass, and natural biomass) was investigated using a thermogravimetric analyzer (TGA). First, the mineral matter, KCl, K{sub 2}CO{sub 3}, Na{sub 2}CO{sub 3}, CaMg(CO{sub 3}){sub 2}, Fe{sub 2}O{sub 3}, and Al{sub 2}O{sub 3}, was mixed respectively with the three main biomass components (hemicellulose, cellulose, and lignin) at a weight ratio (C/W) of 0.1 and its pyrolysis characteristics were investigated. Most of these mineral additives, except for K{sub 2}CO{sub 3}, demonstrated negligible influence. Adding K{sub 2}CO{sub 3} inhibited the pyrolysis of hemicellulose by lowering its mass loss ratemore » by 0.3 wt%/{sup o}C, while it enhanced the pyrolysis of cellulose by shifting the pyrolysis to a lower temperature. With increased K{sub 2}CO{sub 3} added, the weight loss of cellulose in the lower temperature zone (200-315 {sup o}C) increased greatly, and the activation energies of hemicellulose and cellulose pyrolysis decreased notably from 204 to 42 kJ/mol. Second, studies on the synthetic biomass of hemicellulose, cellulose, lignin, and K{sub 2}CO{sub 3} (as a representative of minerals) indicated that peaks of cellulose and hemicellulose pyrolysis became overlapped with addition of K{sub 2}CO{sub 3} (at C/W=0.05-0.1), due to the catalytic effect of K{sub 2}CO{sub 3} lowering cellulose pyrolysis to a lower temperature. Finally, a local representative biomass--palm oil waste (in the forms of original material and material pretreated through water washing or K{sub 2}CO{sub 3} addition)--was studied. Water washing shifted pyrolysis of palm oil waste to a higher temperature by 20 {sup o}C, while K{sub 2}CO{sub 3} addition lowered the peak temperature of pyrolysis by {approx}50{sup o}C. It was therefore concluded that the obvious catalytic effect of adding K{sub 2}CO{sub 3} might be attributed to certain fundamental changes in terms of chemical structure of hemicellulose or decomposition steps of cellulose in the course of pyrolysis. (author)« less
Temperature influence on the fast pyrolysis of manure samples: char, bio-oil and gases production
NASA Astrophysics Data System (ADS)
Fernandez-Lopez, Maria; Anastasakis, Kostas; De Jong, Wiebren; Valverde, Jose Luis; Sanchez-Silva, Luz
2017-11-01
Fast pyrolysis characterization of three dry manure samples was studied using a pyrolyzer. A heating rate of 600°C/s and a holding time of 10 s were selected to reproduce industrial conditions. The effect of the peak pyrolysis temperature (600, 800 and 1000°C) on the pyrolysis product yield and composition was evaluated. Char and bio-oil were gravimetrically quantified. Scanning electron microscopy (SEM) was used to analyse the char structure. H2, CH4, CO and CO2 were measured by means of gas chromatography (GC). A decrease in the char yield and an increase of the gas yield were observed when temperature increased. From 800°C on, it was observed that the char yield of samples Dig R and SW were constant, which indicated that the primary devolatilization reactions stopped. This fact was also corroborated by GC analysis. The bio-oil yield slightly increased with temperature, showing a maximum of 20.7 and 27.8 wt.% for samples Pre and SW, respectively, whereas sample Dig R showed a maximum yield of 16.5 wt.% at 800°C. CO2 and CO were the main released gases whereas H2 and CH4 production increased with temperature. Finally, an increase of char porosity was observed with temperature.
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
Characterization of typical heavy metals in pyrolysis MSWI fly ash.
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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
McCown, F.E.
UCC Research Corporation, along with most of the companies involved in coal development, initially was thinking in terms of high pressure systems, flash pyrolysis, and hydrogenation. Most goverment funding has also been provided for projects using these techniques. However, information from several sources, only recently available to UCC Research Corporation, has effected a change in our recommended direction on the subject project. First, information being obtained in-house at UCC Research on another project using low temperature/pressure pyrolysis looked very favorable. Secondly, the initial review of the design, cost and capabilities of the pyrolysis equipment originally proposed indicated that substantial advantagesmore » could be gained at only a modest increase in cost, by changing to a low pressure unit. Finally, it was discovered that a company in England, using almost identical pyrolysis conditions as those being used at UCC Research, was producing coal liquids commercially, and had been in business many years. In consideration of the above information, UCC Research is recommending that the pyrolysis system for the subject project be changed to a low pressure/temperature design, utilizing the information obtained via our in-house research and from the company in England.« less
NASA Astrophysics Data System (ADS)
Chen, Shuyi; Lu, Huigong; Wu, Yi-nan; Gu, Yifan; Li, Fengting; Morlay, Catherine
2016-09-01
Alumina-hercynite nano-spinel powders were prepared via one-step pyrolysis of iron-acetylacetone-doped Al-based metal-organic framework (MOF), i.e., MIL-53(Al). Organic ferric source, iron acetylacetone, was incorporated in situ into the framework of MIL-53(Al) during the solvothermal synthesis process. Under high-temperature pyrolysis, alumina derived from the MIL-53(Al) matrix and ferric oxides originated from the decomposition of organic ferric precursor in the framework were thermally converted into hercynite (FeAl2O4). The prepared samples were characterized using transmission electron microscopy, X-ray diffraction, N2 sorption, thermogravimetry, Raman spectroscopy and X-ray photoelectron spectroscopy. The final products were identified to be composed of alumina, hercynite and trace amounts of carbon depending on pyrolysis temperature. The experimental results showed that hercynite phase can be obtained and stabilized at low temperatures between 900 and 1100 °C under inert atmosphere. The final products were composed of nano-sized particles with an average size below 100 nm of individual crystal and specific surface areas of 18-49 m2 g-1.
Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; ...
2016-07-05
Cycloheptatrienyl (tropyl) radical, C 7H 7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. In this study, the pyrolysis products resulting from C 7H 7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C 7H 7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals domore » not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C 7H 7) radicals but rather only benzyl (C 6H 5CH 2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C 6H 5CH 2, C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2. Finally, analysis of the temperature dependence for the pyrolysis of the isotopic species (C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less
Generation of functional structures by laser pyrolysis of polysilazane
NASA Astrophysics Data System (ADS)
Krauss, Hans-Joachim; Otto, Andreas
2002-06-01
The pyrolysis of polysilazanes by laser power represents an innovative technique for the generation of ceramic-like coatings and structures. The dissolved polysilazanes can be easily applied by painting techniques such as dipping or spraying. In the following pyrolysis the polysilazane layer transforms into an amorphous ceramic-like coating. The laser power is absorbed in the precursor layer, which leads to the latter's ceramization without damaging the substrate by thermal load. While plane laser pyrolysis creates a protective coating, selective pyrolysis creates a raised and adherent ceramic-like structure that remains after the unexposed polymer layer has been removed. The flexibility of a writing laser system in conjunction with a suitable handling system makes it possible to inscribe any kind of 2D structure on nearly any complexly shaped part. Some of the chemical, magnetic, and electrical structure properties can be adjusted by the pyrolysis parameters and special types of filler particles. Especially the possibility to control electric conductivity should make it possible to create structure dielectric films or planar resistors, inductors or capacitors, which are basically written on the surface of the part. Because of their ceramic nature of the structures are resistant against high temperatures and corrosive media. Thus, this new additive structuring technique could finally strike a new path in creating corrosion resistant high- temperature sensors and control systems.
Park, J H; Ok, Y S; Kim, S H; Cho, J S; Heo, J S; Delaune, R D; Seo, D C
2015-12-01
The phosphorus (P) adsorption characteristic of sesame straw biochar prepared with different activation agents and pyrolysis temperatures was evaluated. Between 0.109 and 0.300 mg L(-1) in the form of inorganic phosphate was released from raw sesame straw biochar in the first 1 h. The release of phosphate was significantly enhanced from 62.6 to 168.2 mg g(-1) as the pyrolysis temperature increased. Therefore, sesame straw biochar cannot be used as an adsorbent for P removal without change in the physicochemical characteristics. To increase the P adsorption of biochar in aqueous solution, various activation agents and pyrolysis temperatures were applied. The amount of P adsorbed from aqueous solution by biochar activated using different activation agents appeared in the order ZnCl2 (9.675 mg g(-1)) > MgO (8.669 mg g(-1)) ⋙ 0.1N-HCl > 0.1N-H2SO4 > K2SO4 ≥ KOH ≥ 0.1N-H3PO4, showing ZnCl2 to be the optimum activation agent. Higher P was adsorbed by the biochar activated using ZnCl2 under different pyrolysis temperatures in the order 600 °C > 500 °C > 400 °C > 300 °C. Finally, the amount of adsorbed P by activated biochar at different ratios of biochar to ZnCl2 appeared in the order 1:3 ≒ 1:1 > 3:1. As a result, the optimum ratio of biochar to ZnCl2 and pyrolysis temperature were found to be 1:1 and 600 °C for P adsorption, respectively. The maximum P adsorption capacity by activated biochar using ZnCl2 (15,460 mg kg(-1)) was higher than that of typical biochar, as determined by the Langmuir adsorption isotherm. Therefore, the ZnCl2 activation of sesame straw biochar was suitable for the preparation of activated biochar for P adsorption.
Ansah, Emmanuel; Wang, Lijun; Shahbazi, Abolghasem
2016-10-01
The thermogravimetric and calorimetric characteristics during pyrolysis of wood, paper, textile and polyethylene terephthalate (PET) plastic in municipal solid wastes (MSW), and co-pyrolysis of biomass-derived and plastic components with and without torrefaction were investigated. The active pyrolysis of the PET plastic occurred at a much higher temperature range between 360°C and 480°C than 220-380°C for the biomass derived components. The plastic pyrolyzed at a heating rate of 10°C/min had the highest maximum weight loss rate of 18.5wt%/min occurred at 420°C, followed by 10.8wt%/min at 340°C for both paper and textile, and 9.9wt%/min at 360°C for wood. At the end of the active pyrolysis stage, the final mass of paper, wood, textile and PET was 28.77%, 26.78%, 21.62% and 18.31%, respectively. During pyrolysis of individual MSW components at 500°C, the wood required the least amount of heat at 665.2J/g, compared to 2483.2J/g for textile, 2059.4J/g for paper and 2256.1J/g for PET plastic. The PET plastic had much higher activation energy of 181.86kJ/mol, compared to 41.47kJ/mol for wood, 50.01kJ/mol for paper and 36.65kJ/mol for textile during pyrolysis at a heating rate of 10°C/min. H2O and H2 peaks were observed on the MS curves for the pyrolysis of three biomass-derived materials but there was no obvious H2O and H2 peaks on the MS curves of PET plastic. There was a significant interaction between biomass and PET plastic during co-pyrolysis if the biomass fraction was dominant. The amount of heat required for the co-pyrolysis of the biomass and plastic mixture increased with the increase of plastic mass fraction in the mixture. Torrefaction at a proper temperature and time could improve the grindability of PET plastic. The increase of torrefaction temperature and time did not affect the temperature where the maximum pyrolytic rates occurred for both biomass and plastic but decreased the maximum pyrolysis rate of biomass and increased the maximum pyrolysis rate of PET plastic. The amount of heat for the pyrolysis of biomass and PET mixture co-torrefied at 280°C for 30min was 4365J/g at 500°C, compared to 1138J/g for the pyrolysis of raw 50% wood and 50% PET mixture at the same condition. Copyright © 2016 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Izzatie, N. I.; Basha, M. H.; Uemura, Y.; Hashim, M. S. M.; Amin, N. A. M.; Hamid, M. F.
2017-10-01
In this work, co-pyrolysis of rice straw and polyethylene terephthalate (PET) was carried out at different temperatures (450,500,550, and 600°C) at ratio 1:1 by using fixed bed drop-type pyrolyzer. The purpose of this work is to determine the effect of pyrolysis temperature on the product yield. As the temperature increased, the pyrolysis oil increased until it reaches certain high temperature (600°C), the pyrolysis oil decreased as of more NCG were produced. The temperature 550°C is considered as the optimum pyrolysis temperature since it produced the highest amount of pyrolysis oil with 36 wt.%. In pyrolysis oil, the calorific value (13.98kJ/g) was low because of the presence of high water content (52.46 wt.%). Main chemicals group from pyrolysis oil were an aldehyde, ketones, acids, aromatics, and phenol and all compound have abundant of hydrogen and carbon were identified. Co-pyrolysis of rice straw and PET produced a higher amount of carbon oxides and recycling back the NCG could increase liquid and char yields.
Microwave-assisted pyrolysis of Mississippi coal: A comparative study with conventional pyrolysis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Abdelsayed, Victor; Shekhawat, Dushyant; Smith, Mark W.
Pyrolysis conditions greatly affect the structure-reactivity relationship of char during coal gasification. Here, this work investigated the effect of temperature and microwave heating on the structural properties of the chars generated during pyrolysis, as well as gaseous and tar products. Results showed that microwave pyrolysis of Mississippi coal produced more gaseous products and less tars compared to conventional pyrolysis. Higher CO/CO 2 ratio (>1) was observed under microwave pyrolysis compared to conventional pyrolysis (CO/CO2 < 1), which may be explained by a greater extent of gasification between solid carbon and the CO 2 formed during microwave pyrolysis. Additionally, in microwavemore » pyrolysis, the oil tars generated exhibited lower concentrations of polar oxygenates, while the wax tars showed higher concentrations of non-polar alkanes, as observed from the intensity of CH vibrations in FTIR. The product compositions and FTIR analysis of the tars (oils and waxes) suggest that the microwave interacted preferentially with these polar species, which have relatively higher dielectric properties compared to alkanes. The structure–reactivity relationship of the chars produced was also investigated using a variety of characterization tools such as XRD, BET, SEM, EDS, and FTIR. Finally, the char reactivity towards combustion suggested that microwave-produced chars have a higher thermal stability, likely due to lower O/C ratios, and could be utilized in the metallurgical industry.« less
Microwave-assisted pyrolysis of Mississippi coal: A comparative study with conventional pyrolysis
Abdelsayed, Victor; Shekhawat, Dushyant; Smith, Mark W.; ...
2018-01-13
Pyrolysis conditions greatly affect the structure-reactivity relationship of char during coal gasification. Here, this work investigated the effect of temperature and microwave heating on the structural properties of the chars generated during pyrolysis, as well as gaseous and tar products. Results showed that microwave pyrolysis of Mississippi coal produced more gaseous products and less tars compared to conventional pyrolysis. Higher CO/CO 2 ratio (>1) was observed under microwave pyrolysis compared to conventional pyrolysis (CO/CO2 < 1), which may be explained by a greater extent of gasification between solid carbon and the CO 2 formed during microwave pyrolysis. Additionally, in microwavemore » pyrolysis, the oil tars generated exhibited lower concentrations of polar oxygenates, while the wax tars showed higher concentrations of non-polar alkanes, as observed from the intensity of CH vibrations in FTIR. The product compositions and FTIR analysis of the tars (oils and waxes) suggest that the microwave interacted preferentially with these polar species, which have relatively higher dielectric properties compared to alkanes. The structure–reactivity relationship of the chars produced was also investigated using a variety of characterization tools such as XRD, BET, SEM, EDS, and FTIR. Finally, the char reactivity towards combustion suggested that microwave-produced chars have a higher thermal stability, likely due to lower O/C ratios, and could be utilized in the metallurgical industry.« less
Reprint of: Pyrolysis technologies for municipal solid waste: a review.
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.
Deflagration of thermite - ammonium nitrate based propellant mixture
NASA Astrophysics Data System (ADS)
Duraes, Luisa; Morgado, Joel; Portugal, Antonio; Campos, Jose
2001-06-01
Reaction between iron oxide (Fe2O3) and aluminum (Al) is the reference of the classic thermite compositions. The efficency of the reaction, for a given initial composition of Fe2O3 and Al, is evaluated by the final temperature and by the mass ratio of Al2O3 /AlO in products of combustion (in condensed phase). In order to increase pressure in products of thermite reaction, the original composition is mixed, with an original twin screw extruder, with a propellant binder composed of ammonium and sodium nitrates, initialy solved in formamide (CH3NO) and mixed with a polyurethane solution. The products of combustion and pyrolysis of this binder, reacting with thermite products, generates high pressure and high temperature conditions. These experimental conditions are also predicted using THOR code. The study presents DSC and TGA results of components and mixtures, and correlates them to the ignition phenomena and reaction properties. The regression rate of combustion and final attained temperature and pressure, in a closed confinement, as a function of composition of thermite components/propellant binder, are presented and discussed. They show the influence of gaseous combustion and pyrolysis products of binder in final reaction.
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
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
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.
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.
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.
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.
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.
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.
The slow and fast pyrolysis of cherry seed.
Duman, Gozde; Okutucu, Cagdas; Ucar, Suat; Stahl, Ralph; Yanik, Jale
2011-01-01
The slow and fast pyrolysis of cherry seeds (CWS) and cherry seeds shells (CSS) was studied in fixed-bed and fluidized bed reactors at different pyrolysis temperatures. The effects of reactor type and temperature on the yields and composition of products were investigated. In the case of fast pyrolysis, the maximum bio-oil yield was found to be about 44 wt% at pyrolysis temperature of 500 °C for both CWS and CSS, whereas the bio yields were of 21 and 15 wt% obtained at 500 °C from slow pyrolysis of CWS and CSS, respectively. Both temperature and reactor type affected the composition of bio-oils. The results showed that bio-oils obtained from slow pyrolysis of CWS and CSS can be used as a fuel for combustion systems in industry and the bio-oil produced from fast pyrolysis can be evaluated as a chemical feedstock. Copyright © 2010 Elsevier Ltd. All rights reserved.
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.
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.
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.
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.
Pyrolysis of polystyrene - polyphenylene oxide to recover styrene and useful products
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.
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.
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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hutton, Phillip N.
This report describes research into an innovative laser-enhanced catalytic pyrolysis technology that has the potential to significantly decrease the cost of cracking ethane and other alkanes found in shale gas ethylene. Similar to how water is resonantly heated by microwaves, a CO 2 laser can resonantly heat ethylene, producing radicals that convert ethane to ethylene at lower reactor temperatures. Proof of concept experiments were performed to determine if commercial grade CO 2 lasers at one-twenty fifth the cost of scientific grade lasers could crack ethane at lower temperatures than conventional technology. Cr doped MgO catalyst was then inserted in themore » reaction chamber to further increase conersion rates.« less
Chen, Handing; Chen, Xueli; Qin, Yueqiang; Wei, Juntao; Liu, Haifeng
2017-03-01
The influence of torrefaction on the physicochemical characteristics of char during raw and water washed rice straw pyrolysis at 800-1200°C is investigated. Pore structure, aromaticity and gasification activity of pyrolysis chars are compared between raw and torrefied samples. For raw straw, BET specific surface area decreases with the increased torrefaction temperature at the same pyrolysis temperature and it approximately increases linearly with weight loss during pyrolysis. The different pore structure evolutions relate to the different volatile matters and pore structures between raw and torrefied straw. Torrefaction at higher temperature would bring about a lower graphitization degree of char during pyrolysis of raw straw. Pore structure and carbon crystalline structure evolutions of raw and torrefied water washed straw are different from these of raw straw during pyrolysis. For both raw and water washed straw, CO 2 gasification activities of pyrolysis chars are different between raw and torrefied samples. Copyright © 2016 Elsevier Ltd. All rights reserved.
Method and apparatus for producing pyrolysis oil having improved stability
Baird, Lance A.; Brandvold, Timothy A.; Muller, Stefan
2016-12-27
Methods and apparatus to improve hot gas filtration to reduce the liquid fuel loss caused by prolonged residence time at high temperatures are described. The improvement can be obtained by reducing the residence time at elevated temperature by reducing the temperature of the pyrolysis vapor, by reducing the volume of the pyrolysis vapor at the elevated temperature, by increasing the volumetric flow rate at constant volume of the pyrolysis vapor, or by doing a combination of these.
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.
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.
Effect of torrefaction pretreatment on the pyrolysis of rubber wood sawdust analyzed by Py-GC/MS.
Chen, Wei-Hsin; Wang, Chao-Wen; Kumar, Gopalakrishnan; Rousset, Patrick; Hsieh, Tzu-Hsien
2018-07-01
The aim of this study was to investigate the effect of torrefaction on the pyrolysis of rubber wood sawdust (RWS) using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Three typical torrefaction temperatures (200, 250, and 300 °C) and pyrolysis temperatures (450, 500, and 550 °C) were considered. The results suggested that only diethyl phthalate, belonging to esters, was detected at the torrefaction temperatures of 200 and 250 °C, revealing hemicellulose degradation. With the torrefaction temperature of 300 °C, esters, aldehydes, and phenols were detected, suggesting the predominant decomposition of hemicellulose and lignin. The double-shot pyrolysis indicated that the contents of oxy-compounds such as acids and aldehydes in pyrolysis bio-oil decreased with rising torrefaction temperature, implying that increasing torrefaction severity abated oxygen content in the bio-oil. With the torrefaction temperature of 300 °C, relatively more cellulose was retained in the biomass because the carbohydrate content in the pyrolysis bio-oil increased significantly. Copyright © 2018 Elsevier Ltd. All rights reserved.
Artificial maturation of oil shale: The Irati Formation from the Parana Basin, Brazil
NASA Astrophysics Data System (ADS)
Gayer, James L.
Oil shale samples from the Irati Formation in Brazil were evaluated from an outcrop block, denoted Block 003. The goals of this thesis include: 1) Characterizing the Irati Formation, 2) Comparing the effects of two different types of pyrolysis, anhydrous and hydrous, and 3) Utilizing a variety of geophysical experiments to determine the changes associated with each type of pyrolysis. Primary work included determining total organic carbon, source rock analysis, mineralogy, computer tomography x-ray scans, and scanning electron microscope images before and after pyrolysis, as well as acoustic properties of the samples during pyrolysis. Two types of pyrolysis (hydrous and anhydrous) were performed on samples cored at three different orientations (0°, 45°, and 90°) with respect to the axis of symmetry, requiring six total experiments. During pyrolysis, the overall effective pressure was maintained at 800 psi, and the holding temperature was 365°C. The changes and deformation in the hydrous pyrolysis samples were greater compared to the anhydrous pyrolysis. The velocities gave the best indication of changes occurring during pyrolysis, but it was difficult to maintain the same amplitude and quality of waveforms at higher temperatures. The velocity changes were due to a combination of factors, including thermal deformation of the samples, fracture porosity development, and the release of adsorbed water and bitumen from the sample. Anhydrous pyrolysis in this study did not reduce TOC, while TOC was reduced due to hydrous pyrolysis by 5%, and velocities in the hydrous pyrolysis decreased by up to 30% at 365°C compared to room temperature. Data from this study and future data that can be acquired with the improved high-temperature, high-pressure experiment will assist in future economic production from oil shale at lower temperatures under hydrous pyrolysis conditions.
Wang, Xiubin; Zhou, Wei; Liang, Guoqing; Song, Dali; Zhang, Xiaoya
2015-12-15
In this study, the characteristics of maize biochar produced at different pyrolysis temperatures (300, 450 and 600°C) and its effects on organic carbon, nitrogen and enzymatic activities after addition to fluvo-aquic soil were investigated. As pyrolysis temperature increased, ash content, pH, electrical conductivity, surface area, pore volume and aromatic carbon content of biochar increased while yield, ratios of oxygen:carbon and hydrogen: carbon and alkyl carbon content decreased. During incubation, SOC, total N, and ammonium-N contents increased in all biochar-amended treatments compared with the urea treatment; however, soil nitrate-N content first increased and then decreased with increasing pyrolysis temperature of the applied biochar. Extracellular enzyme activities associated with carbon transformation first increased and then decreased with biochars pyrolyzed at 450 and 600°C. Protease activity markedly increased with increased pyrolysis temperatures, whereas pyrolysis temperature had limited effect on soil urease activity. The results indicated that the responses of extracellular enzymes to biochar were dependent on the pyrolysis temperature, the enzyme itself and incubation time as well. Copyright © 2015. Published by Elsevier B.V.
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.
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.
Volatile Analysis by Pyrolysis of Regolith for Planetary Resource Exploration
NASA Technical Reports Server (NTRS)
Glavin, Daniel P.; Malespin, Charles; ten Kate, Inge L.; Getty, Stephanie A.; Holmes, Vincent E.; Mumm, Erik; Franz, Heather B.; Noreiga, Marvin; Dobson, Nick; Southard, Adrian E.;
2012-01-01
The extraction and identification of volatile resources that could be utilized by humans including water, oxygen, noble gases, and hydrocarbons on the Moon, Mars, and small planetary bodies will be critical for future long-term human exploration of these objects. Vacuum pyrolysis at elevated temperatures has been shown to be an efficient way to release volatiles trapped inside solid samples. In order to maximize the extraction of volatiles, including oxygen and noble gases from the breakdown of minerals, a pyrolysis temperature of 1400 C or higher is required, which greatly exceeds the maximum temperatures of current state-of-the-art flight pyrolysis instruments. Here we report on the recent optimization and field testing results of a high temperature pyrolysis oven and sample manipulation system coupled to a mass spectrometer instrument called Volatile Analysis by Pyrolysis of Regolith (VAPoR). VAPoR is capable of heating solid samples under vacuum to temperatures above 1300 C and determining the composition of volatiles released as a function of temperature.
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.
Li, Hao; Mahyoub, Samah Awadh Ali; Liao, Wenjie; Xia, Shuqian; Zhao, Hechuan; Guo, Mengya; Ma, Peisheng
2017-01-01
The magnetic biochars were easily fabricated by thermal pyrolysis of Fe(NO 3 ) 3 and distillation residue derived from rice straw pyrolysis oil at 400, 600 and 800°C. The effects of pyrolysis temperature on characteristics of magnetic biochars as well as adsorption capacity for aromatic contaminants (i.e., anisole, phenol and guaiacol) were investigated carefully. The degree of carbonization of magnetic biochars become higher as pyrolysis temperature increasing. The magnetic biochar reached the largest surface area and pore volume at the pyrolysis temperature of 600°C due to pores blocking in biochar during pyrolysis at 800°C. Based on batch adsorption experiments, the used adsorbent could be magnetically separated and the adsorption capacity of anisole on magnetic biochars was stronger than that of phenol and guaiacol. The properties of magnetic biochar, including surface area, pore volume, aromaticity, grapheme-like-structure and iron oxide (γ-Fe 2 O 3 ) particles, showed pronounced effects on the adsorption performance of aromatic contaminants. Copyright © 2016 Elsevier Ltd. All rights reserved.
Zhang, Yanhong; Huang, Hong; Xia, Zhengbin; Chen, Huanqin
2008-07-01
Thermal degradation of pyrolysis of waste circuit boards was investigated by high-resolution pyrolysis gas chromatography-mass spectrometry (PyGC-MS) and thermogravimetry (TG). In helium atmosphere, the products of FR-4 waste printed circuit board were pyrolyzed at 350, 450, 550, 650, and 750 degrees degrees C, separately, and the pyrolysis products were identified by online MS. The results indicated that the pyrolysis products of the FR-4 waste circuit board were three kinds of substances, such as the low boiling point products, phenol, bisphenol and their related products. Moreover, under 300 degrees degrees C, only observed less pyrolysis products. As the increase of pyrolysis temperature, the relative content of the low boiling point products increased. In the range of 450-650 degrees degrees C, the qualitative analysis and character were similar, and the relative contents of phenol and bisphenol were higher. The influence of pyrolysis temperature on pyrolyzate yields was studied. On the basis of the pyrolyzate profile and the dependence of pyrolyzate yields on pyrolysis temperature, the thermal degradation mechanism of brominated epoxy resin was proposed.
Pyrolysis polygeneration of poplar wood: Effect of heating rate and pyrolysis temperature.
Chen, Dengyu; Li, Yanjun; Cen, Kehui; Luo, Min; Li, Hongyan; Lu, Bin
2016-10-01
The pyrolysis of poplar wood were comprehensively investigated at different pyrolysis temperatures (400, 450, 500, 550, and 600°C) and at different heating rates (10, 30, and 50°C/min). The results showed that BET surface area of biochar, the HHV of non-condensable gas and bio-oil reached the maximum values of 411.06m(2)/g, 14.56MJ/m(3), and 14.39MJ/kg, under the condition of 600°C and 30°C/min, 600°C and 50°C/min, and 550°C and 50°C/min, respectively. It was conducive to obtain high mass and energy yield of bio-oil at 500°C and higher heating rate, while lower pyrolysis temperature and heating rate contributed towards obtaining both higher mass yield and energy yield of biochar. However, higher pyrolysis temperature and heating rate contributed to obtain both higher mass yield and energy yield of the non-condensable gas. In general, compared to the heating rate, the pyrolysis temperature had more effect on the product properties. Copyright © 2016 Elsevier Ltd. All rights reserved.
Gulab, Hussain; Jan, Muhammad Rasul; Shah, Jasmin; Manos, George
2010-01-01
This paper presents results regarding the effect of various process conditions on the performance of a zeolite catalyst in pyrolysis of high density polyethylene. The results show that polymer catalytic degradation can be operated at relatively low catalyst content reducing the cost of a potential industrial process. As the polymer to catalyst mass ratio increases, the system becomes less active, but high temperatures compensate for this activity loss resulting in high conversion values at usual batch times and even higher yields of liquid products due to less overcracking. The results also show that high flow rate of carrier gas causes evaporation of liquid products falsifying results, as it was obvious from liquid yield results at different reaction times as well as the corresponding boiling point distributions. Furthermore, results are presented regarding temperature effects on liquid selectivity. Similar values resulted from different final reactor temperatures, which are attributed to the batch operation of the experimental equipment. Since polymer and catalyst both undergo the same temperature profile, which is the same up to a specific time independent of the final temperature. Obviously, this common temperature step determines the selectivity to specific products. However, selectivity to specific products is affected by the temperature, as shown in the corresponding boiling point distributions, with higher temperatures showing an increased selectivity to middle boiling point components (C(8)-C(9)) and lower temperatures increased selectivity to heavy components (C(14)-C(18)).
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.
1994-01-01
from polymer systems. Investigation of mechanisms of high-temperature pyrolysis and combustion reactions of network polymethacrylates. Rubailo V.L...are widely spread among agricultural important crops (i.e. cereals, fruits, grapevine, potato, cotton, tomato , leguminous) and ornamental plants
Jeong, Jae-Yong; Lee, Uen-Do; Chang, Won-Seok; Jeong, Soo-Hwa
2016-11-01
In this study, palm residues were pyrolyzed in a bench-scale (3kg/h) fast pyrolysis plant equipped with a fluidized bed reactor and bio-oil separation system for the production of bio-oil rich in acetic acid and phenol. Pyrolysis experiments were performed to investigate the effects of reaction temperature and the types and amounts of activated carbon on the bio-oil composition. The maximum bio-oil yield obtained was approximately 47wt% at a reaction temperature of 515°C. The main compounds produced from the bio-oils were acetic acid, hydroxyacetone, phenol, and phenolic compounds such as cresol, xylenol, and pyrocatechol. When coal-derived activated carbon was applied, the acetic acid and phenol yields in the bio-oils reached 21 and 19wt%, respectively. Finally, bio-oils rich in acetic acid and phenol could be produced separately by using an in situ bio-oil separation system and activated carbon as an additive. Copyright © 2016 Elsevier Ltd. All rights reserved.
Giudicianni, Paola; Pindozzi, Stefania; Grottola, Corinna Maria; Stanzione, Fernando; Faugno, Salvatore; Fagnano, Massimo; Fiorentino, Nunzio; Ragucci, Raffaele
2017-03-01
Biomasses to be used in the phytoremediation process are generally selected to match agronomic parameters and heavy metals uptake ability. A proper selection can be made greatly effective if knowledge of the properties of the residual char from pyrolysis is available to identify possible valorization routes. In this study a comparative analysis of the yields and characteristics of char obtained from slow pyrolysis of five uncontaminated biomasses (Populus nigra, Salix alba, Fraxinus oxyphylla, Eucalyptus occidentalis and Arundo donax) was carried out under steam atmosphere to better develop char porosity. Moreover, the dependence of the properties of solid residue on the process final temperature was studied for E. occidentalis in the temperature range of 688-967K. The results demonstrate that, among the studied biomasses, chars from P. nigra and E. occidentalis have to be preferred for applications regulated by surface phenomena given their highest surface area (270-300m 2 /g), whereas char from E. occidentalis is the best choice when the goal is to maximize energy recovery. Copyright © 2017 Elsevier Ltd. All rights reserved.
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
Shi, Lingna; Wang, Lijun; Zhang, Tao; Li, Jianfa; Huang, Xiaoyi; Cai, Jing; Lü, Jinhong; Wang, Yue
2017-10-01
For the purpose of safe disposal of biomass contaminated by biosorption of heavy metals, phosphate-assisted pyrolysis of water hyacinth biomass contaminated by lead (Pb) was tried to reduce the bioavailability and leaching potential of Pb, using direct pyrolysis without additive as a control method. Direct pyrolysis of the contaminated biomass at low temperatures (300 and 400°C) could reduce the bioavailability of Pb, but the leaching potential of Pb was increased with the rising pyrolysis temperature. While phosphate-assisted pyrolysis significantly enhanced the recovery and stability of Pb in the char. Specifically, the percentages of bioavailable Pb and leachable Pb in the chars obtained by phosphate-assisted pyrolysis at low temperatures were reduced to less than 5% and 7%, respectively. The sequential extraction test indicated the transformation of Pb into more stable fractions after phosphate-assisted pyrolysis, which was related to the formation of Pb phosphate minerals including pyromorphite and lead-substituted hydroxyapatite. Copyright © 2017 Elsevier Ltd. All rights reserved.
Wei, Lan; Huang, Yufen; Li, Yanliang; Huang, Lianxi; Mar, Nyo Nyo; Huang, Qing; Liu, Zhongzhen
2017-02-01
Rice husk biochar (RHBC) was prepared for use as adsorbents for the herbicide metolachlor. The characteristics and sorption properties of metolachlor adsorbed by the RHBC prepared at different pyrolysis temperatures were determined by analysis of physico-chemical characteristics, Fourier transform infrared spectroscopy (FTIR), Boehm titration, scanning electron microscopy (SEM), and thermodynamics and kinetics adsorption. With increasing pyrolysis temperature, the RHBC surface area greatly increased (from 2.57 to 53.08 m 2 g -1 ). RHBC produced at the highest temperature (750 °C) had the greatest surface area; SEM also showed the formation of a porous surface on RH-750 biochar. The sorption capacity of RHBC also increased significantly with increasing pyrolysis temperature and was characterized by the Freundlich constant K f for the adsorption capacity increasing from 125.17-269.46 (pyrolysis at 300 °C) to 339.94-765.24 (pyrolysis at 750 °C). The results indicated that the surface area and pore diameter of RHBC produced with high pyrolysis temperature (i.e., 750 °C) had the greatest impact on the adsorption of metolachlor. The FTIR, Boehm titration, and SEM analysis showed that the greatest number of surface groups were on RHBC produced at the lowest temperature (300 °C). The biochars produced at different pyrolysis temperatures had different mechanisms of adsorbing metolachlor, which exhibited a transition from hydrogen bonds dominant at low pyrolytic temperature to pore-filling dominant at higher pyrolytic temperature.
Chen, Nanwei; Ren, Jie; Ye, Ziwei; Xu, Qizhi; Liu, Jingyong; Sun, Shuiyu
2016-12-01
This study was carried out to investigate the kinetics of coffee industrial residue (CIR) pyrolysis, the effect of pyrolysis factors on yield of bio-oil component and components separation of bio-oil. The kinetics of CIR pyrolysis was analyzed using distributed activation energy model (DAEM), based on the experiments in thermogravimetric analyzer (TGA), and it indicated that the average of activation energy (E) is 187.86kJ·mol -1 . The bio-oils were prepared from CIR pyrolysis in vacuum tube furnace, and its components were determined by gas chromatography/mass spectrometry (GC-MS). Among pyrolysis factors, pyrolysis temperature is the most influential factor on components yield of bio-oil, directly concerned with the volatilization and yield of components (palmitic acid, linoleic acid, oleic acid, octadecanoic acid and caffeine). Furthermore, a new method (sequencing temperature-raising pyrolysis) was put forward and applied to the components separation of bio-oil. Based on experiments, a solution of components separation of bio-oil was come out. Copyright © 2016 Elsevier Ltd. All rights reserved.
Effects of torrefaction and densification on switchgrass pyrolysis products
Yang, Zixu; Sarkar, Madhura; Kumar, Ajay; ...
2014-12-01
Abstract The pyrolysis behaviors of four types of pretreated switchgrass (torrefied at 230 and 270 °C, densification, and torrefaction at 270 ºC followed by densification) were studied at three temperatures (500, 600, 700 ºC) using a pyroprobe attached to a gas chromatogram mass spectroscopy (Py-GC/MS). The torrefaction of switchgrass improved its oxygen to carbon ratio and energy content. Contents of anhydrous sugars and phenols in pyrolysis products of torrefied switchgrass were higher than those in pyrolysis products of raw switchgrass. As the torrefaction temperature increased from 230 to 270 °C, the contents of anhydrous sugars and phenols in pyrolysis productsmore » increased whereas content of guaiacols decreased. High pyrolysis temperature (600 and 700 °C as compared to 500 °C) enhanced decomposition of lignin and anhydrous sugars, leading to increase in phenols, aromatics and furans. Densification enhanced depolymerization of cellulose and hemicellulose during pyrolysis.« less
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.
Xu, Gang; Zhang, You; Shao, Hongbo; Sun, Junna
2016-11-01
Phosphorus (P) recycling or reuse by pyrolyzing crop residue has recently elicited increased research interest. However, the effects of feedstock and pyrolysis conditions on P species have not been fully understood. Such knowledge is important in identifying the agronomic and environmental uses of biochar. Residues of three main Chinese agricultural crops and the biochars (produced at 300°C-600°C) derived from these crops were used to determine P transformations during pyrolysis. Hedley sequential fractionation and (31)P NMR analyses were used in the investigation. Our results showed that P transformation in biochar was significantly affected by pyrolysis temperature regardless of feedstock (Wheat straw, maize straw and peanut husk). Pyrolysis treatment transformed water soluble P into a labile (NaHCO3-Pi) or semi-labile pool (NaOH-Pi) and into a stable pool (Dil. HCl P and residual-P). At the same time, organic P was transformed into inorganic P fractions which was identified by the rapid decomposition of organic P detected with solution (31)P NMR. The P transformation during pyrolysis process suggested more stable P was formed at a higher pyrolysis temperature. This result was also evidenced by the presence of less soluble or stable P species, such as such as poly-P, crandallite (CaAl3(OH)5(PO4)2) and Wavellite (Al3(OH)3(PO4)2·5H2O), as detected by solid-state (31)P NMR in biochars formed at a higher pyrolysis temperature. Furthermore, a significant proportion of less soluble pyrophosphate was identified by solution (2%-35%) and solid-state (8%-53%) (31)P NMR, which was also responsible for the stable P forms at higher pyrolysis temperature although their solubility or stability requires further investigation. Results suggested that a relatively lower pyrolysis temperature retains P availability regardless of feedstock during pyrolysis process. Copyright © 2016. Published by Elsevier B.V.
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.
Santella, Chiara; Cafiero, Lorenzo; De Angelis, Doina; La Marca, Floriana; Tuffi, Riccardo; Vecchio Ciprioti, Stefano
2016-08-01
Pyrolysis seems a promising route for recycling of heterogeneous, contaminated and additives containing plastics from waste electrical and electronic equipment (WEEE). This study deals with the thermal and catalytic pyrolysis of a synthetic mixture containing real waste plastics, representative of polymers contained in small WEEE. Two zeolite-based catalysts were used at 400°C: HUSY and HZSM-5 with a high silica content, while three different temperatures were adopted for the thermal cracking: 400, 600 and 800°C. The mass balance showed that the oil produced by pyrolysis is always the main product regardless the process conditions selected, with yields ranging from 83% to 93%. A higher yield was obtained when pyrolysis was carried out with HZSM-5 at 400°C and without catalysts, but at 600 and 800°C. Formation of a significant amount of solid residue (about 13%) is observed using HUSY. The oily liquid product of pyrolysis, analysed by GC-MS and GC-FID, as well as by elemental analysis and for energy content, appeared lighter, less viscous and with a higher concentration of monoaromatics under catalytic condition, if compared to the liquid product derived from thermal degradation at the same temperature. HZSM-5 led to the production of a high yield of styrene (17.5%), while HUSY favoured the formation of ethylbenzene (15%). Energy released by combustion of the oil was around 39MJ/kg, thus suggesting the possibility to exploit it as a fuel, if the recovery of chemical compounds could not be realised. Elemental and proximate analysis of char and GC-TCD analysis of the gas were also performed. Finally, it was estimated to what extent these two products, showing a relevant ability to release energy, could fulfil the energy demand requested in pyrolysis. Copyright © 2016 Elsevier Ltd. All rights reserved.
Muradov, Nazim; Fidalgo, Beatriz; Gujar, Amit C; T-Raissi, Ali
2010-11-01
The aim of this work was to conduct the experimental study of pyrolysis of fast-growing aquatic biomass -Lemna minor (commonly known as duckweed) with the emphasis on the characterization of main products of pyrolysis. The yields of pyrolysis gas, pyrolytic oil (bio-oil) and char were determined as a function of pyrolysis temperature and the sweep gas (Ar) flow rate. Thermogravimetric/differential thermogravimetric (TG/DTG) analyses of duckweed samples in inert (helium gas) and oxidative (air) atmosphere revealed differences in the TG/DTG patterns obtained for duckweed and typical plant biomass. The bio-oil samples produced by duckweed pyrolysis at different reaction conditions were analyzed using GC-MS technique. It was found that pyrolysis temperature had minor effect on the bio-oil product slate, but exerted major influence on the relative quantities of the individual pyrolysis products obtained. While, the residence time of the pyrolysis vapors had negligible effect on the yield and composition of the duckweed pyrolysis products. Copyright 2010 Elsevier Ltd. All rights reserved.
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
Effects of hydrothermal treatment on the pyrolysis behavior of Chinese fan palm.
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.
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
Investigating pyrolysis characteristics of moso bamboo through TG-FTIR and Py-GC/MS.
Liang, Fang; Wang, Ruijuan; Hongzhong, Xiang; Yang, Xiaomeng; Zhang, Tao; Hu, Wanhe; Mi, Bingbing; Liu, Zhijia
2018-05-01
This study was carried out to investigate pyrolysis characteristics of moso bamboo (Phyllostachys pubescens), including outer layer (OB), middle layer (MB) and inner layer (IB) and bamboo leaves (BL), through TG-FTIR and Py-GC/MS. The results showed that 70% of weight loss occurred at rapid pyrolysis stage with temperature of 200-400 °C. With increase in heating rate, pyrolysis process shifted toward higher temperature. IB, OB, MB and BL had a different activation energy at different conversion rates. BL had a higher activation energy than IB, OB and MB. The volatiles of bamboo was complicated with 2-30 of C atoms. IB, OB and MB mainly released benzofuran, hydroxyacetaldehyde and 2-Pentanone. BL released furan, acetic acid and phenol. The main pyrolysis products included H 2 O, CH 4 , CO 2 , CO, carboxylic acids, NO, NO 2 . Pyrolysis products of IB was the most and that of BL was the lowest. MB had the lowest pyrolysis temperature. Copyright © 2018 Elsevier Ltd. All rights reserved.
Experimental study on the heat transfer characteristics of waste printed circuit boards pyrolysis.
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.
Cho, Jung Sang; Lee, Jeong-Cheol; Rhee, Sang-Hoon
2016-02-01
In the synthesis of hydroxyapatite powders by spray pyrolysis, control of the particle size was investigated by varying the initial concentration of the precursor solution and the pyrolysis temperature. Calcium phosphate solutions (Ca/P ratio of 1.67) with a range of concentrations from 0.1 to 2.0 mol/L were prepared by dissolving calcium nitrate tetrahydrate and diammonium hydrogen phosphate in deionized water and subsequently adding nitric acid. Hydroxyapatite powders were then synthesized by spray pyrolysis at 900°C and at 1500°C, using these calcium phosphate precursor solutions, under the fixed carrier gas flow rate of 10 L/min. The particle size decreased as the precursor concentration decreased and the spray pyrolysis temperature increased. Sinterability tests conducted at 1100°C for 1 h showed that the smaller and denser the particles were, the higher the relative densities were of sintered hydroxyapatite disks formed from these particles. The practical implication of these results is that highly sinterable small and dense hydroxyapatite particles can be synthesized by means of spray pyrolysis using a low-concentration precursor solution and a high pyrolysis temperature under a fixed carrier gas flow rate. © 2015 Wiley Periodicals, Inc.
Effect of pyrolysis temperature and air flow on toxicity of gases from a polycarbonate polymer
NASA Technical Reports Server (NTRS)
Hilado, C. J.; Brick, V. E.; Brauer, D. P.
1978-01-01
A polycarbonate polymer was evaluated for toxicity of pyrolysis gases generated at various temperatures without forced air flow and with 1 L/min air flow, using the toxicity screening test method developed at the University of San Francisco. Time to various animal responses decreased with increasing pyrolysis temperature over the range from 500 C to 800 C. There appeared to be no significant toxic effects at 400 C and lower temperatures.
Oil production by entrained pyrolysis of biomass and processing of oil and char
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.
Tucker RNG: Little machine, big impact
Maureen Essen; Caroline Morris; Nathaniel Anderson
2014-01-01
When the Tucker RNG thermal conversion unit connected to the power grid for the first time April 23 in Charlotte, N.C., Richard Tucker, president of Tucker Engineering Associates, could feel the weight of the world coming off his shoulders. After more than a decade of developing his high-temperature, fast pyrolysis system, he was finally seeing it export electricity...
Thompson, Logan C.; Ciesielski, Peter N.; Jarvis, Mark W.; ...
2017-07-12
Here, biomass particles can experience variable thermal conditions during fast pyrolysis due to differences in their size and morphology, and from local temperature variations within a reactor. These differences lead to increased heterogeneity of the chemical products obtained in the pyrolysis vapors and bio-oil. Here we present a simple, high-throughput method to investigate the thermal history experienced by large ensembles of particles during fast pyrolysis by imaging and quantitative image analysis. We present a correlation between the surface luminance (darkness) of the biochar particle and the highest temperature that it experienced during pyrolysis. Next, we apply this correlation to large,more » heterogeneous ensembles of char particles produced in a laminar entrained flow reactor (LEFR). The results are used to interpret the actual temperature distributions delivered by the reactor over a range of operating conditions.« less
Study on the combined sewage sludge pyrolysis and gasification process: mass and energy balance.
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.
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.
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.
A Comparative study of microwave-induced pyrolysis of lignocellulosic and algal biomass.
Wang, Nan; Tahmasebi, Arash; Yu, Jianglong; Xu, Jing; Huang, Feng; Mamaeva, Alisa
2015-08-01
Microwave (MW) pyrolysis of algal and lignocellulosic biomass samples were studied using a modified domestic oven. The pyrolysis temperature was recorded continuously by inserting a thermocouple into the samples. Temperatures as high as 1170 and 1015°C were achieved for peanut shell and Chlorella vulgaris. The activation energy for MW pyrolysis was calculated by Coats-Redfern method and the values were 221.96 and 214.27kJ/mol for peanut shell and C. vulgaris, respectively. Bio-oil yields reached to 27.7wt.% and 11.0wt.% during pyrolysis of C. vulgaris and peanut shell, respectively. The bio-oil samples from pyrolysis were analyzed by a gas chromatography-mass spectrometry (GC-MS). Bio-oil from lignocellulosic biomass pyrolysis contained more phenolic compounds while that from microalgae pyrolysis contained more nitrogen-containing species. Fourier transform infrared spectroscopy (FTIR) analysis results showed that concentration of OH, CH, CO, OCH3, and CO functional groups in char samples decreased significantly after pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.
Experimental study of thermal conductivity of pyrolysised materials by means of a flat layer
NASA Astrophysics Data System (ADS)
Vaniushkin, V. D.; Popov, S. K.; Sidenkov, D. V.
2017-11-01
Recycling of tires is currently a very important task. One of the areas of recycling tires is their low-temperature pyrolysis to produce marketable products - liquid fraction and a solid coke residue. For the development of the pyrolysis installation it is important to know the thermal conductivity of the coke residue at different temperatures of pyrolysis of initial material. As a property of matter, thermal conductivity depends in general on temperature and pressure. For materials with some structure, such as porous materials, the thermal conductivity depends on the characteristics of the structure. The thermal conductivity of the porous coke residue at pyrolysis temperatures of 300 0C, 400 0C, 500 0C and atmospheric pressure was studied experimentally at the laboratory unit of the department of “Theoretical basis of heat engineering” using the method of the flat layer in the temperature range 5…100 0C. Experimentally proved temperature dependencies of the coefficient of thermal conductivity of the coke residue are built to improve the accuracy of calculations of constructive and regime parameters of the pyrolysis installation.
Claoston, N; Samsuri, A W; Ahmad Husni, M H; Mohd Amran, M S
2014-04-01
Biochar has received great attention recently due to its potential to improve soil fertility and immobilize contaminants as well as serving as a way of carbon sequestration and therefore a possible carbon sink. In this work, a series of biochars were produced from empty fruit bunch (EFB) and rice husk (RH) by slow pyrolysis at different temperatures (350, 500, and 650°C) and their physicochemical properties were analysed. The results indicate that porosity, ash content, electrical conductivity (EC), and pH value of both EFB and RH biochars were increased with temperature; however, yield, cation exchange capacity (CEC), and H, C, and N content were decreased with increasing pyrolysis temperature. The Fourier transform IR spectra were similar for both RH and EFB biochars but the functional groups were more distinct in the EFB biochar spectra. There were reductions in the amount of functional groups as pyrolysis temperature increased especially for the EFB biochar. However, total acidity of the functional groups increased with pyrolysis temperature for both biochars.
Chemical yields from low-temperature pyrolysis of CCA-treated wood
Qirong Fu; Dimitris Argyropolous; Lucian Lucia; David Tilotta; Stan Lebow
2009-01-01
Low-temperature pyrolysis offers a feasible option for wood-waste management and the recovery of a variety of useful chemicals. The effect of chromated copper arsenate (CCA) wood preservative on the yield and composition of various pyrolysis products was investigated in the present research. A novel quantitative 31P nuclear magnetic resonance (...
Pyrolysis of flax straw: Characterization of char, liquid, and gas as fuel
NASA Astrophysics Data System (ADS)
Tushar, Mohammad Shahed Hasan Khan
The demand for energy continues to outstrip its supply and necessitates the development of renewable energy options. Biomass has been recognized as a major renewable energy source to supplement the declining fossil fuel source of energy. It is the most popular form of renewable energy and, currently, biofuel production is becoming more promising. Being carbon neutral, readily available, and low in sulphur content makes biomass a very promising source of renewable energy. In the present research, both the isothermal and non-isothermal pressurized pyrolysis of flax straw is studied for the first time. In case of isothermal pyrolysis, the influence of pyrolysis temperature and reaction time on char yield and morphology was investigated. The applied pyrolysis temperature was varied between 300 and 500°C. The reaction time was varied from 15 to 60 min. The char yield was found to decrease as pyrolysis temperature and reaction time increased. The char structure and surface morphology were thoroughly investigated by means of x-ray diffraction (XRD), temperature-programmed oxidation (TPO), and scanning electron microscopy (SEM). The degree of porosity and graphitization increased as pyrolysis temperature and time increased. In fact, the experiment performed at 500°C for 1h duration did not yield any char; only residual ash could be obtained. The TPO studies on the char samples corroborated the XRD findings and showed the presence of two types of carbon, namely, amorphous filamentous carbon and graphitic carbon. A thermogravimetric analysis (TGA) of the char was performed to gain an understanding of combustion kinetics and reactivity. It implied that the reactivity of the char decreases as temperature increases, and this finding is well supported by the TPO, TGA, SEM, and XRD characterization data. Furthermore, an empirical global model was devised based on the power law to estimate activation energy and other kinetic parameters. For the non-isothermal pressurized pyrolysis of flax straw, the experiments were carried out at different pressures, ranging from 10 to 40 psig. The three types of products thus obtained (gas, liquid, char) were thoroughly quantified and analyzed. The yields of the products were found to be dependent on the experimental conditions. It was observed that 10 psig of pressure gave the maximum yield of bio-oil, while 20 psig pressure lead to maximum char yield. The gaseous products were analyzed using an online GC, while the bio-oils were characterized using an offline GC/MS. SEM studies were performed to study the char morphology and porosity. The main gaseous products observed were CO, H2, CO2, CH 4, and C3. The bio-oils were mainly composed of phenolic compounds, carboxylic acids, and furfural. The pH and density of the bio-oils was found to increase as pyrolysis pressure increased. SEM investigation gave insights into the porosity of chars; as pressure increased, an increase in the porosity of char was noted. XRD studies showed that amorphous hydrocarbon and graphitic carbons are the major constituents of char, which was supported by TPO experiments. A TGA study showed two reaction zones for char oxidation. The kinetic parameters of oxidation were estimated using a power law model, which was also used for isothermal pyrolysis and isothermal char oxidation kinetics. Based on the data generated, the pressure of 10 psig was found to be optimum for bio-oil production, while a pressure of 20 psig was optimum for char production. With the increase in pressure, the production of individual gas components increased within the pressure range studied. Finally, with the increase in reaction pressure, temperature and time, the produced chars became less reactive.
Lee, Kyong-Hwan; Shin, Dae-Hyun
2007-01-01
Pyrolysis of a waste plastic mixture (high-density polyethylene: low-density polyethylene: polypropylene: polystyrene = 3:2:3:1) into a liquid product was carried out in a stirred semi-batch reactor at low (350 degrees C) and high (400 degrees C) temperatures. The effect of lapse time of reaction in the reactor and also degradation temperature on the characteristics of the liquid product from pyrolysis of the mixture was investigated. Liquid products were described by cumulative amount distribution, paraffin, olefin, naphthene and aromatic (PONA) distribution and molecular weight distribution. Their characteristic was quite differed with a lapse time of reaction and also at a low and high degradation temperatures, because of the different physicochemical properties of the plastic types in the mixture. With increase of lapse time of reaction, the order for the main products in PONA components obtained at 350 degrees C was firstly aromatic products and then olefin products, while at 400 degrees C the order was firstly aromatic products, then olefin products and finally paraffin products. The experiments also showed from the molecular weight distribution of liquid PONA components that the paraffin and olefin products had a wide distribution by mainly random scission of polymer, but in the case of olefin products were produced by an end-chain scission mechanism as well as random scission mechanism, as evidenced by much more light olefin products. This phenomenon was evident at a higher degradation temperature. Also, both the light olefin and naphthene products with a molecular weight of around 120, as a main product, showed a similar trend as a function of lapse time, which had a maximum fraction at 343 min (at 350 degrees C) and 83 min (at 400 degrees C). Among PONA components, the highest concentrations of aromatic products were obtained with a molecular weight of around 100 at the fastest lapse time of reaction, regardless of degradation temperature. It was concluded that the characteristics of liquid product on the pyrolysis of plastic mixtures were strongly influenced by lapse time of reaction and degradation temperature.
Chiang, Hung-Lung; Lin, Kuo-Hsiung; Lai, Nina; Shieh, Zhu-Xin
2014-05-15
Biosludge can be pyrolyzed to produce liquid oil as an alternative fuel. The content of five major elements, 22 trace elements and 16 PAHs was investigated in oven-dried raw material, pyrolysis residues and pyrolysis liquid products. Results indicated 39% carbon, 4.5% hydrogen, 4.2% nitrogen and 1.8% sulfur were in oven dried biosludge. Biosludge pyrolysis, carried out at temperatures from 400 to 800°C, corresponded to 34-14% weight in pyrolytic residues, 32-50% weight in liquid products and 31-40% weight in the gas phase. The carbon, hydrogen and nitrogen decreased and the sulfur content increased with an increase in the pyrolysis temperature at 400-800°C. NaP (2 rings) and AcPy (3 rings) were the major PAHs, contributing 86% of PAHs in oven-dried biosludge. After pyrolysis, the PAH content increased with the increase of pyrolysis temperature, which also results in a change in the PAH species profile. In pyrolysis liquid oil, NaP, AcPy, Flu and PA were the major species, and the content of the 16 PAHs ranged from 1.6 to 19 μg/ml at pyrolysis temperatures ranging from 400 to 800°C. Ca, Mg, Al, Fe and Zn were the dominant trace elements in the raw material and the pyrolysis residues. In addition, low toxic metal (Cd, V, Co, and Pb) content was found in the liquid oil, and its heat value was 7,800-9,500 kcal/kg, which means it can be considered as an alternative fuel. Copyright © 2014 Elsevier B.V. All rights reserved.
Microwave-assisted co-pyrolysis of brown coal and corn stover for oil production.
Zhang, Yaning; Fan, Liangliang; Liu, Shiyu; Zhou, Nan; Ding, Kuan; Peng, Peng; Anderson, Erik; Addy, Min; Cheng, Yanling; Liu, Yuhuan; Li, Bingxi; Snyder, John; Chen, Paul; Ruan, Roger
2018-07-01
The controversial synergistic effect between brown coal and biomass during co-pyrolysis deserves further investigation. This study detailed the oil production from microwave-assisted co-pyrolysis of brown coal (BC) and corn stover (CS) at different CS/BC ratios (0, 0.33, 0.50, 0.67, and 1) and pyrolysis temperatures (500, 550, and 600 °C). The results showed that a higher CS/BC ratio resulted in higher oil yield, and a higher pyrolysis temperature increased oil yield for brown coal and coal/corn mixtures. Corn stover and brown coal showed different pyrolysis characteristics, and positive synergistic effect on oil yield was observed only at CS/BC ratio of 0.33 and pyrolysis temperature of 600 °C. Oils from brown coal mainly included hydrocarbons and phenols whereas oils from corn stover and coal/corn mixtures were dominated by ketones, phenols, and aldehydes. Positive synergistic effects were observed for ketones, aldehydes, acids, and esters whereas negative synergistic effects for hydrocarbons, phenols and alcohols. Copyright © 2018 Elsevier Ltd. All rights reserved.
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.
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
Molecular-Level Processing of Si-(B)-C Materials with Tailored Nano/Microstructures.
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.
Analysis and comparison of biomass pyrolysis/gasification condensates: Final report
DOE Office of Scientific and Technical Information (OSTI.GOV)
Elliott, D.C.
1986-06-01
This report provides results of chemical and physical analysis of condensates from eleven biomass gasification and pyrolysis systems. The samples were representative of the various reactor configurations being researched within the Department of Energy, Biomass Thermochemical Conversion program. The condensates included tar phases and aqueous phases. The analyses included gross compositional analysis (elemental analysis, ash, moisture), physical characterization (pour point, viscosity, density, heat of combustion, distillation), specific chemical analysis (gas chromatography/mass spectrometry, infrared spectrophotometry, proton and carbon-13 nuclear magnetic resonance spectrometry) and biological activity (Ames assay and mouse skin tumorigenicity tests). These results are the first step of a longermore » term program to determine the properties, handling requirements, and utility of the condensates recovered from biomass gasification and pyrolysis. The analytical data demonstrates the wide range of chemical composition of the organics recovered in the condensates and suggests a direct relationship between operating temperature and chemical composition of the condensates. A continuous pathway of thermal degradation of the tar components as a function of temperature is proposed. Variations in the chemical composition of the organic components in the tars are reflected in the physical properties of tars and phase stability in relation to water in the condensate. The biological activity appears to be limited to the tars produced at high temperatures. 56 refs., 25 figs., 21 tabs.« less
Supercritical water pyrolysis of sewage sludge.
Ma, Wenchao; Du, Guiyue; Li, Jian; Fang, Yuanhao; Hou, Li'an; Chen, Guanyi; Ma, Degang
2017-01-01
Municipal sewage sludge (SS) from wastewater treatment plant containing high water content (>85wt.%), lead to the difficulty of co-combustion with MSW or coal due to the high cost of drying. This study explores an alternative method by supercritical water (SCW) pyrolysis of sewage sludge (SS) in a high pressure reaction vessel. The effects of temperature and moisture content of SS on yield and composition of the products (bio-oil, bio char and non-condensable gas) were studied. A temperature of 385°C and moisture content of 85wt.% were found to be the optimum conditions for the maximum bio-oil production of 37.23wt.%, with a higher heating value of 31.08MJ/kg. In the optimum condition, the yields of aliphatic hydrocarbon and phenols were about 29.23wt.% and 12.51wt.%, respectively. The physical and chemical properties of bio-char were analyzed by using XRF and BET. Results of GC analyses of NCG showed that it has the maximum HHV of 13.39MJ/m 3 at 445°C and moisture content of 85wt.%. The reaction path from SS to bio-oil through SCW pyrolysis was given. Moreover, carbon balance was calculated for the optimal condition, and finding out that 64.27wt.% of the carbon content was transferred from SS to bio-oil. Finally, this work demonstrates that the SCW pyrolysis is a promising disposal method for SS. Copyright © 2016. Published by Elsevier Ltd.
Char yield on pyrolysis of cellulose
A. Broido; Maxine A. Nelson
1975-01-01
Whether the pyrolysis of cellulose is conducted in an inert medium or in air, partial pyrolysis at a lower temperature increases the char yield subsequently obtained after 1 hour at 370°C. The results are consistent with a pyrolysis scheme in which two competing sequences of cellulose pyrolysis reactions are initiated by (1) an intermolecular dehydration leading to...
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% (
Hu, Guangji; Li, Jianbing; Zhang, Xinying; Li, Yubao
2017-05-01
The treatment of waste biomass (sawdust) through co-pyrolysis with refinery oily sludge was carried out in a fixed-bed reactor. Response surface method was applied to evaluate the main and interaction effects of three experimental factors (sawdust percentage in feedstock, temperature, and heating rate) on pyrolysis oil and char yields. It was found that the oil and char yields increased with sawdust percentage in feedstock. The interaction between heating rate and sawdust percentage as well as between heating rate and temperature was significant on the pyrolysis oil yield. The higher heating value of oil originated from sawdust during co-pyrolysis at a sawdust/oily sludge ratio of 3:1 increased by 5 MJ/kg as compared to that during sawdust pyrolysis alone, indicating a synergistic effect of co-pyrolysis. As a result, petroleum sludge can be used as an effective additive in the pyrolysis of waste biomass for improving its energy recovery. Copyright © 2017 Elsevier Ltd. All rights reserved.
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.
Synthesis, characterization and ellipsometric study of ultrasonically sprayed Co3O4 films
NASA Astrophysics Data System (ADS)
Gençyılmaz, O.; Taşköprü, T.; Atay, F.; Akyüz, İ.
2015-10-01
In the present study, cobalt oxide (Co3O4) films were produced using ultrasonic spray pyrolysis technique onto the glass substrate at different temperatures (200-250-300-350 °C). The effect of substrate temperature on the structural, optical, surface and electrical properties of Co3O4 films was reported. Thickness, refractive index and extinction coefficient of the films were determined by spectroscopic ellipsometry, and X-ray diffraction analyses revealed that Co3O4 films were polycrystalline fcc structure and the substrate temperature significantly improved the crystal structure of Co3O4 films. The films deposited at 350 °C substrate temperature showed the best structural quality. Transmittance, absorbance and reflectance spectra were taken by means of UV-Vis spectrophotometer, and optical band gap values were calculated using optical method. Surface images and roughness values of the films were taken by atomic force microscopy to see the effect of deposition temperature on surface properties. The resistivity of the films slightly decreases with increase in the substrate temperature from 1.08 × 104 to 1.46 × 102 Ω cm. Finally, ultrasonic spray pyrolysis technique allowed production of Co3O4 films, which are alternative metal oxide film for technological applications, at low substrate temperature.
A study on experimental characteristic of microwave-assisted pyrolysis of microalgae.
Hu, Zhifeng; Ma, Xiaoqian; Chen, Chunxiang
2012-03-01
The microwave-assisted pyrolysis of Chlorella vulgaris was carried out under different microwave power levels, catalysts and contents of activated carbon and solid residue. The products, pyrolysis temperature and temperature rising rate were analyzed in order to obtain the optimal conditions. The results indicated that the higher the microwave power level was, the higher the maximum temperature rising rate and pyrolysis temperature were. The maximum bio-oil yield (35.83 wt.%) and gas yield (52.37%) were achieved under the microwave power of 1500 W and 2250 W, respectively. And 2250 W was the optimal power to obtain bio-fuel product. High microwave power level and catalyst can enhance the production of gas. Catalysts can promote the pyrolysis of C. vulgaris, and activated carbon was the best among the tested catalysts followed by the solid residue. The optimal content of activated carbon is 5% with the maximum bio-fuel yield of 87.47%. Copyright © 2011 Elsevier Ltd. All rights reserved.
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.
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
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.
Co-pyrolysis of rice straw and polypropylene using fixed-bed pyrolyzer
NASA Astrophysics Data System (ADS)
Izzatie, N. I.; Basha, M. H.; Uemura, Y.; Mazlan, M. A.; Hashim, M. S. M.; Amin, N. A. M.; Hamid, M. F.
2016-11-01
The present work encompasses the impact of temperature (450, 500, 550, 600 °C) on the properties of pyrolysis oil and on other product yield for the co-pyrolysis of Polypropylene (PP) plastics and rice straw. Co-pyrolysis of PP plastic and rice straw were conducted in a fixed-bed drop type pyrolyzer under an inert condition to attain maximum oil yield. Physically, the pyrolysis oil is dark-brown in colour with free flowing and has a strong acrid smell. Copyrolysis between these typically obtained in maximum pyrolysis oil yields up to 69% by ratio 1:1 at a maximum temperature of 550 °C. From the maximum yield of pyrolysis oil, characterization of pyrolysis product and effect of biomass type of the composition were evaluated. Pyrolysis oil contains a high water content of 66.137 wt.%. Furfural, 2- methylnaphthalene, tetrahydrofuran (THF), toluene and acetaldehyde were the major organic compounds found in pyrolysis oil of rice straw mixed with PP. Bio-char collected from co-pyrolysis of rice straw mixed with PP plastic has high calorific value of 21.190 kJ/g and also carbon content with 59.02 wt.% and could contribute to high heating value. The non-condensable gases consist of hydrogen, carbon monoxide, and methane as the major gas components.
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.
NASA Astrophysics Data System (ADS)
Williams, E. K.; Rosenheim, B. E.
2011-12-01
Ramped pyrolysis methodology, such as that used in the programmed-temperature pyrolysis/combustion system (PTP/CS), improves radiocarbon analysis of geologic materials devoid of authigenic carbonate compounds and with low concentrations of extractable authochthonous organic molecules. The approach has improved sediment chronology in organic-rich sediments proximal to Antarctic ice shelves (Rosenheim et al., 2008) and constrained the carbon sequestration potential of suspended sediments in the lower Mississippi River (Roe et al., in review). Although ramped pyrolysis allows for separation of sedimentary organic material based upon relative reactivity, chemical information (i.e. chemical composition of pyrolysis products) is lost during the in-line combustion of pyrolysis products. A first order approximation of ramped pyrolysis/combustion system CO2 evolution, employing a simple Gaussian decomposition routine, has been useful (Rosenheim et al., 2008), but improvements may be possible. First, without prior compound-specific extractions, the molecular composition of sedimentary organic matter is unknown and/or unidentifiable. Second, even if determined as constituents of sedimentary organic material, many organic compounds have unknown or variable decomposition temperatures. Third, mixtures of organic compounds may result in significant chemistry within the pyrolysis reactor, prior to introduction of oxygen along the flow path. Gaussian decomposition of the reaction rate may be too simple to fully explain the combination of these factors. To relate both the radiocarbon age over different temperature intervals and the pyrolysis reaction thermograph (temperature (°C) vs. CO2 evolved (μmol)) obtained from PTP/CS to chemical composition of sedimentary organic material, we present a modeling framework developed based upon the ramped pyrolysis decomposition of simple mixtures of organic compounds (i.e. cellulose, lignin, plant fatty acids, etc.) often found in sedimentary organic material to account for changes in thermograph shape. The decompositions will be compositionally verified by 13C NMR analysis of pyrolysis residues from interrupted reactions. This will allow for constraint of decomposition temperatures of individual compounds as well as chemical reactions between volatilized moieties in mixtures of these compounds. We will apply this framework with 13C NMR analysis of interrupted pyrolysis residues and radiocarbon data from PTP/CS analysis of sedimentary organic material from a freshwater marsh wetland in Barataria Bay, Louisiana. We expect to characterize the bulk chemical composition during pyrolysis and as well as diagenetic changes with depth. Most importantly, we expect to constrain the potential and the limitations of this modeling framework for application to other depositional environments.
Conventional and fast pyrolysis of automobile shredder residues (ASR).
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.
Ma, Hongrui; Gao, Mao; Hua, Li; Chao, Hao; Xu, Jing
2015-11-01
Tannery sludge contained plenty of organic matter, and the organic substance stability had direct impact on its derived chars' utilization. In this paper, the stabilization of tannery sludge and the variation of humic acid-like (HAL) extracted by different methods were investigated in a magnetic stirring reactor under low temperature pyrolysis of 100-400 °C. Results showed that the aromatic structure of pyrolysis chars increased with the increase of temperature and time. The char contained highly aromatic structure and relatively small dissolved organic matters (DOM) at 300 °C. The similar behaviors appeared in two HAL series by different extraction methods. The N content, H/C value, and aliphatic structures of HAL decreased with the increase of pyrolysis temperature, while the C/N value and aromatic structures increased with the rise of pyrolysis temperature. The composition and functional groups of HAL were similar with the purchased humic acid (HA). The fluorescence spectra revealed that two main peaks were found at Ex/Em = 239/363-368 nm and 283/359-368 nm in each HAL series from raw and 100 °C pyrolysis tannery sludge, representing a protein-like matter. The new peak appeared at Ex/Em = 263-283/388 nm in each HAL series from 200 °C pyrolysis tannery sludge-represented humic acid-like matter. The fluorescence intensity increased strongly compared to the other two peak intensity. Therefore, the humification of organic matter was increased by pyrolyzing. Notably, the HAL from 200 °C pyrolysis tannery sludge contained simple molecular structure, and the polycondensation increased but with a relative lower humification degree compared to soil HAL and purchased HA. Therefore, the sludge needs further oxidation. The humic substance was negligible by direct extraction when the temperature was 300 and 400 °C.
Hwang, In-Hee; Kobayashi, Jun; Kawamoto, Katsuya
2014-02-01
Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products. The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500°C but the polycyclic aromatic hydrocarbons became the major compounds at 900°C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700°C under steam gasification condition. For WBC, both char utilization by pyrolysis at low temperature (500°C) and syngas recovery by steam gasification at higher temperature (900°C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500°C) might be one of viable options. Steam gasification at 900°C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered. Copyright © 2013 Elsevier Ltd. All rights reserved.
Samorì, Chiara; Torri, Cristian; Fabbri, Daniele; Falini, Giuseppe; Faraloni, Cecilia; Galletti, Paola; Spera, Silvia; Tagliavini, Emilio; Torzillo, Giuseppe
2012-08-01
Acid catalysts were prepared by sulfonation of carbon materials obtained from the pyrolysis of sugar beet molasses, a cheap, viscous byproduct in the processing of sugar beets into sugar. Conditions for the pyrolysis of molasses (temperature and time) influenced catalyst performance; the best combination came from pyrolysis at low temperature (420 °C) for a relatively long time (8-15 h), which ensured better stability of the final material. The most effective molasses catalyst was highly active in the esterification of fatty acids with methanol (100 % yield after 3 h) and more active than common solid acidic catalysts in the transesterification of vegetable oils with 25-75 wt % of acid content (55-96 % yield after 8 h). A tandem process using a solid acid molasses catalyst and potassium hydroxide in methanol was developed to de-acidificate and transesterificate algal oils from Chlamydomonas reinhardtii, Nannochloropsis gaditana, and Phaeodactylum tricornutum, which contain high amounts of free fatty acids. The amount of catalyst required for the de-acidification step was influenced by the chemical composition of the algal oil, thus operational conditions were determined not only in relation to free fatty acids content in the oil, but according to the composition of the lipid extract of each algal species. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Yang, Xuewei; Ma, Fuying; Yu, Hongbo; Zhang, Xiaoyu; Chen, Shulin
2011-02-01
The thermal decomposition of biopretreated corn stover during the low temperature has been studied by using the Py-GC/MS analysis and thermogravimetric analysis with the distributed activation energy model (DAEM). Results showed that biopretreatment with white-rot fungus Echinodontium taxodii 2538 can improve the low-temperature pyrolysis of biomass, by increasing the pyrolysis products of cellulose, hemicellulose (furfural and sucrose increased up to 4.68-fold and 2.94-fold respectively) and lignin (biophenyl and 3,7,11,15-tetramethyl-2-hexadecen-1-ol increased 2.45-fold and 4.22-fold, respectively). Calculated by DAEM method, it showed that biopretreatment can decrease the activation energy during the low temperature range, accelerate the reaction rate and start the thermal decomposition with lower temperature. ATR-FTIR results showed that the deconstruction of lignin and the decomposition of the main linkages between hemicellulose and lignin could contribute to the improvement of the pyrolysis at low temperature. Copyright © 2010 Elsevier Ltd. All rights reserved.
Solar heated oil shale pyrolysis process
NASA Technical Reports Server (NTRS)
Qader, S. A. (Inventor)
1985-01-01
An improved system for recovery of a liquid hydrocarbon fuel from oil shale is presented. The oil shale pyrolysis system is composed of a retort reactor for receiving a bed of oil shale particules which are heated to pyrolyis temperature by means of a recycled solar heated gas stream. The gas stream is separated from the recovered shale oil and a portion of the gas stream is rapidly heated to pyrolysis temperature by passing it through an efficient solar heater. Steam, oxygen, air or other oxidizing gases can be injected into the recycle gas before or after the recycle gas is heated to pyrolysis temperature and thus raise the temperature before it enters the retort reactor. The use of solar thermal heat to preheat the recycle gas and optionally the steam before introducing it into the bed of shale, increases the yield of shale oil.
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.
Biomass fast pyrolysis for bio-oil production in a fluidized bed reactor under hot flue atmosphere.
Li, Ning; Wang, Xiang; Bai, Xueyuan; Li, Zhihe; Zhang, Ying
2015-10-01
Fast pyrolysis experiments of corn stalk were performed to investigate the optimal pyrolysis conditions of temperature and bed material for maximum bio-oil production under flue gas atmosphere. Under the optimized pyrolysis conditions, furfural residue, xylose residue and kelp seaweed were pyrolyzed to examine their yield distributions of products, and the physical characteristics of bio-oil were studied. The best flow rate of the flue gas at selected temperature is obtained, and the pyrolysis temperature at 500 degrees C and dolomite as bed material could give a maximum bio-oil yield. The highest bio-oil yield of 43.3% (W/W) was achieved from corn stalk under the optimal conditions. Two main fractions were recovered from the stratified bio-oils: light oils and heavy oils. The physical properties of heavy oils from all feedstocks varied little. The calorific values of heavy oils were much higher than that of light oils. The pyrolysis gas could be used as a gaseous fuel due to a relatively high calorific value of 6.5-8.5 MJ/m3.
Pyrolysis of softwood carbohydrates in a fluidized bed reactor.
Aho, Atte; Kumar, Narendra; Eränen, Kari; Holmbom, Bjarne; Hupa, Mikko; Salmi, Tapio; Murzin, Dmitry Yu
2008-09-01
In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood), was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5 degrees C/min) was applied to the heating until a reactor temperature of 460 degrees C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure.
Pyrolysis of Softwood Carbohydrates in a Fluidized Bed Reactor
Aho, Atte; Kumar, Narendra; Eränen, Kari; Holmbom, Bjarne; Hupa, Mikko; Salmi, Tapio; Murzin, Dmitry Yu.
2008-01-01
In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood), was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5 °C/min) was applied to the heating until a reactor temperature of 460 °C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure. PMID:19325824
Yuan, G; Chen, D; Yin, L; Wang, Z; Zhao, L; Wang, J Y
2014-06-01
In this research a gas-liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas-liquid fluidized bed reactor was running at 280-320 °C, where hot N2 was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N2 to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N2 gas was set around 0.47-0.85 Nm(3) kg(-1) for the molten PVC. Larger N2 flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N2 flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas-liquid fluidized bed reactor for dechlorination. Copyright © 2013 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Aston, Steve; Doerr, Stefan; Street-Perrott, Alayne
2013-04-01
The production of biochar and its application to soil has the potential to make a significant contribution to climate change mitigation whilst simultaneously improving soil fertility, crop yield and soil water-holding capacity. Biochar is produced from various biomass feedstock materials at varying pyrolysis temperatures, but relatively little is known about how these parameters affect the properties of the resultant biochars and their impact on the properties of the soils to which they are subsequently applied. Salix viminalis, M. giganteus and Picea sitchensis feedstocks were chipped then sieved to 2 - 5 mm, oven dried to constant weight, then pyrolyzed at 350, 500, 600 and 800° C in a nitrogen-purged tube furnace. Biochar yields were measured by weighing the mass of each sample before and after pyrolysis. Biochar hydrophobicity was assessed by using a goniometer to measure water-droplet contact-angles. Cation-exchange-capacity (CEC) was measured using the ammonium acetate method. Biochars were also produced in a rotary kiln from softwood pellets at 400, 500, 600 and 700° C then ground to 0.4 - 1 mm and applied to a sandy loam at a rate of 50 g kg-1. Bulk densities of these soil-biochar mixtures were measured on a tapped, dry, basis. The water-holding-capacity (WHC) of each mixture was measured gravimetrically following saturation and free-draining. The filter paper method was used to assess how pyrolysis temperature influences the effect of biochar application on matric suction. For all feedstocks, large decreases in biochar yield were observed between the pyrolysis temperatures of 350° C and 500° C. For Salix viminalis and M. giganteus feedstocks, subsequent reductions in the yield with increasing pyrolysis temperature were much lower. There were significant differences in hydrophobicity between biochars produced from different biomass and mean biochar hydrophobicity decreased with increasing pyrolysis temperature for all feedstocks. Results for CEC and WHC measurements will also be presented. With water contents of 0.04, 0.08 and 0.16 cm3 cm-3, the mean matric suctions of a sandy loam were higher when biochar was added. However, the differences were only statistically significant at a water content of 0.16 cm3 cm-3, where biochar produced at 500° C had the highest suction. Biochar additions always lowered the mean bulk density of a sandy loam, but there were significant differences in the extent to which biochars produced at different temperatures did this. Biochar yields and hydrophobicity vary according to feedstock type and decrease with increasing pyrolysis temperature. Application of biochar can significantly reduce bulk density but the extent of this effect varies according to the pyrolysis temperature at which the biochar is produced. Pyrolysis temperature can have a significant influence on how biochars affect soil suction. Acknowledgements: This study was funded by a UK Natural Environment Research Council (NERC) Doctoral Training Grant: NE/H525154/1.
Zwetsloot, Marie J; Lehmann, Johannes; Solomon, Dawit
2015-01-01
Pyrolysis of slaughterhouse waste could promote more sustainable phosphorus (P) usage through the development of alternative P fertilizers. This study investigated how pyrolysis temperature (220, 350, 550 and 750 °C), rendering before pyrolysis, and wood or corn biomass additions affect P chemistry in bone char, plant availability, and its potential as P fertilizer. Linear combination fitting of synchrotron-based X-ray absorption near edge structure spectra demonstrated that higher pyrolysis temperatures decreased the fit with organic P references, but increased the fit with a hydroxyapatite (HA) reference, used as an indicator of high calcium phosphate (CaP) crystallinity. The fit to the HA reference increased from 0% to 69% in bone with meat residue and from 20% to 95% in rendered bone. Biomass additions to the bone with meat residue reduced the fit to the HA reference by 83% for wood and 95% for corn, and additions to rendered bone by 37% for wood. No detectable aromatic P forms were generated by pyrolysis. High CaP crystallinity was correlated with low water-extractable P, but high formic acid-extractable P indicative of high plant availability. Bone char supplied available P which was only 24% lower than Triple Superphosphate fertilizer and two- to five-fold higher than rock phosphate. Pyrolysis temperature and biomass additions can be used to design P fertilizer characteristics of bone char through changing CaP crystallinity that optimize P availability to plants. © 2014 Society of Chemical Industry.
Tran, Hai Nguyen; Lee, Chung-Kung; Nguyen, Tien Vinh; Chao, Huan-Ping
2017-08-24
Three saccharides (glucose, sucrose, and xylose) were used as pure precursors for synthesizing spherical biochars (GB, SB, and XB), respectively. The two-stage synthesis process comprised: (1) the hydrothermal carbonization of saccharides to produce spherical hydrochar' and (2) pyrolysis of the hydrochar at different temperatures from 300°C to 1200°C. The results demonstrated that the pyrolysis temperatures insignificantly affected the spherical morphology and surface chemistry of biochar. The biochar' isoelectric point ranged from 2.64 to 3.90 (abundant oxygen-containing functionalities). The Brunauer-Emmett-Teller (BET)-specific surface areas (S BET ) and total pore volumes (V total ) of biochar increased with the increasing pyrolysis temperatures. The highest S BET and V total were obtained at a pyrolysis temperature of 900°C for GB (775 m 2 /g and 0.392 cm 3 /g), 500°C for SB (410 m 2 /g and 0.212 cm 3 /g), and 600°C for XB (426 m 2 /g and 0.225 cm 3 /g), respectively. The spherical biochar was a microporous material with approximately 71-98% micropore volume. X-ray diffraction results indicated that the biochar' structure was predominantly amorphous. The spherical biochar possessed the graphite structure when the pyrolysis temperature was higher than 600°C. The adsorption capacity of GB depended strongly on the pyrolysis temperature. The maximum Langmuir adsorption capacities ([Formula: see text]) of 900GB exhibited the following selective order: phenol (2.332 mmol/g) > Pb 2+ (1.052 mmol/g) > Cu 2+ (0.825 mmol/g) > methylene green 5 (0.426 mmol/g) > acid red 1 (0.076 mmol/g). This study provides a simple method to prepare spherical biochar - a new and potential adsorbent for adsorbing heavy metals and aromatic contaminants.
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.
Production and characterization of chars from cherry pulp via pyrolysis.
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.
NASA Astrophysics Data System (ADS)
Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney
2016-07-01
Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H513CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H513CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).
DOE Office of Scientific and Technical Information (OSTI.GOV)
Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg
2016-07-05
Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 us. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures upmore » to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 13CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 13CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ormond, Thomas K.; Scheer, Adam M.; Nimlos, Mark R.
2015-07-16
The thermal decomposition of cyclopentadienone (C5H4-O) has been studied in a flash pyrolysis continuous flow microreactor. Passing dilute samples of o-phenylene sulfite (C6H4O2SO) in He through the microreactor at elevated temperatures yields a relatively clean source of C5H4-O. The pyrolysis of C5H4-O was investigated over the temperature range 1000-2000 K.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Thompson, Logan C.; Ciesielski, Peter N.; Jarvis, Mark W.
Here, biomass particles can experience variable thermal conditions during fast pyrolysis due to differences in their size and morphology, and from local temperature variations within a reactor. These differences lead to increased heterogeneity of the chemical products obtained in the pyrolysis vapors and bio-oil. Here we present a simple, high-throughput method to investigate the thermal history experienced by large ensembles of particles during fast pyrolysis by imaging and quantitative image analysis. We present a correlation between the surface luminance (darkness) of the biochar particle and the highest temperature that it experienced during pyrolysis. Next, we apply this correlation to large,more » heterogeneous ensembles of char particles produced in a laminar entrained flow reactor (LEFR). The results are used to interpret the actual temperature distributions delivered by the reactor over a range of operating conditions.« less
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.
Comparison of the pyrolysis behavior of lignins from different tree species.
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.
Derivation of hydrous pyrolysis kinetic parameters from open-system pyrolysis
NASA Astrophysics Data System (ADS)
Tseng, Yu-Hsin; Huang, Wuu-Liang
2010-05-01
Kinetic information is essential to predict the temperature, timing or depth of hydrocarbon generation within a hydrocarbon system. The most common experiments for deriving kinetic parameters are mainly by open-system pyrolysis. However, it has been shown that the conditions of open-system pyrolysis are deviant from nature by its low near-ambient pressure and high temperatures. Also, the extrapolation of heating rates in open-system pyrolysis to geological conditions may be questionable. Recent study of Lewan and Ruble shows hydrous-pyrolysis conditions can simulate the natural conditions better and its applications are supported by two case studies with natural thermal-burial histories. Nevertheless, performing hydrous pyrolysis experiment is really tedious and requires large amount of sample, while open-system pyrolysis is rather convenient and efficient. Therefore, the present study aims at the derivation of convincing distributed hydrous pyrolysis Ea with only routine open-system Rock-Eval data. Our results unveil that there is a good correlation between open-system Rock-Eval parameter Tmax and the activation energy (Ea) derived from hydrous pyrolysis. The hydrous pyrolysis single Ea can be predicted from Tmax based on the correlation, while the frequency factor (A0) is estimated based on the linear relationship between single Ea and log A0. Because the Ea distribution is more rational than single Ea, we modify the predicted single hydrous pyrolysis Ea into distributed Ea by shifting the pattern of Ea distribution from open-system pyrolysis until the weight mean Ea distribution equals to the single hydrous pyrolysis Ea. Moreover, it has been shown that the shape of the Ea distribution is very much alike the shape of Tmax curve. Thus, in case of the absence of open-system Ea distribution, we may use the shape of Tmax curve to get the distributed hydrous pyrolysis Ea. The study offers a new approach as a simple method for obtaining distributed hydrous pyrolysis Ea with only routine open-system Rock-Eval data, which will allow for better estimating hydrocarbon generation.
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.
Mu, Lin; Chen, Jianbiao; Yao, Pikai; Zhou, Dapeng; Zhao, Liang; Yin, Hongchao
2016-12-01
Co-pyrolysis characteristics of petrochemical wastewater sludge and Huolinhe lignite were investigated using thermogravimetric analyzer and packed-bed reactor coupled with Fourier transform infrared spectrometer and gas chromatography. The pyrolysis characteristics of the blends at various sludge blending ratios were compared with those of the individual materials. Thermogravimetric experiments showed that the interactions between the blends were beneficial to generate more residues. In packed-bed reactor, synergetic effects promoted the release of gas products and left less liquid and solid products than those calculated by additive manner. Fourier transform infrared spectrometer analysis showed that main functional groups in chars gradually disappeared with pyrolysis temperatures increasing, and H 2 O, CH 4 , CO, and CO 2 appeared in volatiles during pyrolysis. Gas compositions analysis indicated that, the yields of H 2 and CO clearly increased as the pyrolysis temperature and sludge blending ratio increasing, while the changes of CH 4 and CO 2 yields were relatively complex. Copyright © 2016 Elsevier Ltd. All rights reserved.
Chi, Yongchao; Xue, Junjie; Zhuo, Jiankun; Zhang, Dahu; Liu, Mi; Yao, Qiang
2018-08-15
Fast pyrolysis is one of the most economical and efficient technologies to convert biomass to bio-oil and valuable chemical products. Co-pyrolysis with hydrogen rich materials such as plastics over zeolite catalysts is one of the significant solutions to various problems of bio-oil such as high oxygen content, low heat value and high acid content. This paper studied pyrolysis of cellulose and polypropylene (PP) separately and co-pyrolysis of cellulose and PP over MCM-41 and Al-MCM-41. The pyrolysis over different heating rates (10K/min, 20K/min, 30K/min) was studied by Thermogravimetry Analysis (TGA) and kinetic parameters were obtained by Coats-Redfern method and isoconversion method. TG and DTG data shows that the two catalysts advance the pyrolysis reaction of PP significantly and reduce its peak temperature of DTG curve from 458°C to 341°C. The activation energy of pyrolysis of PP also has a remarkable reduction over the two catalysts. Py-GC/MS method was used to obtain the product distribution of pyrolysis of cellulose and PP separately and co-pyrolysis of cellulose and PP over MCM-41 and Al-MCM-41 at constant temperature of 650°C. Experiment results proved that co-pyrolysis with PP bring significant changes to the product distribution of cellulose. Oxygenated compounds such as furans are decreased, while yields of olefins and aromatics increase greatly. The yield of furans increases with the catalysis of MCM-41 as for the pyrolysis of cellulose and co-pyrolysis, while the yield of olefins and aromatics both experience significant growth over Al-MCM-41, which can be explained by the abundant acid centers in Al-MCM-41. Copyright © 2018 Elsevier B.V. All rights reserved.
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.
Analysis of Low-Pressure Gas-Phase Pyrolytic Reactions by Mass Spectrometric Techniques,
1989-01-01
temperatures and pressures known only as a polymeric substance, is similarly obtained in high purity by heating the polymer to its melting point (105-110’ C...filaments for Curie- point pyrolysis’ J.Anal.Appl.Pyrolysis. 5 (1983) 1-7 (with Helge Egsgaard) 4) ’Heterogeneous catalysis in gas phase reactions studied...by Curie- point pyrolysis. Gas phase pyrolysis of methyl dithio- acetat’ J.Anal.Appl.Pyrolysis. 5 (1983) 257-259 (with Helge Egsgaard) 5) ’Continuous
Formation of nanocarbon spheres by thermal treatment of woody char from fast pyrolysis process
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....
Shang, Guofeng; Liu, Liang; Chen, Ping; Shen, Guoqing; Li, Qiwu
2016-05-01
The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperature has great influence on the adsorption of H2S. At the different pyrolysis temperature, the H2S removal efficiency of rice hull-derived biochar was different. The adsorption capacities of biochar were 2.09 mg·g(-1), 2.65 mg·g(-1), 16.30 mg·g(-1), 20.80 mg·g(-1), and 382.70 mg·g(-1), which their pyrolysis temperatures were 100 °C, 200 °C, 300 °C, 400 °C and 500 °C respectively. Based on the Yoon-Nelson model, it analyzed the mass transfer mechanism of hydrogen sulfide adsorption by biochar. The paper focuses on the biochar derived from rice hull-removed hydrogen sulfide (H2S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperatures have great influence on the adsorption of H2S. At the different pyrolysis temperatures, the H2S removal efficiency of rice hull-derived biohar was different. The adsorption capacities of biochar were 2.09, 2.65, 16.30, 20.80, and 382.70 mg·g(-1), and their pyrolysis temperatures were 100, 200, 300, 400, and 500 °C, respectively. Based on the Yoon-Nelson model, the mass transfer mechanism of hydrogen sulfide adsorption by biochar was analyzed.
An optically accessible pyrolysis microreactor
NASA Astrophysics Data System (ADS)
Baraban, J. H.; David, D. E.; Ellison, G. Barney; Daily, J. W.
2016-01-01
We report an optically accessible pyrolysis micro-reactor suitable for in situ laser spectroscopic measurements. A radiative heating design allows for completely unobstructed views of the micro-reactor along two axes. The maximum temperature demonstrated here is only 1300 K (as opposed to 1700 K for the usual SiC micro-reactor) because of the melting point of fused silica, but alternative transparent materials will allow for higher temperatures. Laser induced fluorescence measurements on nitric oxide are presented as a proof of principle for spectroscopic characterization of pyrolysis conditions.
Innovative Processing of Composites for Ultra-High Temperature Applications. Book 1
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
An optically accessible pyrolysis microreactor
DOE Office of Scientific and Technical Information (OSTI.GOV)
Baraban, J. H.; Ellison, G. Barney; David, D. E.
2016-01-15
We report an optically accessible pyrolysis micro-reactor suitable for in situ laser spectroscopic measurements. A radiative heating design allows for completely unobstructed views of the micro-reactor along two axes. The maximum temperature demonstrated here is only 1300 K (as opposed to 1700 K for the usual SiC micro-reactor) because of the melting point of fused silica, but alternative transparent materials will allow for higher temperatures. Laser induced fluorescence measurements on nitric oxide are presented as a proof of principle for spectroscopic characterization of pyrolysis conditions.
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.
Mahadevan, Ravishankar; Adhikari, Sushil; Shakya, Rajdeep; ...
2016-10-27
Torrefaction is a low-temperature process considered as an effective pretreatment technique to improve the grindability of biomass as well as enhance the production of aromatic hydrocarbons from Catalytic Fast Pyrolysis (CFP). For this paper, this study was performed to understand the effect of torrefaction temperature on structural changes in the lignin macromolecule and its subsequent influence on in-situ CFP process. Lignin extracted from southern pine and switchgrass (via organosolv treatment) was torrefied at four different temperatures (150, 175, 200 and 225 °C) in a tubular reactor. Between the two biomass types studied, lignin from pine appeared to have greater thermalmore » stability during torrefaction when compared with switchgrass lignin. The structural changes in lignin as a result of torrefaction were followed by using FTIR spectroscopy, solid state CP/MAS 13C NMR, 31P NMR spectroscopy and it was found that higher torrefaction temperature (200 and 225 °C) caused polycondensation and de-methoxylation of the aromatic units of lignin. Gel permeation chromatography analysis revealed that polycondensation during torrefaction resulted in an increase in the molecular weight and polydispersity of lignin. The torrefied lignin was subsequently used in CFP experiments using H +ZSM-5 catalyst in a micro-reactor (Py-GC/MS) to understand the effect of torrefaction on the product distribution from pyrolysis. It was observed that although the selectivity of benzene-toluene-xylene compounds from CFP of pine improved from 58.3% (torrefaction temp at 150 °C) to 69.0% (torrefaction temp at 225 °C), the severity of torrefaction resulted in a loss of overall aromatic hydrocarbon yield from 11.6% to 4.9% under same conditions. Torrefaction at higher temperatures also increased the yield of carbonaceous residues from 63.9% to 72.8%. Finally, overall, torrefying lignin caused structural transformations in both type of lignins (switchgrass and pine), which is ultimately detrimental to achieving a higher aromatic hydrocarbon yield from CFP.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mahadevan, Ravishankar; Adhikari, Sushil; Shakya, Rajdeep
Torrefaction is a low-temperature process considered as an effective pretreatment technique to improve the grindability of biomass as well as enhance the production of aromatic hydrocarbons from Catalytic Fast Pyrolysis (CFP). For this paper, this study was performed to understand the effect of torrefaction temperature on structural changes in the lignin macromolecule and its subsequent influence on in-situ CFP process. Lignin extracted from southern pine and switchgrass (via organosolv treatment) was torrefied at four different temperatures (150, 175, 200 and 225 °C) in a tubular reactor. Between the two biomass types studied, lignin from pine appeared to have greater thermalmore » stability during torrefaction when compared with switchgrass lignin. The structural changes in lignin as a result of torrefaction were followed by using FTIR spectroscopy, solid state CP/MAS 13C NMR, 31P NMR spectroscopy and it was found that higher torrefaction temperature (200 and 225 °C) caused polycondensation and de-methoxylation of the aromatic units of lignin. Gel permeation chromatography analysis revealed that polycondensation during torrefaction resulted in an increase in the molecular weight and polydispersity of lignin. The torrefied lignin was subsequently used in CFP experiments using H +ZSM-5 catalyst in a micro-reactor (Py-GC/MS) to understand the effect of torrefaction on the product distribution from pyrolysis. It was observed that although the selectivity of benzene-toluene-xylene compounds from CFP of pine improved from 58.3% (torrefaction temp at 150 °C) to 69.0% (torrefaction temp at 225 °C), the severity of torrefaction resulted in a loss of overall aromatic hydrocarbon yield from 11.6% to 4.9% under same conditions. Torrefaction at higher temperatures also increased the yield of carbonaceous residues from 63.9% to 72.8%. Finally, overall, torrefying lignin caused structural transformations in both type of lignins (switchgrass and pine), which is ultimately detrimental to achieving a higher aromatic hydrocarbon yield from CFP.« less
An Optically Accessible Pyrolysis Microreactor
NASA Astrophysics Data System (ADS)
Baraban, Joshua H.; David, Donald E.; Ellison, Barney; Daily, John W.
2016-06-01
We report an optically accessible pyrolysis micro-reactor suitable for in situ laser spectroscopic measurements. A radiative heating design allows for completely unobstructed views of the micro-reactor along two axes. The maximum temperature demonstrated here is only 1300 K (as opposed to 1700 K for the usual SiC micro-reactor) because of the melting point of fused silica, but alternative transparent materials will allow for higher temperatures. Laser induced fluorescence measurements on nitric oxide are presented as a proof of principle for spectroscopic characterization of pyrolysis conditions. (This work has been published in J. H. Baraban, D. E. David, G. B. Ellison, and J. W. Daily. An Optically Accessible Pyrolysis Micro-Reactor. Review of Scientific Instruments, 87(1):014101, 2016.)
NASA Technical Reports Server (NTRS)
Noyes, G. P.; Cusick, R. J.
1985-01-01
The three steps in pyrolytic carbon formation are: (1) gaseous hydrocarbon polymerization and aromatic formation; (2) gas-phase condensation and surface adsorption/impingement of polyaromatic hydrocarbon; and (3) final dehydration to carbon. The structure of the carbon in the various stages of formation is examined. The apparatuses and experimental procedures for the pyrolysis of methane in a 60 cm long quartz reactor tube at temperatures ranging from 1400-1600 K are described. The percentage of carbon converted and its density are calculated and tabularly presented. The results reveal that dense carbon formation is maximized and soot eliminated by this procedure. It is observed that conversion efficiency depends on the composition of the inlet gas and conversion increases with increasing temperature. Based on the experimental data a three-man carbon reactor subsystem (CRS) is developed; the functions of the Sabatier Methanation Reactor, two carbon formation reactors and fluid handling components of the CRS are analyzed. The CRS forms 16 kg of carbon at a rate of 0.8 kg/day for 20 days in a two percent volume density quartz wool packing at temperature of 1500-1600 K.
Effect of pyrolysis temperature on the chemical oxidation stability of bamboo biochar.
Chen, Dengyu; Yu, Xinzhi; Song, Chao; Pang, Xiaoli; Huang, Jing; Li, Yanjun
2016-10-01
Biochar produced by biomass pyrolysis has the advantage of carbon sequestration. However, some of the carbon atoms in biochar are not very stable. In this study, the effect of pyrolysis temperature on the chemical oxidation stability of bamboo biochar was investigated using the atomic ratios of H/C and O/C, Fourier transform infrared spectroscopy, and potassium dichromate (K2Cr2O7) oxidation spectrophotometric method. The results show that the carbon yield and ratios of H/C and O/C decreased from 71.72%, 0.71, and 0.32 to 38.48%, 0.22, and 0.06, respectively, as the temperature was increased from 300°C to 700°C. Moreover, the main oxygen-containing functional groups gradually decreased, while the degree of aromatization increased accordingly. The biochar showed a better stability at a higher pyrolysis temperature. The proportion of carbon loss, i.e., the amount of oxidized carbon with respect to the total carbon of the biochar, decreased from 16.52% to 6.69% with increasing temperature. Copyright © 2016 Elsevier Ltd. All rights reserved.
Vacuum pyrolysis of waste tires with basic additives.
Zhang, Xinghua; Wang, Tiejun; Ma, Longlong; Chang, Jie
2008-11-01
Granules of waste tires were pyrolyzed under vacuum (3.5-10 kPa) conditions, and the effects of temperature and basic additives (Na2CO3, NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48 wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50 wt% was achieved at 480 degrees C by adding 3 wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39 wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na2CO3 addition. Pyrolysis gas was mainly composed of H2, CO, CH4, CO2, C2H4 and C2H6. Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5 wt%) was much higher.
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.
Rafiq, Muhammad Khalid; Bachmann, Robert Thomas; Rafiq, Muhammad Tariq; Shang, Zhanhuan; Joseph, Stephen; Long, Ruijun
2016-01-01
This study examined the influence of pyrolysis temperature on biochar characteristics and evaluated its suitability for carbon capture and energy production. Biochar was produced from corn stover using slow pyrolysis at 300, 400 and 500°C and 2 hrs holding time. The experimental biochars were characterized by elemental analysis, BET, FTIR, TGA/DTA, NMR (C-13). Higher heating value (HHV) of feedstock and biochars was measured using bomb calorimeter. Results show that carbon content of corn stover biochar increased from 45.5% to 64.5%, with increasing pyrolysis temperatures. A decrease in H:C and O:C ratios as well as volatile matter, coupled with increase in the concentration of aromatic carbon in the biochar as determined by FTIR and NMR (C-13) demonstrates a higher biochar carbon stability at 500°C. It was estimated that corn stover pyrolysed at 500°C could provide of 10.12 MJ/kg thermal energy. Pyrolysis is therefore a potential technology with its carbon-negative, energy positive and soil amendment benefits thus creating win- win scenario.
Gaurh, Pramendra; Pramanik, Hiralal
2018-01-01
A new and innovative approach was adopted to increase the yield of aromatics like, benzene, toluene and xylene (BTX) in the catalytic pyrolysis of waste polyethylene (PE). The BTX content was significantly increased due to effective interaction between catalystZSM-5 and target molecules i.e., lower paraffins within the reactor. The thermal and catalytic pyrolysis both were performed in a specially designed semi-batch reactor at the temperature range of 500 °C-800 °C. Catalytic pyrolysis were performed in three different phases within the reactor batch by batch systematically, keeping the catalyst in A type- vapor phase, B type- liquid phase and C type- vapor and liquid phase (multiphase), respectively. Total aromatics (BTX) of 6.54 wt% was obtained for thermal pyrolysis at a temperature of 700 °C. In contrary, for the catalytic pyrolysis A, B and C types reactor arrangement, the aromatic (BTX) contents were progressively increased, nearly 6 times from 6.54 wt% (thermal pyrolysis) to 35.06 wt% for C-type/multiphase (liquid and vapor phase). The pyrolysis oil were characterized using GC-FID, FT-IR, ASTM distillation and carbon residue test to evaluate its end use and aromatic content. Copyright © 2017 Elsevier Ltd. All rights reserved.
Development of chemically vapor deposited rhenium emitters of (0001) preferred crystal orientation
NASA Technical Reports Server (NTRS)
Yang, L.; Hudson, R. G.
1973-01-01
Rhenium thermionic emitters were prepared by the pyrolysis of rhenium chlorides formed by the chlorination of rhenium pellets. The impurity contents, microstructures, degrees of (0001) preferred crystal orientation, and vacuum electron work functions of these emitters were determined as a function of deposition parameters, such as substrate temperature, rhenium pellet temperature and chlorine flow rate. A correlation between vacuum electron work function and degree of (0001) preferred crystal orientation was established. Conditions for depositing porosity-free rhenium emitters of high vacuum electron work functions were defined. Finally, three cylindrical rhenium emitters were prepared under the optimum deposition conditions.
Method for fabrication of crack-free ceramic dielectric films
Ma, Beihai; Narayanan, Manoj; Balachandran, Uthamalingam; Chao, Sheng; Liu, Shanshan
2016-05-31
The invention provides a process for forming crack-free dielectric films on a substrate. The process comprises the application of a dielectric precursor layer of a thickness from about 0.3 .mu.m to about 1.0 .mu.m to a substrate. The deposition is followed by low temperature heat pretreatment, prepyrolysis, pyrolysis and crystallization step for each layer. The deposition, heat pretreatment, prepyrolysis, pyrolysis and crystallization are repeated until the dielectric film forms an overall thickness of from about 1.5 .mu.m to about 20.0 .mu.m and providing a final crystallization treatment to form a thick dielectric film. The process provides a thick crack-free dielectric film on a substrate, the dielectric forming a dense thick crack-free dielectric having an overall dielectric thickness of from about 1.5 .mu.m to about 20.0 .mu.m.
Method for fabrication of crack-free ceramic dielectric films
Ma, Beihai; Balachandran, Uthamalingam; Chao, Sheng; Liu, Shanshan; Narayanan, Manoj
2014-02-11
The invention provides a process for forming crack-free dielectric films on a substrate. The process comprise the application of a dielectric precursor layer of a thickness from about 0.3 .mu.m to about 1.0 .mu.m to a substrate. The deposition is followed by low temperature heat pretreatment, prepyrolysis, pyrolysis and crystallization step for each layer. The deposition, heat pretreatment, prepyrolysis, pyrolysis and crystallization are repeated until the dielectric film forms an overall thickness of from about 1.5 .mu.m to about 20.0 .mu.m and providing a final crystallization treatment to form a thick dielectric film. Also provided was a thick crack-free dielectric film on a substrate, the dielectric forming a dense thick crack-free dielectric having an overall dielectric thickness of from about 1.5 .mu.m to about 20.0 .mu.m.
Irfan, Muhammad; Chen, Qun; Yue, Yan; Pang, Renzhong; Lin, Qimei; Zhao, Xiaorong; Chen, Hao
2016-07-01
In the present study, pyrolysis of Achnatherum splendens L. was performed under three different pyrolysis temperature (300, 500, and 700°C) to investigate the characteristics of biochar, bio-oil, and syngas. Biochar yield decreased from 48% to 24%, whereas syngas yield increased from 34% to 54% when pyrolysis temperature was increased from 300 to 700°C. Maximum bio-oil yield (27%) was obtained at 500°C. The biochar were characterized for elemental composition, surface, and adsorption properties. The results showed that obtained biochar could be used as a potential soil amendment. The bio-oil and syngas co-products will be evaluated in the future as bioenergy sources. Overall, our results suggests that A. splendens L. could be utilized as a potential feedstock for biochar and bioenergy production through pyrolytic route. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.
Release behavior and formation mechanism of polycyclic aromatic hydrocarbons during coal pyrolysis.
Gao, Meiqi; Wang, Yulong; Dong, Jie; Li, Fan; Xie, Kechang
2016-09-01
Polycyclic aromatic hydrocarbons (PAHs) are major environmental pollutants. They have attracted considerable attention due to their severe potential carcinogenic, mutagenic and genotoxic effects on human health. In this study, five different rank coals from China were pyrolyzed using pyro-probe CDS 5250 and the release behavior of 16 PAHs under different pyrolysis conditions were studied by Gas Chromatography-Mass Spectrometer (GC-MS). The structural characteristics of the five coals were determined by Cross-Polarization/Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS (13)C NMR) spectroscopy, and then the factors influencing the formation of PAHs during coal pyrolysis were discussed together with the coal structural data. It was shown that the amount of PAHs generated during coal pyrolysis was largely related to coal rank and followed the order of medium metamorphic coal > low metamorphic coal > high metamorphic coal. The amount of total PAHs varied as the temperature was increased from 400 °C to 1200 °C, which showed a trend of first increasing and then decreasing, with the maximum value at 800 °C. Moreover, the species of PAHs released varied with pyrolysis temperatures. When the temperature was lower than 800 °C, the small ring PAHs were the most abundant, while the proportion of heavy rings increased at higher temperature. The results indicate that the formation of PAHs during coal pyrolysis depends on the structure of the coal. The species and amounts of PAHs generated during coal pyrolysis are closely related to the contents of protonated aromatic carbons and bridging ring junction aromatic carbons present in the coal structure. Copyright © 2016 Elsevier Ltd. All rights reserved.
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.
Tar-free fuel gas production from high temperature pyrolysis of sewage sludge
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Leguan; Xiao, Bo; Hu, Zhiquan
2014-01-15
Highlights: • High temperature pyrolysis of sewage sludge was efficient for producing tar-free fuel gas. • Complete tar removal and volatile matter release were at elevated temperature of 1300 °C. • Sewage sludge was converted to residual solid with high ash content. • 72.60% of energy conversion efficiency for gas production in high temperature pyrolysis. • Investment and costing for tar cleaning were reduced. - Abstract: Pyrolysis of sewage sludge was studied in a free-fall reactor at 1000–1400 °C. The results showed that the volatile matter in the sludge could be completely released to gaseous product at 1300 °C. Themore » high temperature was in favor of H{sub 2} and CO in the produced gas. However, the low heating value (LHV) of the gas decreased from 15.68 MJ/N m{sup 3} to 9.10 MJ/N m{sup 3} with temperature increasing from 1000 °C to 1400 °C. The obtained residual solid was characterized by high ash content. The energy balance indicated that the most heating value in the sludge was in the gaseous product.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bozkurt, Y.; Misirlioglu, Z.; Sinag, A.
The reactivities of chars obtained by pyrolysis of Bursa Mustafa Kemal Pasa Alpagut lignite and Balkesir Dursunbey Cakiirca lignite (Turkey) at different temperatures were determined by CO{sub 2} gasification and by combustion with O{sub 2}. Catalytic effect of Na{sub 2}CO{sub 3} on the CO{sub 2} and O{sub 2} gasification reactivity of chars was investigated. Gasification tests were performed in the fixed bed reactors operating at ambient pressure. Reactivity of chars during the CO{sub 2} gasification reactions was determined by calculating the reaction rate constants and reactivity of chars during the O{sub 2} gasification was determined by using ignition temperatures ofmore » the samples. Activation energies and Arrhenius constants of the chars on the CO{sub 2} gasification reactions were also calculated by the help of Arrhenius curves. The activation energy for CO{sub 2} gasification was generally decreased with pyrolysis temperature, due to the different surface characteristics and different nature of carbon atoms gasified as the gasification reactions proceed. Generally, the increase in pyrolysis temperature leads to an increase in gasification reactivity with CO{sub 2}. The reactivity of chars in catalytic gasification was higher than the corresponding non-catalytic reactivity of the same chars. Ignition temperature increased with increasing pyrolysis temperature.« less
Wang, Huihui; Wang, Xin; Cui, Yanshan; Xue, Zhongcai; Ba, Yuxin
2018-05-11
Slow pyrolysis of bamboo was conducted at 400-600 °C and pyrolysis products were characterized with FTIR, BET, XRD, SEM, EDS and GC to establish a pyrolysis product yield prediction model and biochar formation mechanism. Pyrolysis biochar yield was predicted based on content of cellulose, hemicellulose and lignin in biomass with their carbonization index of 0.20, 0.35 and 0.45. The formation mechanism of porous structure in pyrolysis biochar was established based on its physicochemical property evolution and emission characteristics of pyrolysis gas. The main components (cellulose, hemicellulose and lignin) had different pyrolysis or chemical reaction pathways to biochar. Lignin had higher aromatic structure, which resulted higher biochar yield. It was the main biochar precursor during biomass pyrolysis. Cellulose was likely to improve porous structure of pyrolysis biochar due to its high mass loss percentage. Higher pyrolysis temperatures (600 °C) promoted inter- and intra-molecular condensation reactions and aromaticity in biochar. Copyright © 2018 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Buckingham, Grant T.; National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden Colorado 80401; Porterfield, Jessica P.
2016-07-07
Cycloheptatrienyl (tropyl) radical, C{sub 7}H{sub 7}, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C{sub 7}H{sub 7} were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C{sub 7}H{sub 7} are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize tomore » benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C{sub 7}H{sub 7}) radicals but rather only benzyl (C{sub 6}H{sub 5}CH{sub 2}). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C{sub 6}H{sub 5}CH{sub 2}, C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less
Pattiya, Adisak; Suttibak, Suntorn
2012-07-01
This article reports experimental results of rapid or fast pyrolysis of rice straw (RS) and rice husk (RH) in a fluidised-bed reactor unit incorporated with a hot vapour filter. The objective of this research was to investigate the effects of pyrolysis temperatures and the use of glass wool hot vapour filtration on pyrolysis products. The results showed that the optimum pyrolysis temperatures for RS and RH were 405 and 452 °C, which gave maximum bio-oil yields of 54.1 and 57.1 wt.% on dry biomass basis, respectively. The use of the hot filter led to a reduction of 4-7 wt.% bio-oil yield. Nevertheless, the glass wool hot filtered bio-oils appeared to have better quality in terms of initial viscosity, solids content and ash content than the non-filtered ones. Copyright © 2012 Elsevier Ltd. All rights reserved.
Bio-oil production from fast pyrolysis of waste furniture sawdust in a fluidized bed.
Heo, Hyeon Su; Park, Hyun Ju; Park, Young-Kwon; Ryu, Changkook; Suh, Dong Jin; Suh, Young-Woong; Yim, Jin-Heong; Kim, Seung-Soo
2010-01-01
The amount of waste furniture generated in Korea was over 2.4 million tons in the past 3 years, which can be used for renewable energy or fuel feedstock production. Fast pyrolysis is available for thermo-chemical conversion of the waste wood mostly into bio-oil. In this work, fast pyrolysis of waste furniture sawdust was investigated under various reaction conditions (pyrolysis temperature, particle size, feed rate and flow rate of fluidizing medium) in a fluidized-bed reactor. The optimal pyrolysis temperature for increased yields of bio-oil was 450 degrees C. Excessively smaller or larger feed size negatively affected the production of bio-oil. Higher flow and feeding rates were more effective for the production of bio-oil, but did not greatly affect the bio-oil yields within the tested ranges. The use of product gas as the fluidizing medium had a potential for increased bio-oil yields.
Study on vacuum pyrolysis of coffee industrial residue for bio-oil production
NASA Astrophysics Data System (ADS)
Chen, Nanwei; Ren, Jie; Ye, Ziwei; Xu, Qizhi; Liu, Jingyong; Sun, Shuiyu
2017-03-01
Coffee industrial residue (CIR) is a biomass with high volatile content (64.94 wt.%) and heating value (21.3 MJ·kg-1). This study was carried out to investigate the pyrolysis condition and products of CIR using thermogravimetric analyser (TGA) and vacuum tube furnace. The influence of pyrolysis temperature, time, pressure and heating rate on the yield of pyrolysis products were discussed. There was an optimal pyrolysis condition: CIR was heated from normal temperature to 400 °C for 60 min, with 10 °C·min-1 heating rate and a pressure of 30 kPaabs. In this condition, the yields of bio-oil, char and non-condensable gas were 42.29, 33.14 and 24.57 wt.%, respectively. The bio-oil contained palmitic acid (47.48 wt.%), oleic acid (17.45 wt.%), linoleic acid (11.34 wt.%), octadecanoic acid (7.62 wt.%) and caffeine (5.18 wt.%).
A steady state model of agricultural waste pyrolysis: A mini review.
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.
NASA Technical Reports Server (NTRS)
Ehrenfreund, P.; Boon, J. J.; Commandeur, J.; Sagan, C.; Thompson, W. R.; Khare, B.
1995-01-01
Comparative pyrolysis mass spectrometric data of Titan aerosol analogs, called 'tholins', are presented. The Titan tholins were produced in the laboratory at Cornell by irradiation of simulated Titan atmospheres with high energy electrons in plasma discharge. Mass-spectrometry measurements were performed at FOM of the solid phase of various tholins by Curie-point pyrolysis Gas-Chromatography/Mass-Spectrometry (GCMS) and by temperature resolved in-source Pyrolysis Mass-Spectrometry to reveal the composition and evolution temperature of the dissociation products. The results presented here are used to further define the ACP (Aerosol Collector Pyrolyser)-GCMS experiment and provide a basis for modelling of aerosol composition on Titan and for the iterpretation of Titan atmosphere data from the Huygens probe in the future.
Ecotoxicological characterization of biochars: role of feedstock and pyrolysis temperature.
Domene, X; Enders, A; Hanley, K; Lehmann, J
2015-04-15
Seven contrasting feedstocks were subjected to slow pyrolysis at low (300 or 350°C) and high temperature (550 or 600°C), and both biochars and the corresponding feedstocks tested for short-term ecotoxicity using basal soil respiration and collembolan reproduction tests. After a 28-d incubation, soil basal respiration was not inhibited but stimulated by additions of feedstocks and biochars. However, variation in soil respiration was dependent on both feedstock and pyrolysis temperature. In the last case, respiration decreased with pyrolysis temperature (r=-0.78; p<0.0001, n=21) and increased with a higher volatile matter content (r=0.51; p<0.017), these two variables being correlated (r=-0.86, p<0.0001). Collembolan reproduction was generally unaffected by any of the additions, but when inhibited, it was mostly influenced by feedstock, and generally without any influence of charring itself and pyrolysis temperature. Strong inhibition was only observed in uncharred food waste and resulting biochars. Inhibition effects were probably linked to high soluble Na and NH4 concentrations when both feedstocks and biochars were considered, but mostly to soluble Na when only biochars were taken into account. The general lack of toxicity of the set of slow pyrolysis biochars in this study at typical field application rates (≤20 Mg ha(-1)) suggests a low short-term toxicity risk. At higher application rates (20-540 Mg ha(-1)), some biochars affected collembolan reproduction to some extent, but only strongly in the food waste biochars. Such negative impacts were not anticipated by the criteria set in currently available biochar quality standards, pointing out the need to consider ecotoxicological criteria either explicitly or implicitly in biochar characterization schemes or in management recommendations. Copyright © 2014 Elsevier B.V. All rights reserved.
Waste tyre pyrolysis: modelling of a moving bed reactor.
Aylón, E; Fernández-Colino, A; Murillo, R; Grasa, G; Navarro, M V; García, T; Mastral, A M
2010-12-01
This paper describes the development of a new model for waste tyre pyrolysis in a moving bed reactor. This model comprises three different sub-models: a kinetic sub-model that predicts solid conversion in terms of reaction time and temperature, a heat transfer sub-model that calculates the temperature profile inside the particle and the energy flux from the surroundings to the tyre particles and, finally, a hydrodynamic model that predicts the solid flow pattern inside the reactor. These three sub-models have been integrated in order to develop a comprehensive reactor model. Experimental results were obtained in a continuous moving bed reactor and used to validate model predictions, with good approximation achieved between the experimental and simulated results. In addition, a parametric study of the model was carried out, which showed that tyre particle heating is clearly faster than average particle residence time inside the reactor. Therefore, this fast particle heating together with fast reaction kinetics enables total solid conversion to be achieved in this system in accordance with the predictive model. Copyright © 2010 Elsevier Ltd. All rights reserved.
Lin, Li; Chen, Guang; Chen, Yuhong
2011-07-01
A method was established for the determination of iodine and its species in plant samples using ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP/ MS). Alkaline extraction and IC-ICP/MS were applied as the sample pre-treatment method and the detection technique respectively, for iodate and iodide determination. Moreover, high-temperature pyrolysis absorption was adopted as the pre-treatment method for total iodine analysis, which finally converted all the iodine species into iodide and measured the iodide by IC-ICP/MS. The recoveries of iodine for alkaline extraction and high-temperature pyrolysis absorption were 89.6%-97.5% and 95.2%-111.2%, respectively. The results were satisfactory. The detection limit of iodine was 0.010 mg/kg. The iodine and its speciation contents in several kinds of plant samples such as seaweeds, kelp, cabbage, tea leaf and spinach were investigated. It was shown that the iodine in seaweeds mainly existed as organic iodine; while the ones in kelp, cabbage, tea leaf and spinach mainly existed as inorganic iodine.
Choi, Gyung-Goo; Oh, Seung-Jin; Lee, Soon-Jang; Kim, Joo-Sik
2015-02-01
A fraction of palm kernel shells (PKS) was pyrolyzed in a fluidized bed reactor. The experiments were performed in a temperature range of 479-555 °C to produce bio-oil, biochar, and gas. All the bio-oils were analyzed quantitatively and qualitatively by GC-FID and GC-MS. The maximum content of phenolic compounds in the bio-oil was 24.8 wt.% at ∼500 °C. The maximum phenol content in the bio-oil, as determined by the external standard method, was 8.1 wt.%. A bio-oil derived from the pyrolysis of PKS was used in the synthesis of phenolic resin, showing that the bio-oil could substitute for fossil phenol up to 25 wt.%. The biochar was activated using CO2 at a final activation temperature of 900 °C with different activation time (1-3 h) to produce activated carbon. Activated carbons produced were microporous, and the maximum surface area of the activated carbons produced was 807 m(2)/g. Copyright © 2014 Elsevier Ltd. All rights reserved.
USDA-ARS?s Scientific Manuscript database
In this study, we used a commercial pilot-scale pyrolysis reactor system to produce combustible gas and biochar at 620 degrees Celsium from three sources (chicken litter, swine solids, mixture of swine solids with rye grass). Pyrolysis of swine solids produced gas with the greatest higher heating va...
Development of bio-fuel from palm frond via fast pyrolysis
NASA Astrophysics Data System (ADS)
Solikhah, M. D.; Raksodewanto, A. A.; Kismanto, A.; Karuana, F.; Heryana, Y.; Riza; Pratiwi, F. T.
2017-05-01
In order to fulfill the fuel demand in the future, Indonesia has to find a sustainable alternative for its energy. Energy source in the form of biomass is a promising alternative since its availability is abundance in this tropical country. Biomass can be converted into liquid fuel via fast pyrolysis by contacting the solid biomass into hot medium in the absence of oxygen. Hot sand is the common heat carrier for fast pyrolysis purposes but it is very abrasive and required high pyrolysis temperature (450-600 °C). This paper will discuss on the equipment design and experiment of fast pyrolysis of palm frond using high boiling point thermal oil as heat carrier. Experiments show that by using thermal oil as heat carrier, bio-oil can be produced at lower pyrolysis temperature of 350 °C, compared to the one using hot sand as heating carrier. The yield of bio-oil production is 36.4 % of biomass feeding. The water content of bio-oil is 52.77 % mass while heating value is 10.25 MJ/kg.
Effect of operating parameters on bio-fuel production from waste furniture sawdust.
Uzun, Basak Burcu; Kanmaz, Gülin
2013-04-01
Fast pyrolysis is an effective technology for conversion of biomass into energy and value-added chemicals instead of burning them directly. In this study, fast pyrolysis of waste furniture sawdust (pine sawdust) was investigated under various reaction conditions (reaction time, pyrolysis temperature, heating rate, residence time and particle size) in a tubular reactor. The optimum reaction conditions for bio-oil production was found as reaction time of 5 min, pyrolysis temperature of 500 °C, heating rate of 300 °C min(-1) under nitrogen flow rate of 400 cm(3) min(-1). At these conditions, maximum bio-oil yield was obtained as 42.09%. Pyrolysis oils were characterized by using various elemental analyses, fourier - transformation infrared (FT-IR) spectrometry and gas chromatography-mass spectrometry (GC-MS). The results of the GC-MS showed that cracking of large molecular phenolics was followed by partial conversion into phenol and alkylated phenols (45%) during the pyrolysis. According to the experimental and characterization results; the liquid product could be used as feedstock for the chemical industry or petroleum crude for refinery.
Sulfur Transformation during Microwave and Conventional Pyrolysis of Sewage Sludge.
Zhang, Jun; Zuo, Wei; Tian, Yu; Chen, Lin; Yin, Linlin; Zhang, Jie
2017-01-03
The sulfur distributions and evolution of sulfur-containing compounds in the char, tar and gas fractions were investigated during the microwave and conventional pyrolysis of sewage sludge. Increased accumulation of sulfur in the char and less production of H 2 S were obtained from microwave pyrolysis at higher temperatures (500-800 °C). Three similar conversion pathways were identified for the formation of H 2 S during microwave and conventional pyrolysis. The cracking of unstable mercaptan structure in the sludge contributed to the release of H 2 S below 300 °C. The decomposition of aliphatic-S compounds in the tars led to the formation of H 2 S (300-500 °C). The thermal decomposition of aromatic-S compounds in the tars generated H 2 S from 500 to 800 °C. However, the secondary decomposition of thiophene-S compounds took place only in conventional pyrolysis above 700 °C. Comparing the H 2 S contributions from microwave and conventional pyrolysis, the significant increase of H 2 S yields in conventional pyrolysis was mainly attributed to the decomposition of aromatic-S (increasing by 10.4%) and thiophene-S compounds (11.3%). Further investigation on the inhibition mechanism of H 2 S formation during microwave pyrolysis confirmed that, with the special heating characteristics and relative shorter residence time, microwave pyrolysis promoted the retention of H 2 S on CaO and inhibited the secondary cracking of thiophene-S compounds at higher temperatures.
Removal of Congo Red and Methylene Blue from Aqueous Solutions by Vermicompost-Derived Biochars.
Yang, Gang; Wu, Lin; Xian, Qiming; Shen, Fei; Wu, Jun; Zhang, Yanzong
2016-01-01
Biochars, produced by pyrolyzing vermicompost at 300, 500, and 700°C were characterized and their ability to adsorb the dyes Congo red (CR) and Methylene blue (MB) in an aqueous solution was investigated. The physical and chemical properties of biochars varied significantly based on the pyrolysis temperatures. Analysis of the data revealed that the aromaticity, polarity, specific surface area, pH, and ash content of the biochars increased gradually with the increase in pyrolysis temperature, while the cation exchange capacity, and carbon, hydrogen, nitrogen and oxygen contents decreased. The adsorption kinetics of CR and MB were described by pseudo-second-order kinetic models. Both of Langmuir and Temkin model could be employed to describe the adsorption behaviors of CR and MB by these biochars. The biochars generated at higher pyrolysis temperature displayed higher CR adsorption capacities and lower MB adsorption capacities than those compared with the biochars generated at lower pyrolysis temperatures. The biochar generated at the higher pyrolytic temperature displayed the higher ability to adsorb CR owing to its promoted aromaticity, and the cation exchange is the key factor that positively affects adsorption of MB.
Removal of Congo Red and Methylene Blue from Aqueous Solutions by Vermicompost-Derived Biochars
Yang, Gang; Wu, Lin; Xian, Qiming; Shen, Fei; Wu, Jun; Zhang, Yanzong
2016-01-01
Biochars, produced by pyrolyzing vermicompost at 300, 500, and 700°C were characterized and their ability to adsorb the dyes Congo red (CR) and Methylene blue (MB) in an aqueous solution was investigated. The physical and chemical properties of biochars varied significantly based on the pyrolysis temperatures. Analysis of the data revealed that the aromaticity, polarity, specific surface area, pH, and ash content of the biochars increased gradually with the increase in pyrolysis temperature, while the cation exchange capacity, and carbon, hydrogen, nitrogen and oxygen contents decreased. The adsorption kinetics of CR and MB were described by pseudo-second-order kinetic models. Both of Langmuir and Temkin model could be employed to describe the adsorption behaviors of CR and MB by these biochars. The biochars generated at higher pyrolysis temperature displayed higher CR adsorption capacities and lower MB adsorption capacities than those compared with the biochars generated at lower pyrolysis temperatures. The biochar generated at the higher pyrolytic temperature displayed the higher ability to adsorb CR owing to its promoted aromaticity, and the cation exchange is the key factor that positively affects adsorption of MB. PMID:27144922
Herawan, S G; Hadi, M S; Ayob, Md R; Putra, A
2013-01-01
Activated carbons can be produced from different precursors, including coals of different ranks, and lignocellulosic materials, by physical or chemical activation processes. The objective of this paper is to characterize oil-palm shells, as a biomass byproduct from palm-oil mills which were converted into activated carbons by nitrogen pyrolysis followed by CO2 activation. The effects of no holding peak pyrolysis temperature on the physical characteristics of the activated carbons are studied. The BET surface area of the activated carbon is investigated using N2 adsorption at 77 K with selected temperatures of 500, 600, and 700°C. These pyrolysis conditions for preparing the activated carbons are found to yield higher BET surface area at a pyrolysis temperature of 700°C compared to selected commercial activated carbon. The activated carbons thus result in well-developed porosities and predominantly microporosities. By using this activation method, significant improvement can be obtained in the surface characteristics of the activated carbons. Thus this study shows that the preparation time can be shortened while better results of activated carbon can be produced.
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.
Pyrolysis temperature influences ameliorating effects of biochars on acidic soil.
Wan, Qing; Yuan, Jin-Hua; Xu, Ren-Kou; Li, Xing-Hui
2014-02-01
The biochars were prepared from straws of canola, corn, soybean, and peanut at different temperatures of 300, 500, and 700 °C by means of oxygen-limited pyrolysis.Amelioration effects of these biochars on an acidic Ultisol were investigated with incubation experiments, and application rate of biochars was 10 g/kg. The incorporation of these biochars induced the increase in soil pH, soil exchangeable base cations, base saturation, and cation exchange capacity and the decrease in soil exchangeable acidity and exchangeable Al. The ameliorating effects of biochars on acidic soil increased with increase in their pyrolysis temperature. The contribution of oxygen-containing functional groups on the biochars to their ameliorating effects on the acidic soil decreased with the rise in pyrolysis temperature, while the contribution from carbonates in the biochars changed oppositely. The incorporation of the biochars led to the decrease in soil reactive Al extracted by 0.5mol/L CuCl2, and the content of reactive Al was decreased with the increase in pyrolysis temperature of incorporated biochars. The biochars generated at 300 °C increased soil organically complexed Al due to ample quantity of oxygen-containing functional groups such as carboxylic and phenolic groups on the biochars, while the biochars generated at 500 and 700 °C accelerated the transformation of soil exchangeable Al to hydroxyl-Al polymers due to hydrolysis of Al at higher pH. Therefore, the crop straw-derived biochars can be used as amendments for acidic soils and the biochars generated at relatively high temperature have great ameliorating effects on the soils.
Rafiq, Muhammad Khalid; Bachmann, Robert Thomas; Rafiq, Muhammad Tariq; Shang, Zhanhuan; Joseph, Stephen; Long, Ruijun
2016-01-01
This study examined the influence of pyrolysis temperature on biochar characteristics and evaluated its suitability for carbon capture and energy production. Biochar was produced from corn stover using slow pyrolysis at 300, 400 and 500°C and 2 hrs holding time. The experimental biochars were characterized by elemental analysis, BET, FTIR, TGA/DTA, NMR (C-13). Higher heating value (HHV) of feedstock and biochars was measured using bomb calorimeter. Results show that carbon content of corn stover biochar increased from 45.5% to 64.5%, with increasing pyrolysis temperatures. A decrease in H:C and O:C ratios as well as volatile matter, coupled with increase in the concentration of aromatic carbon in the biochar as determined by FTIR and NMR (C-13) demonstrates a higher biochar carbon stability at 500°C. It was estimated that corn stover pyrolysed at 500°C could provide of 10.12 MJ/kg thermal energy. Pyrolysis is therefore a potential technology with its carbon-negative, energy positive and soil amendment benefits thus creating win- win scenario. PMID:27327870
Pyrolysis process for producing fuel gas
NASA Technical Reports Server (NTRS)
Serio, Michael A. (Inventor); Kroo, Erik (Inventor); Wojtowicz, Marek A. (Inventor); Suuberg, Eric M. (Inventor)
2007-01-01
Solid waste resource recovery in space is effected by pyrolysis processing, to produce light gases as the main products (CH.sub.4, H.sub.2, CO.sub.2, CO, H.sub.2O, NH.sub.3) and a reactive carbon-rich char as the main byproduct. Significant amounts of liquid products are formed under less severe pyrolysis conditions, and are cracked almost completely to gases as the temperature is raised. A primary pyrolysis model for the composite mixture is based on an existing model for whole biomass materials, and an artificial neural network models the changes in gas composition with the severity of pyrolysis conditions.
Methods for deoxygenating biomass-derived pyrolysis oil
Baird, Lance Awender; Brandvold, Timothy A.
2015-06-30
Methods for deoxygenating a biomass-derived pyrolysis oil are provided. A method for deoxygenating a biomass-derived pyrolysis oil comprising the steps of combining a biomass-derived pyrolysis oil stream with a heated low-oxygen-pyoil diluent recycle stream to form a heated diluted pyoil feed stream is provided. The heated diluted pyoil feed stream has a feed temperature of about 150.degree. C. or greater. The heated diluted pyoil feed stream is contacted with a first deoxygenating catalyst in the presence of hydrogen at first hydroprocessing conditions effective to form a low-oxygen biomass-derived pyrolysis oil effluent.
Kalinke, Cristiane; Mangrich, Antonio Sálvio; Marcolino-Junior, Luiz H; Bergamini, Márcio F
2016-11-15
Biochar is a carbonaceous material similar produced by pyrolysis of biomass under oxygen-limited conditions. Pyrolysis temperature is an important parameter that can alters biochar characteristics (e.g. surface area, pore size distribution and surface functional groups) and affects it efficacy for adsorption of several probes. In this work, biochar samples have been prepared from castor oil cake using different temperatures of pyrolysis (200-600°C). For the first time, a voltammetric procedure based on carbon paste modified electrode (CPME) was used to investigate the effect of temperature of pyrolysis on the adsorptive characteristics of biochar for Pb(II), Cd(II) and Cu(II) ions. Besides the electrochemical techniques, several characterizations have been performed to evaluate the physicochemical properties of biochar in function of the increase of the pyrolysis temperature. Results suggest that biochar pyrolized at 400°C (BC400) showed a better potential for ions adsorption. The CPME modified with BC400 showed better relative current signal with adsorption affinity: Pb(II)>Cd(II)>Cu(II). Kinetic studies revealed that the pseudo-second order model describes more accurately the adsorption process suggesting that the surface reactions control the adsorption rate. Values found for amount adsorbed were 15.94±0.09; 4.29±0.13 and 2.38±0.39μgg(-1) for Pb(II), Cd(II) and Cu(II) ions, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.
Transformation Toughening of Composite Ceramics
1992-12-31
Ca 2SiO 4 ) entiwickelt. Als Sili:ium-haltiger Prekursor i’urde has been well studied ’ 2 because of the considerable Siliziumdioxid veruiendet. Diese ...of carbon diffraction (XRD). This was after calcination for formed during the pyrolysis . The thermal decompo- I min at temperatures in the range...ques respectively. Some of the powders were also temperature for 1 min and cooled. At temperatures examined by SEM. below the pyrolysis stage the
Effects of Feedstock and Pyrolysis Temperature on Biochar Adsorption of Ammonium and Nitrate
Gai, Xiapu; Wang, Hongyuan; Liu, Jian; Zhai, Limei; Liu, Shen; Ren, Tianzhi; Liu, Hongbin
2014-01-01
Biochar produced by pyrolysis of biomass can be used to counter nitrogen (N) pollution. The present study investigated the effects of feedstock and temperature on characteristics of biochars and their adsorption ability for ammonium N (NH4 +-N) and nitrate N (NO3 −-N). Twelve biochars were produced from wheat-straw (W-BC), corn-straw (C-BC) and peanut-shell (P-BC) at pyrolysis temperatures of 400, 500, 600 and 700°C. Biochar physical and chemical properties were determined and the biochars were used for N sorption experiments. The results showed that biochar yield and contents of N, hydrogen and oxygen decreased as pyrolysis temperature increased from 400°C to 700°C, whereas contents of ash, pH and carbon increased with greater pyrolysis temperature. All biochars could sorb substantial amounts of NH4 +-N, and the sorption characteristics were well fitted to the Freundlich isotherm model. The ability of biochars to adsorb NH4 +-N followed: C-BC>P-BC>W-BC, and the adsorption amount decreased with higher pyrolysis temperature. The ability of C-BC to sorb NH4 +-N was the highest because it had the largest cation exchange capacity (CEC) among all biochars (e.g., C-BC400 with a CEC of 38.3 cmol kg−1 adsorbed 2.3 mg NH4 +-N g−1 in solutions with 50 mg NH4 + L−1). Compared with NH4 +-N, none of NO3 −-N was adsorbed to biochars at different NO3 − concentrations. Instead, some NO3 −-N was even released from the biochar materials. We conclude that biochars can be used under conditions where NH4 +-N (or NH3) pollution is a concern, but further research is needed in terms of applying biochars to reduce NO3 −-N pollution. PMID:25469875
Effects of feedstock and pyrolysis temperature on biochar adsorption of ammonium and nitrate.
Gai, Xiapu; Wang, Hongyuan; Liu, Jian; Zhai, Limei; Liu, Shen; Ren, Tianzhi; Liu, Hongbin
2014-01-01
Biochar produced by pyrolysis of biomass can be used to counter nitrogen (N) pollution. The present study investigated the effects of feedstock and temperature on characteristics of biochars and their adsorption ability for ammonium N (NH4(+)-N) and nitrate N (NO3(-)-N). Twelve biochars were produced from wheat-straw (W-BC), corn-straw (C-BC) and peanut-shell (P-BC) at pyrolysis temperatures of 400, 500, 600 and 700°C. Biochar physical and chemical properties were determined and the biochars were used for N sorption experiments. The results showed that biochar yield and contents of N, hydrogen and oxygen decreased as pyrolysis temperature increased from 400°C to 700°C, whereas contents of ash, pH and carbon increased with greater pyrolysis temperature. All biochars could sorb substantial amounts of NH4(+)-N, and the sorption characteristics were well fitted to the Freundlich isotherm model. The ability of biochars to adsorb NH4(+)-N followed: C-BC>P-BC>W-BC, and the adsorption amount decreased with higher pyrolysis temperature. The ability of C-BC to sorb NH4(+)-N was the highest because it had the largest cation exchange capacity (CEC) among all biochars (e.g., C-BC400 with a CEC of 38.3 cmol kg(-1) adsorbed 2.3 mg NH4(+)-N g(-1) in solutions with 50 mg NH4(+) L(-1)). Compared with NH4(+)-N, none of NO3(-)-N was adsorbed to biochars at different NO3(-) concentrations. Instead, some NO3(-)-N was even released from the biochar materials. We conclude that biochars can be used under conditions where NH4(+)-N (or NH3) pollution is a concern, but further research is needed in terms of applying biochars to reduce NO3(-)-N pollution.
Characterization and 2D structural model of corn straw and poplar leaf biochars.
Zhao, Nan; Lv, YiZhong; Yang, XiXiang; Huang, Feng; Yang, JianWen
2017-12-22
The integrated experimental methods were used to analyze the physicochemical properties and structural characteristics and to build the 2D structural model of two kinds of biochars. Corn straw and poplar leaf biochars were gained by pyrolysing the raw materials slowly in a furnace at 300, 500, and 700 °C under oxygen-deficient conditions. Scanning electron microscope was applied to observe the surface morphology of the biochars. High temperatures destroyed the pore structures of the biochars, forming a particle mixture of varying sizes. The ash content, yield, pH, and surface area were also observed to describe the biochars' properties. The yield decreases as the pyrolysis temperature increases. The biochars are neutral to alkaline. The biggest surface area is 251.11 m 2 /g for 700 °C corn straw biochar. Elemental analysis, infrared microspectroscopy, solid-state C-13 NMR spectroscopy, and pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) were also used to study the structural characteristics and build the 2D structural models of biochars. The C content in the corn straw and poplar leaf biochars increases with the increase of the pyrolysis temperature. A higher pyrolysis temperature makes the aryl carbon increase, and C=O, OH, and aliphatic hydrocarbon content decrease in the IR spectra. Solid-state C-13 NMR spectra show that a higher pyrolysis temperature makes the alkyl carbon and alkoxy carbon decrease and the aryl carbon increase. The results of IR microspectra and solid-state C-13 NMR spectra reveal that some noticeable differences exist in these two kinds of biochars and in the same type of biochar but under different pyrolysis temperatures. The conceptual elemental compositions of 500 °C corn straw and poplar leaf biochars are C 61 H 33 NO 13 and C 59 H 41 N 3 O 12 , respectively. Significant differences exist in the SEM images, physicochemical properties, and structural characteristics of corn straw and poplar leaf biochars.
Geng, Jing; Wang, Wen-Liang; Yu, Yu-Xiang; Chang, Jian-Min; Cai, Li-Ping; Shi, Sheldon Q
2017-03-01
The composition of pyrolysis vapors obtained from alkali lignin pyrolysis with the additive of nickel formate was examined using the pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). Characterization of bio-chars was performed using X-ray diffraction (XRD). Results showed that the nickel formate significantly increased liquid yield, simplified the types of alkali lignin pyrolysis products and increased individual component contents. The additive of nickel formate increased contents of alkylphenols and aromatics from alkali lignin pyrolysis. With an increase in temperature, a greater amount of the relative contents can be achieved. The nickel formate was thermally decomposed to form hydrogen, resulting in hydrodeoxygenation of alkali lignin during pyrolysis. It was also found that Ni is in favor of producing alkylphenols. The analysis based on the experimental result provided evidences used to propose reaction mechanism for pyrolysis of nickel formate-assisted alkali lignin. Copyright © 2016. Published by Elsevier Ltd.
USDA-ARS?s Scientific Manuscript database
In this study, we used a commercial pilot-scale, skid-mounted pyrolysis reactor system to produce combustible gas and biochar at 620ºC from three sources (chicken litter, swine solids, mixture of swine solids with rye grass). Pyrolysis of swine solids produced gas with the greatest higher heating va...
Mild pyrolysis of P3HB/Switchgrass blends for the production of bio-oil enriched with crotonic acid
USDA-ARS?s Scientific Manuscript database
The mild pyrolysis of switchgrass/poly-3-hydroxybutyrate (P3HB) blends that mimic P3HB-producing switchgrass lines was studied in a pilot scale fluidized bed reactor with the goal of simultaneously producing crotonic acid and switchgrass-based bio-oil. Factors such as pyrolysis temperature, residenc...
Toxicity of pyrolysis gases from polyether sulfone
NASA Technical Reports Server (NTRS)
Hilado, C. J.; Olcomendy, E. M.
1979-01-01
A sample of polyether sulfone was evaluated for toxicity of pyrolysis gases, using the toxicity screening test method developed at the University of San Francisco. Animal response times were relatively short at pyrolysis temperatures of 600 to 800 C, with death occurring within 6 min. The principal toxicant appeared to be a compound other than carbon monoxide.
Method for fabrication of crack-free ceramic dielectric films
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ma, Beihai; Narayanan, Manoj; Balachandran, Uthamalingam
The invention provides a process for forming crack-free dielectric films on a substrate. The process comprises the application of a dielectric precursor layer of a thickness from about 0.3 .mu.m to about 1.0 .mu.m to a substrate. The deposition is followed by low temperature heat pretreatment, prepyrolysis, pyrolysis and crystallization step for each layer. The deposition, heat pretreatment, prepyrolysis, pyrolysis and crystallization are repeated until the dielectric film forms an overall thickness of from about 1.5 .mu.m to about 20.0 .mu.m and providing a final crystallization treatment to form a thick dielectric film. The process provides a thick crack-free dielectricmore » film on a substrate, the dielectric forming a dense thick crack-free dielectric having an overall dielectric thickness of from about 1.5 .mu.m to about 20.0 .mu.m.« less
Self-activation of biochar from furfural residues by recycled pyrolysis gas.
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.
Upgraded bio-oil production via catalytic fast co-pyrolysis of waste cooking oil and tea residual.
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.
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.
Co-pyrolysis of polypropylene waste with Brazilian heavy oil.
Assumpção, Luiz C F N; Carbonell, Montserrat M; Marques, Mônica R C
2011-01-01
To evaluate the chemical recycling of plastic residues, co-pyrolysis of polypropylene (PP) waste with Brazilian crude oil was evaluated varying the temperature (400°C to 500°C) and the amount of PP fed to the reactor. The co-pyrolysis of plastic waste in an inert atmosphere provided around 80% of oil pyrolytic, and of these, half represent the fraction of diesel oil. This study can be used as a reference in chemical recycling of plastics, specially associated with plastics co-pyrolysis.
Chen, Shasha; Jia, Wanglu; Peng, Ping'an
2016-08-15
Carbon isotope analysis of n-alkanes produced by the pyrolysis of oil asphaltenes is a useful tool for characterizing and correlating oil sources. Low-temperature (320-350°C) pyrolysis lasting 2-3 days is usually employed in such studies. Establishing a rapid pyrolysis method is necessary to reduce the time taken for the pretreatment process in isotope analyses. One asphaltene sample was pyrolyzed in sealed ampoules for different durations (60-120 s) at 610°C. The δ(13) C values of the pyrolysates were determined by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The molecular characteristics and isotopic signatures of the pyrolysates were investigated for the different pyrolysis durations and compared with results obtained using the normal pyrolysis method, to determine the optimum time interval. Several asphaltene samples derived from various sources were analyzed using this method. The asphaltene pyrolysates of each sample were similar to those obtained by the flash pyrolysis method on similar samples. However, the molecular characteristics of the pyrolysates obtained over durations longer than 90 s showed intensified secondary reactions. The carbon isotopic signatures of individual compounds obtained at pyrolysis durations less than 90 s were consistent with those obtained from typical low-temperature pyrolysis. Several asphaltene samples from various sources released n-alkanes with distinct carbon isotopic signatures. This easy-to-use pyrolysis method, combined with a subsequent purification procedure, can be used to rapidly obtain clean n-alkanes from oil asphaltenes. Carbon isotopic signatures of n-alkanes released from oil asphaltenes from different sources demonstrate the potential application of this method in 'oil-oil' and 'oil-source' correlations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.
Dai, Zhongmin; Barberán, Albert; Li, Yong; Brookes, Philip C.
2017-01-01
ABSTRACT Microbes that colonize pyrogenic organic matter (PyOM) (also called biochar) play an important role in PyOM mineralization and crucially affect soil biogeochemical cycling, while the microbial community composition associated with PyOM particles is poorly understood. We generated two manure-based PyOMs with different characteristics (PyOM pyrolyzed at the low temperature of 300°C [i.e., PyOM300] and at the high temperature of 700°C [i.e., PyOM700]) and added them to high-carbon (4.15%) and low-C (0.37%) soil for microbial colonization. 16S rRNA gene sequencing showed that Actinobacteria, particularly Actinomycetales, was the dominant taxon in PyOM, regardless of the PyOM pyrolysis temperature and soil type. Bacterial communities associated with PyOM particles from high-C soils were similar to those in non-PyOM-amended soils. PyOM300 had higher total microbial activity and more differential bacterial communities than PyOM700. More bacterial operational taxonomic units (OTUs) preferentially thrived on the low-pyrolysis-temperature PyOM, while some specific OTUs thrived on high-pyrolysis-temperature PyOM. In particular, Chloroflexi species tended to be more prevalent in high-pyrolysis-temperature PyOM in low-C soils. In conclusion, the differences in colonized bacterial community composition between the different PyOMs were strongly influenced by the pyrolysis temperatures of PyOM, i.e., under conditions of easily mineralizable C or fused aromatic C, and by other properties, e.g., pH, surface area, and nutrient content. IMPORTANCE Pyrogenic organic matter (PyOM) is widely distributed in soil and fluvial ecosystems and plays an important role in biogeochemical cycling. Many studies have reported changes in soil microbial communities stimulated by PyOM, but very little is known about the microbial communities associated with PyOM. The microbes that colonize PyOMs can participate in the mineralization of PyOM, so changing its structure affects the fate of PyOMs and contributes to soil biogeochemical cycling. This study identified the bacterial community composition associated with PyOMs on the basis of high-throughput sequencing and demonstrated that both PyOM pyrolysis temperature and the colonization environment determined the bacterial community composition. Our work increases our understanding of the dominant phylogenetic taxa associated with PyOMs, demonstrates mechanisms mediating microbial metabolism and growth in PyOMs, and expands a new research area for pyrogenic organic matter. This study identified the bacterial community composition associated with PyOM, which is widely distributed in the environment. Most bacterial OTUs preferentially thrived on PyOM pyrolyzed at low temperature, while some specific OTUs thrived on PyOM pyrolyzed at high temperature. PMID:28405627
Dai, Zhongmin; Barberán, Albert; Li, Yong; Brookes, Philip C; Xu, Jianming
2017-01-01
Microbes that colonize pyrogenic organic matter (PyOM) (also called biochar) play an important role in PyOM mineralization and crucially affect soil biogeochemical cycling, while the microbial community composition associated with PyOM particles is poorly understood. We generated two manure-based PyOMs with different characteristics (PyOM pyrolyzed at the low temperature of 300°C [i.e., PyOM300] and at the high temperature of 700°C [i.e., PyOM700]) and added them to high-carbon (4.15%) and low-C (0.37%) soil for microbial colonization. 16S rRNA gene sequencing showed that Actinobacteria , particularly Actinomycetales , was the dominant taxon in PyOM, regardless of the PyOM pyrolysis temperature and soil type. Bacterial communities associated with PyOM particles from high-C soils were similar to those in non-PyOM-amended soils. PyOM300 had higher total microbial activity and more differential bacterial communities than PyOM700. More bacterial operational taxonomic units (OTUs) preferentially thrived on the low-pyrolysis-temperature PyOM, while some specific OTUs thrived on high-pyrolysis-temperature PyOM. In particular, Chloroflexi species tended to be more prevalent in high-pyrolysis-temperature PyOM in low-C soils. In conclusion, the differences in colonized bacterial community composition between the different PyOMs were strongly influenced by the pyrolysis temperatures of PyOM, i.e., under conditions of easily mineralizable C or fused aromatic C, and by other properties, e.g., pH, surface area, and nutrient content. IMPORTANCE Pyrogenic organic matter (PyOM) is widely distributed in soil and fluvial ecosystems and plays an important role in biogeochemical cycling. Many studies have reported changes in soil microbial communities stimulated by PyOM, but very little is known about the microbial communities associated with PyOM. The microbes that colonize PyOMs can participate in the mineralization of PyOM, so changing its structure affects the fate of PyOMs and contributes to soil biogeochemical cycling. This study identified the bacterial community composition associated with PyOMs on the basis of high-throughput sequencing and demonstrated that both PyOM pyrolysis temperature and the colonization environment determined the bacterial community composition. Our work increases our understanding of the dominant phylogenetic taxa associated with PyOMs, demonstrates mechanisms mediating microbial metabolism and growth in PyOMs, and expands a new research area for pyrogenic organic matter. This study identified the bacterial community composition associated with PyOM, which is widely distributed in the environment. Most bacterial OTUs preferentially thrived on PyOM pyrolyzed at low temperature, while some specific OTUs thrived on PyOM pyrolyzed at high temperature.
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.
Study on the Inference Factors of Huangling Coking Coal Pyrolysis
NASA Astrophysics Data System (ADS)
Du, Meili; Yang, Zongyi; Fan, Jinwen
2018-01-01
In order to reasonably and efficiently utilize Huangling coking coal resource, coal particle, heating rate, holding time, pyrolysis temperature and others factors were dicussed for the influence of those factor on Huangling coking coal pyrolysis products. Several kinds of coal blending for coking experiments were carried out with different kinds of coal such as Huangling coking coal, Xida coal with high ash low sufur, Xinghuo fat coal with hign sulfur, Zhongxingyi coking coal with high sulfur, Hucun lean coal, mixed meager and lean coal. The results shown that the optimal coal particle size distribution was 0.5~1.5mm, the optimal heating rate was 8°C/min, the optimal holding time was 15min, the optimal pyrolysis temperature was 800°C for Huangling coking coal pyrolysis, the tar yield increased from 4.7% to 11.2%. The maximum tar yield of coal blending for coking under the best single factor experiment condition was 10.65% when the proportio of Huangling coking coal was 52%.
Wang, Shuang; Xia, Zhen; Hu, Yamin; He, Zhixia; Uzoejinwa, Benjamin Bernard; Wang, Qian; Cao, Bin; Xu, Shanna
2017-03-01
Co-pyrolysis conversion of seaweed (Enteromorpha clathrat and Sargassum fusiforme) polysaccharides and cellulose has been investigated. From the Py-GC/MS results, Enteromorpha clathrata (EN) polysaccharides pyrolysis mainly forms furans; while the products of Sargassum fusiforme (SA) polysaccharides pyrolysis are mainly acid esters. The formation mechanisms of H 2 O, CO 2 , and SO 2 during the pyrolysis of seaweed polysaccharides were analyzed using the thermogravimetric-mass spectrometry. Meanwhile the pyrolysis of seaweed polysaccharide based on the Amber and the ReaxFF force fields, has also been proposed and simulated respectively. The simulation results coincided with the experimental results. During the fast pyrolysis, strong synergistic effects among cellulose and seaweed polysaccharide molecules have been simulated. By comparing the experimental and simulation value, it has been found that co-pyrolysis could increase the number of molecular fragments, increase the pyrolysis conversion rate, and increase gas production rate at the middle temperature range. Copyright © 2016 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Al-asadi, M.; Miskolczi, N.
2018-05-01
In this work the pyrolysis of polyethylene terephthalate (PET) containing real waste plastic was investigated using different Ni loaded catalysts: Ni/ZSM-5, Ni/y-zeolite, Ni/β-zeolite and Ni/natural zeolite (clinoptilolite). Raw materials were pyrolyzed in a horizontal tubular reactor between 600 and 900°C using 10% of catalysts. It was found, that both temperature increasing and catalysts presence can increase the gas yields, however owing to gasification reactions, the pyrolysis oil yield decreased with increasing temperature. Ni/y-zeolite catalyst had the most benefit in gas yield increasing at low temperature; however Ni/ZSM-5 showed advanced property in gas yield increasing at high temperature. Gases contained hydrogen, carbon oxides and hydrocarbons, which composition was significantly affected by catalysts. Ni loaded zeolites favoured to the formation of hydrogen and branched hydrocarbons; furthermore the concentrations of both CO and CO2 were also increased as function of elevated temperature. That phenomenon was attributed to the further decomposition of PET, especially to the side chain scission reactions. Owing to the Boudouard reaction, the ratio of CO2/CO can increased with temperature. Pyrolysis oils were the mixtures of n-saturated, n-unsaturated, branched, oxygen free aromatics and oxygenated hydrocarbons. Temperature increasing has a significant effect to the aromatization and isomerization reactions, while the catalysts can efficiently decreased the concentration of oxygen containing compounds.
USDA-ARS?s Scientific Manuscript database
Azimsulfuron is an acidic herbicide with a high water solubility which makes risk of groundwater contamination a concern. Various wood based biochars produced at different pyrolysis temperatures were characterized along with their sorption capacity for the herbicide azimsulfuron. In addition, we com...
Tan, Vincent; De Girolamo, Anthony; Hosseini, Tahereh; Alhesan, Jameel Aljariri; Zhang, Lian
2018-03-16
This paper attempts to develop a modified chemical percolation devolatilization (M-CPD) model that can include heat transfer, primary pyrolysis and the secondary cracking reactions of volatiles together to describe the pyrolysis of waste scrap tyre chip, as well as to examine the influence of operating conditions on the scrap tyre pyrolysis product yields. Such a study has yet to be conducted in the past, thereby leading to a large knowledge gap failing to understand the pyrolysis of the coarse feedstock appropriately. To validate the developed model, a number of operating parameters including reactor configurations, carrier gas compositions (argon and argon blended with CO 2 and/or steam), scrap tyre chip size (0.5-15.0 mm), terminal pyrolysis temperature (400-800 °C) and heating rate (10 °C/min and 110 °C/min) were examined in a lab-scale fixed-bed pyrolyser, with a particular focus on the secondary cracking extents of the liquid tar. Through both experimental investigation and modelling approach, it was found that significant secondary cracking extent occurred upon the increase in the feedstock size, heating rate and residence time. Upon the fast pyrolysis, the average temperature gap between the centres of the coarse particle and reactor wall could reach a maximum of 115 °C for the tyre chips of 6-15 mm. Consequently, its primary volatiles underwent the secondary cracking reaction at an overall extent of 17% at a terminal temperature of 600 °C and a fast heating rate of 110 °C/min. Consequently, the yield of light gases including methane was increased remarkably. The flow rate of inert carrier gas was also influential in the secondary cracking, in which a maximum tar yield (54 wt%) was reached at a carrier gas flow rate of 1.5 L/min. This indicates the occurrence of secondary cracking has been largely minimised. At a pyrolysis temperature of 600 °C, the addition of CO 2 in the carrier gas had an insignificant effect on the product yield distribution under the slow heating scheme. In contrast, the addition of steam resulted in a slight increase of carbon monoxide, presumably due to the occurrence of gasification reaction. Copyright © 2018 Elsevier Ltd. All rights reserved.
Coupled Ablation, Heat Conduction, Pyrolysis, Shape Change and Spallation of the Galileo Probe
NASA Technical Reports Server (NTRS)
Milos, Frank S.; Chen, Y.-K.; Rasky, Daniel J. (Technical Monitor)
1995-01-01
The Galileo probe enters the atmosphere of Jupiter in December 1995. This paper presents numerical methodology and detailed results of our final pre-impact calculations for the heat shield response. The calculations are performed using a highly modified version of a viscous shock layer code with massive radiation coupled with a surface thermochemical ablation and spallation model and with the transient in-depth thermal response of the charring and ablating heat shield. The flowfield is quasi-steady along the trajectory, but the heat shield thermal response is dynamic. Each surface node of the VSL grid is coupled with a one-dimensional thermal response calculation. The thermal solver includes heat conduction, pyrolysis, and grid movement owing to surface recession. Initial conditions for the heat shield temperature and density were obtained from the high altitude rarefied-flow calculations of Haas and Milos. Galileo probe surface temperature, shape, mass flux, and element flux are all determined as functions of time along the trajectory with spallation varied parametrically. The calculations also estimate the in-depth density and temperature profiles for the heat shield. All this information is required to determine the time-dependent vehicle mass and drag coefficient which are necessary inputs for the atmospheric reconstruction experiment on board the probe.
COAL/POLYMER COPROCESSING WITH EFFICIENT USE OF HYDROGEN
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dr. Linda J. Broadbelt; Matthew J. DeWitt; Hsi-Wu Wong
2000-09-30
The final project period was devoted to investigating the binary mixture pyrolysis of polypropylene and polystyrene. Their interactions were assessed in order to provide a baseline for experiments with multicomponent mixtures of polymers with coal. Pyrolysis of polypropylene, polystyrene and their binary mixture was investigated at temperatures of 350 C and 420 C with reaction times from 1 to 180 minutes. Two different loadings, 10 mg and 20 mg, were studied for neat polypropylene and polystyrene to assess the effect of total pressure on product yields and selectivities. For neat pyrolysis of polypropylene, total conversion was much higher at 420more » C, and no significant effect of loading on the total conversion was observed. Four classes of products, alkanes, alkenes, dienes, and aromatic compounds, were observed, and their distribution was explained by a typical free radical mechanism. For neat polystyrene pyrolysis, conversion reached approximately 75% at 350 C, while at 420 C the conversion reached a maximum around 90% at 10 minutes and decreased at longer times because of condensation reactions. The selectivities to major products were slightly different for the two different loadings due to the effect of total reaction pressure on secondary reactions. For binary mixture pyrolysis, the overall conversion was higher than the average of the two neat cases. The conversion of polystyrene remained the same, but a significant enhancement in the polypropylene conversion was observed. This suggests that the less reactive polypropylene was initiated by polystyrene-derived radicals. These results are summarized in detail in an attached manuscript that is currently in preparation. The other results obtained during the lifetime of this grant are documented in the set of attached manuscripts.« less
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.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Solak, Agnieszka; Rutkowski, Piotr, E-mail: piotr.rutkowski@pwr.wroc.pl
2014-02-15
Highlights: • Non-catalytic and catalytic fast pyrolysis of cellulose/polyethylene blend was carried out in a laboratory scale reactor. • Optimization of process temperature was done. • Optimization of clay catalyst type and amount for co-pyrolysis of cellulose and polyethylene was done. • The product yields and the chemical composition of bio-oil was investigated. - Abstract: Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 – montmorillonite K10, KSF – montmorillonite KSF, B – Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500 °C with heating rate of 100 °C/s to produce bio-oil with highmore » yield. The pyrolytic oil yield was in the range of 41.3–79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst.« less
Quality improvement of pyrolysis oil from waste rubber by adding sawdust.
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.
Process for oil shale retorting
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.
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.
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
Chemical and ecotoxicological evaluation of biochar produced from residues of biogas production.
Stefaniuk, Magdalena; Oleszczuk, Patryk; Bartmiński, Piotr
2016-11-15
Analyses were carried out for biochars produced at three temperatures of pyrolysis (400, 600 and 800°C) from solid residue from biogas production (RBP). Separated and non-separated RBP from biogas plants employing different biogas production conditions were pyrolyzed. The contents of heavy metals and polycyclic aromatic hydrocarbons (PAHs) (16 PAH US EPA) were analyzed in biochars. The analyses showed that with an increased pyrolysis temperature, there was an increase in the contents of PAHs and of certain heavy metals (Cr, Cu, Cd, Pb and Mn). In the ecotoxicological tests, it was noted that the effect depended on the temperature of pyrolysis and on the feedstock from which the biochar was produced. The least harmful effect on the test organisms was from biochar produced by separated RBP in a biogas plant operating in mesophilic conditions. The most negative effect on the test organisms was characteristic of biochar produced from non-separated mesophilic RBP. This study shows that the main factors determining the level of toxicity of biochars produced from RBP towards various living organisms are both the method of feedstock production and the temperature at which the process of pyrolysis is conducted. Copyright © 2016 Elsevier B.V. All rights reserved.
Wang, Xiaohua; Liu, Ni; Liu, Yunguo; Jiang, Luhua; Zeng, Guangming; Tan, Xiaofei; Liu, Shaobo; Yin, Zhihong; Tian, Sirong; Li, Jiang
2017-10-11
Rice straw biochar that produced at three pyrolysis temperatures (400, 500 and 600 °C) were used to investigate the adsorption properties of 17β-estradiol (E2). The biochar samples were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), elemental analysis and BET surface area measurements. The influences of pyrolysis temperature, E2 concentration, pH, ionic strength, background electrolyte and humic acid were studied. Kinetic and isotherm results illustrated that the adsorption process could be well described by pseudo-second-order and Freundlich models. Experimental results showed that ionic strength had less influence on the adsorption of E2 by 500 and 600 °C rice straw biochar. Further, multivalent ions had positive impact on E2 removal than monovalent ions and the influence of the pyrolysis temperature was unremarkable when background electrolyte existed in solutions. The adsorption capacity of E2 decreased with the pH ranged from 3.0 to 12.0 and the humic acid concentration from 2 to 10 mg L -1 . Electrostatic attractions and π-π interaction were involved in the adsorption mechanisms. Compared to low-temperature biochar, high-temperature biochar exhibited a better adsorption capacity for E2 in aqueous solution, indicated it had a greater potential for E2 pollution control.
Wang, Xiaohua; Liu, Ni; Liu, Yunguo; Jiang, Luhua; Zeng, Guangming; Tan, Xiaofei; Liu, Shaobo; Yin, Zhihong; Tian, Sirong; Li, Jiang
2017-01-01
Rice straw biochar that produced at three pyrolysis temperatures (400, 500 and 600 °C) were used to investigate the adsorption properties of 17β-estradiol (E2). The biochar samples were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), elemental analysis and BET surface area measurements. The influences of pyrolysis temperature, E2 concentration, pH, ionic strength, background electrolyte and humic acid were studied. Kinetic and isotherm results illustrated that the adsorption process could be well described by pseudo-second-order and Freundlich models. Experimental results showed that ionic strength had less influence on the adsorption of E2 by 500 and 600 °C rice straw biochar. Further, multivalent ions had positive impact on E2 removal than monovalent ions and the influence of the pyrolysis temperature was unremarkable when background electrolyte existed in solutions. The adsorption capacity of E2 decreased with the pH ranged from 3.0 to 12.0 and the humic acid concentration from 2 to 10 mg L−1. Electrostatic attractions and π-π interaction were involved in the adsorption mechanisms. Compared to low-temperature biochar, high-temperature biochar exhibited a better adsorption capacity for E2 in aqueous solution, indicated it had a greater potential for E2 pollution control. PMID:29019933
Pyrolysis characteristics of integrated circuit boards at various particle sizes and temperatures.
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.
Understanding the Behavior of the Oligomeric Fractions During Pyrolysis Oils Upgrading
NASA Astrophysics Data System (ADS)
Stankovikj, Filip
Fast pyrolysis oils represent most viable renewable sources for production of fuels and chemicals, and they could supplement significant portion of the depleting fossil fuels in near future. Progress on their utilization is impeded by their thermal and storage instability, lack of understanding of their complex composition and behavior during upgrading, including the poorly described water soluble fraction (WS). This work offers two new methodologies for simplified, and sensible description of the pyrolysis oils in terms of functional groups and chemical macro-families, augments our understanding of the composition of the WS, and the behavior of the heavy non-volatile fraction during pyrolysis oils stabilization. The concept of analyzing the volatile and non-volatile fraction in terms of functional groups has been introduced, and the quantification power of spectroscopic techniques (FTIR, 1H-NMR, UV fluorescence) for phenols, carbonyl and carboxyl groups was shown. The FT-ICR-MS van Krevelen diagram revealed the importance of dehydration reactions in pyrolysis oils and the presence of "pyrolytic humins" was hypothesized. For the first time the WS was analyzed with plethora of analytical techniques. This lead to proposition of a new characterization scheme based on functional groups, describing 90-100 wt.% of the bio-oils. The structure of idealized "pyrolytic humin" was further described as a random combination of 3-8 units of dehydrated sugars, coniferyl-type phenols, furans, and carboxylic acids attached on a 2,5-dioxo-6-hydroxyhexanal (DHH) backbone rich in carbonyl groups. TG-FTIR studies resulted in defining rules for fitting pyrolysis oils' DTG curves and assignment of TG residue. This second method is reliable for estimation of water content, light volatiles, WS and WIS. Finally, stabilization of two oils was analyzed through the prism of functional groups. Carbonyl and hydroxyl groups interconverted. The first attempt to follow silent 31P-NMR oxygen was presented; the O content reduced from 6 to 2%, which correlated well with the additional water formed. The water formation increased with stabilization temperature (3 to 10%), dominated by repolymerization instead deoxygenation. This last study presents a methodological framework for analysis of pyrolysis oils hydrotreatment; it simplifies modeling of these systems, vital for further understanding of bio-oil upgrading.
Antimony-Doped Tin Oxide Thin Films Grown by Home Made Spray Pyrolysis Technique
NASA Astrophysics Data System (ADS)
Yusuf, Gbadebo; Babatola, Babatunde Keji; Ishola, Abdulahi Dimeji; Awodugba, Ayodeji O.; Solar cell Collaboration
2016-03-01
Transparent conducting antimony-doped tin oxide (ATO) films have been deposited on glass substrates by home made spray pyrolysis technique. The structural, electrical and optical properties of the ATO films have been investigated as a function of Sb-doping level and annealing temperature. The optimum target composition for high conductivity and low resistivity was found to be 20 wt. % SnSb2 + 90 wt. ATO. Under optimized deposition conditions of 450oC annealing temperature, electrical resistivity of 5.2×10-4 Ω -cm, sheet resistance of 16.4 Ω/sq, average optical transmittance of 86% in the visible range, and average optical band-gap of 3.34eV were obtained. The film deposited at lower annealing temperature shows a relatively rough, loosely bound slightly porous surface morphology while the film deposited at higher annealing temperature shows uniformly distributed grains of greater size. Keywords: Annealing, Doping, Homemade spray pyrolysis, Tin oxide, Resistivity
NASA Technical Reports Server (NTRS)
Desai, Tapan G.; Lawson, John W.; Keblinski, Pawel
2010-01-01
Reactive molecular dynamics simulations are used to study initial stage of pyrolysis of ablation materials and their composites with carbon nanotubes and carbon fibers. The products formed during pyrolysis are characterized and water is found as the primary product in all cases. The water formation mechanisms are analyzed and the value of the activation energy for water formation is estimated. A detailed study on graphitic precursor formation reveals the presence of two temperature zones. In the lower temperature zone (less than 2000 K) polymerization occurs resulting in formation of large, stable graphitic precursors, and in the high temperature zone (greater than 2000 K) polymer scission results in formation of short polymer chains/molecules. Simulations performed in the high temperature zone on the phenolic resin composites (with carbon nanotubes and carbon fibers) shows that the presence of interfaces had no substantial effect on the chain scission rate or the activation energy value for water formation.
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
Liu, Tingting; Liu, Zhengang; Zheng, Qingfu; Lang, Qianqian; Xia, Yu; Peng, Nana; Gai, Chao
2018-01-01
The heavy metals distribution during hydrothermal carbonization (HTC) of sewage sludge, and pyrolysis of the resultant hydrochar was investigated and compared with raw sludge pyrolysis. The results showed that HTC reduced exchangeable/acid-soluble and reducible fraction of heavy metals and lowered the potential risk of heavy metals in sewage sludge. The pyrolysis favored the transformation of extracted/mobile fraction of heavy metals to residual form especially at high temperature, immobilizing heavy metals in the chars. Compared to the chars from raw sludge pyrolysis, the chars derived from hydrochar pyrolysis was more alkaline and had lower risk and less leachable heavy metals, indicating that pyrolysis imposed more positive effect on immobilization of heavy metals for the hydrochar than for sewage sludge. The present study demonstrated that HTC is a promising pretreatment prior to pyrolysis from the perspective of immobilization of heavy metals in sewage sludge. Copyright © 2017 Elsevier Ltd. All rights reserved.
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.
Innovative Processing of Composites for Ultra-High Temperature Applications. Book 3
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,
Behavior of sulfur during coal pyrolysis
Shao, D.; Hutchinson, E.J.; Heidbrink, J.; Pan, W.-P.; Chou, C.-L.
1994-01-01
The behavior of sulfur in Illinois coals during pyrolysis was evaluated by thermogravimetry/ Fourier transform-infrared spectroscopy (TG/FT-IR) techniques. SO2, COS, and H2S were major gaseous sulfur-containing products observed during coal pyrolysis. The release rates of the gaseous sulfur species showed several peaks within the temperature ranges, which were due to the emission of different forms of sulfur in coal. ?? 1994.
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.
Structure-mechanics property relationship of waste derived biochars.
Das, Oisik; Sarmah, Ajit K; Bhattacharyya, Debes
2015-12-15
The widespread applications of biochar in agriculture and environmental remediation made the scientific community ignore its mechanical properties. Hence, to examine the scope of biochar's structural applications, its mechanical properties have been investigated in this paper through nanoindentation technique. Seven waste derived biochars, made under different pyrolysis conditions and from diverse feedstocks, were studied via nanoindentation, infrared spectroscopy, X-ray crystallography, thermogravimetry, and electron microscopy. Following this, an attempt was made to correlate the biochars' hardness/modulus with reaction conditions and their chemical properties. The pine wood biochar made at 900°C and 60min residence time was found to have the highest hardness and elastic modulus of 4.29 and 25.01GPa, respectively. It was shown that a combination of higher heat treatment (≥500°C) temperature and longer residence time (~60min) increases the values of hardness and modulus. It was further realized that pyrolysis temperature was a more dominant factor than residence time in determining the final mechanical properties of biochar particles. The degree of aromaticity and crystallinity of the biochar were also correlated with higher values of hardness and modulus. Copyright © 2015 Elsevier B.V. All rights reserved.
Yang, Xuewei; Zeng, Yelin; Ma, Fuying; Zhang, Xiaoyu; Yu, Hongbo
2010-07-01
The thermogravimetric and chemical characterization of corn stover biopretreated by three different species of white-rot fungi have been studied in this research. Results indicated that biopretreatment can optimize the thermal decomposition, decrease the reaction temperature and reduce the gas contamination (SO(x)), making the biomass pyrolysis more efficient and environmentally friendly. Biopretreatment can decrease the activation energy and reacting temperature of the hemicellulose and cellulose pyrolysis (up to 36 degrees C), shorten the temperature range of the active pyrolysis (up to 14 degrees C), and increase the thermal decomposition rate, greatly promoting the reaction and making the biomass pyrolysis easier to start and carry on. On the other hand, by biopretreatment, the sulphur content can decrease up to 46.15%, which can considerably reduce the inventory of SO(x) emission. Moreover, the mechanism of the biopretreatment was also explored that the deconstruction and depolymerization of the recalcitrant linkages of lignin and cellulose by biopretreatment can make the structure of biomass incompact and easier to be pyrolyzed. Copyright (c) 2010 Elsevier Ltd. All rights reserved.
Biswas, Bijoy; Pandey, Nidhi; Bisht, Yashasvi; Singh, Rawel; Kumar, Jitendra; Bhaskar, Thallada
2017-08-01
Pyrolysis studies on conventional biomass were carried out in fixed bed reactor at different temperatures 300, 350, 400 and 450°C. Agricultural residues such as corn cob, wheat straw, rice straw and rice husk showed that the optimum temperatures for these residues are 450, 400, 400 and 450°C respectively. The maximum bio-oil yield in case of corn cob, wheat straw, rice straw and rice husk are 47.3, 36.7, 28.4 and 38.1wt% respectively. The effects of pyrolysis temperature and biomass type on the yield and composition of pyrolysis products were investigated. All bio-oils contents were mainly composed of oxygenated hydrocarbons. The higher area percentages of phenolic compounds were observed in the corn cob bio-oil than other bio-oils. From FT-IR and 1 H NMR spectra showed a high percentage of aliphatic functional groups for all bio-oils and distribution of products is different due to differences in the composition of agricultural biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.
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.
Understanding the fast pyrolysis of lignin.
Patwardhan, Pushkaraj R; Brown, Robert C; Shanks, Brent H
2011-11-18
In the present study, pyrolysis of corn stover lignin was investigated by using a micro-pyrolyzer coupled with a GC-MS/FID (FID=flame ionization detector). The system has pyrolysis-vapor residence times of 15-20 ms, thus providing a regime of minimal secondary reactions. The primary pyrolysis product distribution obtained from lignin is reported. Over 84 % mass balance and almost complete closure on carbon balance is achieved. In another set of experiments, the pyrolysis vapors emerging from the micro-pyrolyzer are condensed to obtain lignin-derived bio-oil. The chemical composition of the bio-oil is analyzed by using GC-MS and gel permeation chromatography techniques. The comparison between results of two sets of experiments indicates that monomeric compounds are the primary pyrolysis products of lignin, which recombine after primary pyrolysis to produce oligomeric compounds. Further, the effect of minerals (NaCl, KCl, MgCl(2), and CaCl(2)) and temperature on the primary pyrolysis product distribution is investigated. The study provides insights into the fundamental mechanisms of lignin pyrolysis and a basis for developing more descriptive models of biomass pyrolysis. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Synthesis and Useful Reactions of Organosilicon Polymeric Precursors for Ceramics
1992-04-05
composites are hot pressing, chemical vapor infiltration , reaction bonding and polymer infiltration / pyrolysis . Thus the inorganic or organometallic...to prepare preceramic polymers whose D; pyrolysis gives -99% SiC , -99.5% Si 3 N4 , or any mixture of the two by appropriate manipulation of the...the standard furnace pyrolysis of the polymer gave a ceramic of composition 96.6% SiC , 1.7% ZrC and 1.7% Si in 71% yield. Finally, (71-C
Comprehensive model for predicting elemental composition of coal pyrolysis products
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ricahrds, Andrew P.; Shutt, Tim; Fletcher, Thomas H.
Large-scale coal combustion simulations depend highly on the accuracy and utility of the physical submodels used to describe the various physical behaviors of the system. Coal combustion simulations depend on the particle physics to predict product compositions, temperatures, energy outputs, and other useful information. The focus of this paper is to improve the accuracy of devolatilization submodels, to be used in conjunction with other particle physics models. Many large simulations today rely on inaccurate assumptions about particle compositions, including that the volatiles that are released during pyrolysis are of the same elemental composition as the char particle. Another common assumptionmore » is that the char particle can be approximated by pure carbon. These assumptions will lead to inaccuracies in the overall simulation. There are many factors that influence pyrolysis product composition, including parent coal composition, pyrolysis conditions (including particle temperature history and heating rate), and others. All of these factors are incorporated into the correlations to predict the elemental composition of the major pyrolysis products, including coal tar, char, and light gases.« less
Production of bio-oil and biochar from soapstock via microwave-assisted co-catalytic fast pyrolysis.
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.
Yuan, Shuai; Chen, Xue-li; Li, Wei-feng; Liu, Hai-feng; Wang, Fu-chen
2011-11-01
Rapid pyrolysis of two types of aquatic biomass (blue-green algae and water hyacinth), and their blends with two coals (bituminous and anthracite) was carried out in a high-frequency furnace. Nitrogen conversions during rapid pyrolysis of the two biomass and the interactions between the biomass and coals on nitrogen conversions were investigated. Results show that little nitrogen retained in char after the biomass pyrolysis, and NH(3) yields were higher than HCN. During co-pyrolysis of biomass and coal, interactions between biomass and coal decreased char-N yields and increased volatile-N yields, but the total yields of NH(3)+HCN in volatile-N were decreased in which HCN formations were decreased consistently, while NH(3) formations were only decreased in the high-temperature range but promoted in the low-temperature range. Interactions between blue-green algae and coals are stronger than those between water hyacinth and coal, and interactions between biomass and bituminous are stronger than those between biomass and anthracite. Copyright © 2011 Elsevier Ltd. All rights reserved.
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.
Duan, Dengle; Wang, Yunpu; Dai, Leilei; Ruan, Roger; Zhao, Yunfeng; Fan, Liangliang; Tayier, Maimaitiaili; Liu, Yuhuan
2017-10-01
Microwave-assisted fast co-pyrolysis of lignin and polypropylene for bio-oil production was conducted using the ex-situ catalysis technology. Effects of catalytic temperature, feedstock/catalyst ratio, and lignin/polypropylene ratio on product distribution and chemical components of bio-oil were investigated. The catalytic temperature of 250°C was the most conducive to bio-oil production in terms of the yield. The bio-oil yield decreased with the addition of catalyst during ex-situ catalytic co-pyrolysis. When the feedstock/catalyst ratio was 2:1, the minimum char and coke values were 21.22% and 1.54%, respectively. The proportion of cycloalkanes decreased and the aromatics increased with the increasing catalyst loading. A positive synergistic effect was observed between lignin and polypropylene. The char yield dramatically deceased and the bio-oil yield improved during co-pyrolysis compared with those during lignin pyrolysis alone. The proportion of oxygenates dramatically and the minimum value of 6.74% was obtained when the lignin/polypropylene ratio was 1:1. Copyright © 2017. Published by Elsevier Ltd.
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.
Girardin, Bertrand; Fontaine, Gaëlle; Duquesne, Sophie; Försth, Michael; Bourbigot, Serge
2015-11-20
The pyrolysis of solid polymeric materials is a complex process that involves both chemical and physical phenomena such as phase transitions, chemical reactions, heat transfer, and mass transport of gaseous components. For modeling purposes, it is important to characterize and to quantify the properties driving those phenomena, especially in the case of flame-retarded materials. In this study, protocols have been developed to characterize the thermal conductivity and the heat capacity of an ethylene-vinyl acetate copolymer (EVA) flame retarded with aluminum tri-hydroxide (ATH). These properties were measured for the various species identified across the decomposition of the material. Namely, the thermal conductivity was found to decrease as a function of temperature before decomposition whereas the ceramic residue obtained after the decomposition at the steady state exhibits a thermal conductivity as low as 0.2 W/m/K. The heat capacity of the material was also investigated using both isothermal modulated Differential Scanning Calorimetry (DSC) and the standard method (ASTM E1269). It was shown that the final residue exhibits a similar behavior to alumina, which is consistent with the decomposition pathway of EVA/ATH. Besides, the two experimental approaches give similar results over the whole range of temperatures. Moreover, the optical properties before decomposition and the heat capacity of the decomposition gases were also analyzed. Those properties were then used as input data for a pyrolysis model in order to predict gasification experiments. Mass losses of gasification experiments were well predicted, thus validating the characterization of the thermo-physical properties of the material.
Girardin, Bertrand; Fontaine, Gaëlle; Duquesne, Sophie; Försth, Michael; Bourbigot, Serge
2015-01-01
The pyrolysis of solid polymeric materials is a complex process that involves both chemical and physical phenomena such as phase transitions, chemical reactions, heat transfer, and mass transport of gaseous components. For modeling purposes, it is important to characterize and to quantify the properties driving those phenomena, especially in the case of flame-retarded materials. In this study, protocols have been developed to characterize the thermal conductivity and the heat capacity of an ethylene-vinyl acetate copolymer (EVA) flame retarded with aluminum tri-hydroxide (ATH). These properties were measured for the various species identified across the decomposition of the material. Namely, the thermal conductivity was found to decrease as a function of temperature before decomposition whereas the ceramic residue obtained after the decomposition at the steady state exhibits a thermal conductivity as low as 0.2 W/m/K. The heat capacity of the material was also investigated using both isothermal modulated Differential Scanning Calorimetry (DSC) and the standard method (ASTM E1269). It was shown that the final residue exhibits a similar behavior to alumina, which is consistent with the decomposition pathway of EVA/ATH. Besides, the two experimental approaches give similar results over the whole range of temperatures. Moreover, the optical properties before decomposition and the heat capacity of the decomposition gases were also analyzed. Those properties were then used as input data for a pyrolysis model in order to predict gasification experiments. Mass losses of gasification experiments were well predicted, thus validating the characterization of the thermo-physical properties of the material. PMID:28793682
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.
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
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.
Zhang, Huiyan; Xiao, Rui; Nie, Jianlong; Jin, Baosheng; Shao, Shanshan; Xiao, Guomin
2015-09-01
Catalytic co-pyrolysis of black-liquor lignin and waste plastics (polyethylene, PE; polypropylene PP; polystyrene, PS) was conducted in a fluidized bed. The effects of temperature, plastic to lignin ratio, catalyst and plastic types on product distributions were studied. Both aromatic and olefin yields increased with increasing PE proportion. Petrochemical yield of co-pyrolysis of PE and lignin was LOSA-1 > spent FCC > Gamma-Al2O3 > sand. The petrochemical yield with LOSA-1 is 43.9% which is more than two times of that without catalyst. The feedstock for co-pyrolysis with lignin is polystyrene > polyethylene > polypropylene. Catalytic co-pyrolysis of black-liquor lignin with PS produced the maximum aromatic yield (55.3%), while co-pyrolysis with PE produced the maximum olefin yield (13%). Copyright © 2015 Elsevier Ltd. All rights reserved.
Kinetic study of corn straw pyrolysis: comparison of two different three-pseudocomponent models.
Li, Zhengqi; Zhao, Wei; Meng, Baihong; Liu, Chunlong; Zhu, Qunyi; Zhao, Guangbo
2008-11-01
With heating rates of 20, 50 and 100 K min(-1), the thermal decomposition of corn straw samples (corn stalks skins, corn stalks cores, corn bracts and corn leaves) were studied using thermogravimetric analysis. The maximum pyrolysis rates increased with the heating rate increasing and the temperature at the peak pyrolysis rate also increased. Assuming the addition of three independent parallel reactions, corresponding to three pseudocomponents linked to the hemicellulose, cellulose and lignin, two different three-pseudocomponent models were used to simulate the corn straw pyrolysis. Model parameters of pyrolysis were given. It was found that the three-pseudocomponent model with n-order kinetics was more accurate than the model with first-order kinetics at most cases. It showed that the model with n-order kinetics was more accurate to describe the pyrolysis of the hemicellulose.
Pyrolysis process for the treatment of scrap tyres: preliminary experimental results.
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.
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.
Process for fixed bed coal gasification
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.
NASA Astrophysics Data System (ADS)
Chen, Chunxiang; Cheng, Zheng; Xu, Qing; Qin, Songheng
2018-04-01
In order to explore the high-efficient utilization of oil shale, the effects of different microwave powers and different kinds of catalysts (metal oxides and metal salts) on the temperature characteristics and product yield towards the oil shale are investigated by microwave catalytic pyrolysis. The results show that the effect of microwave power on the heating and pyrolysis rates of oil shale is significant, and the maximum output of shale oil is 5.1% when the microwave power is 1500W; CaO has a certain effect on the temperature rise of oil shale, and MgO and CuO have a certain degree of inhibition, but the addition of three kinds of metal oxidation is beneficial to increase the shale oil production; From the perspective of unit power consumption and gas production, the catalytic effect order of three kinds of metal oxides is MgO> CaO> CuO; The addition of three kinds of metal salts is favorable for the increase of pyrolysis temperature of oil shale, after adding 5% ZnCl2, the unit power consumption of shale oil and pyrolysis gas increases by 62.60% and 81.96% respectively. After adding 5% NaH2PO3, the unit power consumption of shale oil increases by 64.64%, and reduces by 9.56% by adding 5% MgCl2.
Morgan, Trevor James; Turn, Scott Q.; George, Anthe
2015-08-26
A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amountsmore » of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. In conclusion, the reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali and alkali earth metals (totaling ~2.8 wt% relative to the dry feedstock) which are catalytic and increase cracking reactions during pyrolysis.« less
Morgan, Trevor James; Turn, Scott Q.; George, Anthe
2015-01-01
A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amounts of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. The reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali and alkali earth metals (totaling ~2.8 wt% relative to the dry feedstock) which are catalytic and increase cracking reactions during pyrolysis. PMID:26308860
DOE Office of Scientific and Technical Information (OSTI.GOV)
Morgan, Trevor James; Turn, Scott Q.; George, Anthe
A reactor was designed and commissioned to study the fast pyrolysis behavior of banagrass as a function of temperature and volatiles residence time. Four temperatures between 400 and 600°C were examined as well as four residence times between ~1.0 and 10 seconds. Pyrolysis product distributions of bio-oil, char and permanent gases were determined at each reaction condition. The elemental composition of the bio-oils and chars was also assessed. The greatest bio-oil yield was recorded when working at 450°C with a volatiles residence time of 1.4 s, ~37 wt% relative to the dry ash free feedstock (excluding pyrolysis water). The amountsmore » of char (organic fraction) and permanent gases under these conditions are ~4 wt% and 8 wt% respectively. The bio-oil yield stated above is for 'dry' bio-oil after rotary evaporation to remove solvent, which results in volatiles and pyrolysis water being removed from the bio-oil. The material removed during drying accounts for the remainder of the pyrolysis products. The 'dry' bio-oil produced under these conditions contains ~56 wt% carbon which is ~40 wt% of the carbon present in the feedstock. The oxygen content of the 450°C, 1.4 s 'dry' bio-oil is ~38 wt%, which accounts for ~33 wt% of the oxygen in the feedstock. At higher temperature or longer residence time less bio-oil and char is recovered and more gas and light volatiles are produced. Increasing the temperature has a more significant effect on product yields and composition than increasing the volatiles residence time. At 600°C and a volatiles residence time of 1.2 seconds the bio-oil yield is ~21 wt% of the daf feedstock, with a carbon content of 64 wt% of the bio-oil. The bio-oil yield from banagrass is significantly lower than from woody biomass or grasses such as switchgrass or miscanthus, but is similar to barley straw. In conclusion, the reason for the low bio-oil yield from banagrass is thought to be related to its high ash content (8.5 wt% dry basis) and high concentration of alkali and alkali earth metals (totaling ~2.8 wt% relative to the dry feedstock) which are catalytic and increase cracking reactions during pyrolysis.« less
Production of zinc and manganese oxide particles by pyrolysis of alkaline and Zn-C battery waste.
Ebin, Burçak; Petranikova, Martina; Steenari, Britt-Marie; Ekberg, Christian
2016-05-01
Production of zinc and manganese oxide particles from alkaline and zinc-carbon battery black mass was studied by a pyrolysis process at 850-950°C with various residence times under 1L/minN2(g) flow rate conditions without using any additive. The particular and chemical properties of the battery waste were characterized to investigate the possible reactions and effects on the properties of the reaction products. The thermodynamics of the pyrolysis process were studied using the HSC Chemistry 5.11 software. The carbothermic reduction reaction of battery black mass takes place and makes it possible to produce fine zinc particles by a rapid condensation, after the evaporation of zinc from a pyrolysis batch. The amount of zinc that can be separated from the black mass is increased by both pyrolysis temperature and residence time. Zinc recovery of 97% was achieved at 950°C and 1h residence time using the proposed alkaline battery recycling process. The pyrolysis residue is mainly MnO powder with a low amount of zinc, iron and potassium impurities and has an average particle size of 2.9μm. The obtained zinc particles have an average particle size of about 860nm and consist of hexagonal crystals around 110nm in size. The morphology of the zinc particles changes from a hexagonal shape to s spherical morphology by elevating the pyrolysis temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.
Gao, Zuopeng; Zhang, Hedong; Ao, Wenya; Li, Jing; Liu, Guangqing; Chen, Xiaochun; Fu, Jie; Ran, Chunmei; Liu, Yang; Kang, Qinhao; Mao, Xiao; Dai, Jianjun
2017-09-01
This paper investigated an auger pyrolyser under microwave irradiation using textile dyeing sludge (DS) as the feedstock. Microwave power, temperature, auger speed, gas velocity and addition of catalysts were studied. In terms of ICP-MS, Cu and As concentrations in condensates, depending on pyrolysis temperatures, exceeded the wastewater discharge standard in China. The condensate and oil yields reached maximum (i.e. 12.86 wt% and 0.84 wt%, respectively) at 650 °C. The content of aromatic compounds in the oil increased as temperature increased, up to 88.38% (GC-MS area) at 750 °C. Heterocyclic aromatic compounds containing nitrogen accounted for 20%-58% of the pyrolysis oil. Addition of catalysts such as CaO and Fe decreased pyrolysis oil yield and increased the content of H 2 . The H 2 content increased from 25.39v% without catalyst to 64.17v% with addition of 30 wt% CaO. The electricity consumption was 0.80-2.64 kWh/kg wet sludge from 450 to 750 °C and auger speed range of 1-9 rpm. Higher auger speeds and lower temperatures led to lower electricity consumption. Copyright © 2017 Elsevier Ltd. All rights reserved.
Site-Specific Pyrolysis Induced Cleavage at Aspartic Acid Residue in Peptides and Proteins
Zhang, Shaofeng; Basile, Franco
2011-01-01
A simple and site-specific non-enzymatic method based on pyrolysis has been developed to cleave peptides and proteins. Pyrolytic cleavage was found to be specific and rapid as it induced a cleavage at the C-terminal side of aspartic acid in the temperature range of 220–250 °C in 10 seconds. Electrospray Ionization (ESI) mass spectrometry (MS) and tandem-MS (MS/MS) were used to characterize and identify pyrolysis cleavage products, confirming that sequence information is conserved after the pyrolysis process in both peptides and protein tested. This suggests that pyrolysis-induced cleavage at aspartyl residues can be used as a rapid protein digestion procedure for the generation of sequence specific protein biomarkers. PMID:17388620
Mattonai, Marco; Ribechini, Erika
2018-08-09
Reactive pyrolysis is a technique that provides mechanistic information by performing pyrolysis of the substrate in a sealed glass capsule at elevated temperature and pressure for relatively long time. This technique has already shown great potential for the analysis of biomass, favouring the formation of only the most thermostable compounds. In this work, both fast and reactive pyrolysis with on-line gas chromatography-mass spectrometry analysis (Py-GC/MS) are used to study fructose, inulin and Jerusalem artichoke tubers (Heliantus tuberosus). Interesting differences were found between the two systems, and became even more evident as the reaction time was increased. The most striking result was the formation of di-fructose dianhydrides (DFAs), a class of compounds with interesting biological activities. DFAs were obtained in high yields from reactive pyrolysis, but not from fast pyrolysis. Hypotheses on the pyrolysis mechanisms were made based upon the composition of the pyrolysates. This work describes for the first time the behaviour of fructans under reactive pyrolysis. Copyright © 2018 Elsevier B.V. All rights reserved.
2006-08-01
conditions will necessarily be supercritical fluids . These temperatures and pressures will also cause the fuel to undergo pyrolytic reactions, which...Spectrometric Detection for 5a. CONTRACT NUMBER Analysis of Supercritical Fuels Pyrolysis Products 5b. GRANT NUMBER FA9550-05-1-0253 5c... supercritical pyrolysis experiments with the model fuels 1-methylnaphthalene and toluene. The HPLC/UV/MS instrument facilitated the identification of fifteen 5
Production of valuable hydrocarbons by flash pyrolysis of oil shale
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.
Wei, Juntao; Gong, Yan; Guo, Qinghua; Ding, Lu; Wang, Fuchen; Yu, Guangsuo
2017-03-01
Physicochemical evolution (i.e. pore structure variation, carbon structure change and active AAEM transformation) during rice straw (RS) and Shenfu bituminous coal (SF) co-pyrolysis was quantitatively determined in this work. Moreover, the corresponding char gasification was conducted using a thermogravimetric analyzer (TGA) and relative reactivity was proposed to quantify the co-pyrolysis impact on co-gasification reactivity. The results showed that the development of pore structure in co-pyrolyzed chars was first inhibited and then enhanced with the decrease of SF proportion. The promotion effect of co-pyrolysis on order degree of co-pyrolyzed chars gradually weakened with increasing RS proportion. Co-pyrolysis mainly enhanced active K transformation in co-pyrolyzed chars and the promotion effect was alleviated with increasing RS proportion. The inhibition effect of co-pyrolysis on co-gasification reactivity weakened with increasing RS proportion and gasification temperature, which was mainly attributed to the combination of carbon structure evolution and active AAEM transformation in co-pyrolysis. Copyright © 2016 Elsevier Ltd. All rights reserved.
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
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
NASA Astrophysics Data System (ADS)
Najeh, I.; Ben Mansour, N.; Mbarki, M.; Houas, A.; Nogier, J. Ph.; El Mir, L.
2009-10-01
Electrical conducting carbon (ECC) porous structures were explored by changing the pyrolysis temperature of organic xerogel compounds prepared by sol-gel method from resorcinol-formaldehyde (RF) mixtures in acetone using picric acid as catalyst. The effect of this preparation parameter on the structural and electrical properties of the obtained ECCs was studied. The analysis of the obtained results revealed that the polymeric insulating xerogel phase was transformed progressively with pyrolysis temperature into carbon conducting phase; this means the formation of long continuous conducting path for charge carriers to move inside the structure with thermal treatment and the samples exhibited tangible percolation behaviour where the percolation threshold can be determined by pyrolysis temperature. The temperature-dependent conductivity of the obtained ECC structures shows a semi-conducting behaviour and the I( V) characteristics present a negative differential resistance. The results obtained from STM micrographs revealed that the obtained ECC structures consist of porous electrical conducting carbon materials.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Lu; Lei, Hanwu; Ren, Shoujie
Microwave assisted catalytic pyrolysis was investigated to convert Douglas fir pellets to bio-oils by a ZSM-5 Zeolite catalyst. A central composite experimental design (CCD) was used to optimize the catalytic pyrolysis process. The effects of reaction time, temperature and catalyst to biomass ratio on the bio-oil, syngas, and biochar yields were determined. GC/MS analysis results showed that the bio-oil contained a series of important and useful chemical compounds. Phenols, guaiacols, and aromatic hydrocarbons were the most abundant compounds which were about 50-82 % in bio-oil depending on the pyrolysis conditions. Comparison between the bio-oils from microwave pyrolysis with and withoutmore » catalyst showed that the catalyst increased the content of aromatic hydrocarbons and phenols. A reaction pathway was proposed for microwave assisted catalyst pyrolysis of Douglas fir pellets.« less
Kinetics and evolved gas analysis for pyrolysis of food processing wastes using TGA/MS/FT-IR.
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.
Samolada, M C; Zabaniotou, A A
2014-02-01
For a sustainable municipal sewage sludge management, not only the available technology, but also other parameters, such as policy regulations and socio-economic issues should be taken in account. In this study, the current status of both European and Greek Legislation on waste management, with a special insight in municipal sewage sludge, is presented. A SWOT analysis was further developed for comparison of pyrolysis with incineration and gasification and results are presented. Pyrolysis seems to be the optimal thermochemical treatment option compared to incineration and gasification. Sewage sludge pyrolysis is favorable for energy savings, material recovery and high added materials production, providing a 'zero waste' solution. Finally, identification of challenges and barriers for sewage sludge pyrolysis deployment in Greece was investigated. Copyright © 2013 Elsevier Ltd. All rights reserved.
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.
NASA Astrophysics Data System (ADS)
Fetherolf, B. L.; Litzinger, T. A.; Lu, Y.-C.; Kuo, Kenneth K.
1993-11-01
The RDX-based composite propellants XM39 and M43 are similar in composition but exhibit significant differences in burning behavior. Experimental studies of the physical and chemical processes governing the CO2 laser-induced pyrolysis and deflagration of these two materials were conducted to characterize these differences in behavior and to gain some insight into the mechanisms responsible for the observed differences. Tests were conducted at one, three, and five atmospheres and laser heat fluxes of 100 - 1000 W/sq cm. Quantitative gaseous species profiles were measured with a microprobe/mass spectrometer system and both gas-phase temperature profiles and surface temperatures were measured with fine-wire thermocouples. Both materials exhibited similar gas-phase reaction chemistry to that of RDX with a primary nonluminous flame zone due to the reaction of CH2O and NO2 and a final luminous flame zone where HCN, NO, and a smaller amount of N2O were consumed to form the final products. However, the gas-phase zonal structure was significantly stretched out in comparison to the structure for pure RDX. The luminous flame was only observed above three atmospheres for M43 and above five atmospheres for XM39. Species and temperature measurements at the surfaces of the pyrolyzing propellants appeared to indicate more reaction in the condensed phase (i.e., melt layer) for M43 than for XM39. Subsurface gas species were measured by placing a probe within a hole drilled partway through a sample of XM39. The results indicated substantially less H2O, CH2O, HCN, and NO2 than were measured directly above the surface. This result and the observation of a temperature rise of about 100 degrees within the first 150 microns above the surface for both XM39 and M43 support the possible existence of a thin gas-phase reaction zone directly above the propellant surface.
Influence of pressure on pyrolysis of black liquor: 2. Char yields and component release.
Whitty, Kevin; Kullberg, Mika; Sorvari, Vesa; Backman, Rainer; Hupa, Mikko
2008-02-01
This is the second in a series of papers concerning the behavior of black liquor during pyrolysis at elevated pressures. Two industrial black liquors were pyrolyzed under pressurized conditions in two laboratory-scale devices, a pressurized single-particle reactor and a pressurized grid heater. Temperatures ranging between 650 and 1100 degrees C and pressures in the range 1-20 bar were studied. Char yields were calculated and based on analysis of some of the chars the fate of carbon, sodium, potassium and sulfur was determined as a function of pyrolysis pressure. At temperatures below 800 degrees C little variation in char yield was observed at different pressures. At higher temperatures char yield increased with pressure due to slower decomposition of sodium carbonate. For the same reason, sodium release decreased with pressure. Sulfur release, however, increased with pressure primarily because there was less opportunity for its capture in the less-swollen chars.
NASA Technical Reports Server (NTRS)
Graham, D. G.; Muenow, D. W.; Gibson, E. K., Jr.
1979-01-01
Mass pyrograms obtained from high-temperature, mass psectrometric pyrolysis of a glassy theoleiitic submarine basalt and a tektite, ground in air to less than 64 microns, have shown N2 and SO release patterns very similar to those from the pyrolysis of mature lunar soil fines. The N2 and CO release behavior from the terrestrial samples reproduces the biomodal, high-temperature (approximately 700 and 1050 C) features from the lunar samples. Unground portions of the basalt and tektite show no release of N2 and CO during pyrolysis. Grinding also alters the release behavior and absolute amounts of H2O and CO2. It is suggested that adsorption of atmospheric gases in addition to solar wind implantation of ions may account for the wide range of values in previously reported concentrations of carbon and nitrogen from lunar fines.
Modeling the pyrolysis study of non-charring polymers under reduced pressure environments
NASA Astrophysics Data System (ADS)
Zong, Ruowen; Kang, Ruxue; Hu, Yanghui; Zhi, Youran
2018-04-01
In order to study the pyrolysis of non-charring polymers under reduced pressure environments, a series of experiments based on black acrylonitrile butadiene styrene (ABS) was conducted in a reduced pressure chamber under different external heat fluxes. The temperatures of the top surface and the bottom of the sample and the mass loss during the whole process were measured in real time. A one-dimensional numerical model was developed to predict the top surface and the bottom surface temperatures of ABS during the pyrolysis at different reduced pressures and external heat fluxes, and the model was validated by the experimental data. The results of the study indicate that the profiles of the top surface and the bottom surface temperatures are different at different pressures and heat fluxes. The temperature and the mass loss rate of the sample under a lower heat flux decreased significantly as the pressure was increased. However, under a higher heat flux, the temperature and the mass loss rate showed little sensitivity to the pressure. The simulated results fitted the experimental results better at the higher heat flux than at the lower heat flux.
Kearns, J P; Wellborn, L S; Summers, R S; Knappe, D R U
2014-10-01
Batch isotherm experiments were conducted with chars to study adsorption of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Chars generated from corncobs, bamboo and wood chips in a laboratory pyrolyzer at 400-700 °C were compared with traditional kiln charcoals collected from villages in S/SE Asia and with activated carbons (ACs). 2,4-D uptake by laboratory chars obtained from bamboo and wood chips after 14 h of pyrolysis at 700 °C, from wood chips after 96 h of pyrolysis at 600 °C, and one of the field-collected chars (basudha) was comparable to ACs. H:C and O:C ratios declined with pyrolysis temperature and duration while surface area increased to >500 m(2)/g. Increasing pyrolysis intensity by increasing temperature and/or duration of heating was found to positively influence adsorption capacity yield (mg(2,4-D/g(feedstock))) over the range of conditions studied. Economic analysis showed that high temperature chars can be a cost-effective alternative to ACs for water treatment applications. Copyright © 2014 Elsevier Ltd. All rights reserved.
Co-pyrolysis of corn cob and waste cooking oil in a fixed bed.
Chen, Guanyi; Liu, Cong; Ma, Wenchao; Zhang, Xiaoxiong; Li, Yanbin; Yan, Beibei; Zhou, Weihong
2014-08-01
Corn cob (CC) and waste cooking oil (WCO) were co-pyrolyzed in a fixed bed. The effects of various temperatures of 500 °C, 550 °C, 600 °C and CC/WCO mass ratios of 1:0, 1:0.1, 1:0.5, 1:1 and 0:1 were investigated, respectively. Results show that co-pyrolysis of CC/WCO produce more liquid and less bio-char than pyrolysis of CC individually. Bio-oil and bio-char yields were found to be largely dependent on temperature and CC/WCO ratios. GC/MS of bio-oil show it consists of different classes and amounts of organic compounds other than that from CC pyrolysis. Temperature of 550 °C and CC/WCO ratio of 1:1 seem to be the optimum considering high bio-oil yields (68.6 wt.%) and good bio-oil properties (HHV of 32.78 MJ/kg). In this case, bio-char of 24.96 MJ/kg appears attractive as a renewable source, while gas with LHV of 16.06 MJ/Nm(3) can be directly used in boilers as fuel. Copyright © 2014 Elsevier Ltd. All rights reserved.
Catalyzed pyrolysis of grape and olive bagasse. Influence of catalyst type and chemical treatment
DOE Office of Scientific and Technical Information (OSTI.GOV)
Encinar, J.M.; Beltran, F.J.; Ramiro, A.
1997-10-01
Catalyzed pyrolysis of grape and olive bagasse under different experimental conditions has been studied. Variables investigated were temperature and type and concentration of catalysts. Experiments were carried out in an isothermal manner. Products of pyrolysis are gases (H{sub 2}, CO, CO{sub 2}, and CH{sub 4}), liquids (methanol, acetone, furfurylic alcohol, phenol, furfural, naphthalene, and o-cresol), and solids (chars). Temperature is a significant variable, yielding increases of fixed carbon content, gases, and to a lesser extent, ash percentage. Catalyst presence also yields increases of solid phase content, but the amount of liquid components decrease. Among catalysts applied those of Fe andmore » Zn are the most advisable to obtain gases. Chemical treatment of bagasses with sulfuric or phosphoric acid washing leads to lower char yields, although fixed carbon content is higher and ash presence diminishes with respect to catalyst pyrolysis without chemical pretreatment. A pyrolysis kinetic study based on gas generation from thermal decomposition of residues has been carried out. From the model proposed, rate constants for the formation of each gas, reaction order of the catalyst, and activation energies were determined.« less
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.
New applications of X-ray tomography in pyrolysis of biomass: Biochar imaging
Jones, Keith; Ramakrishnan, Girish; Uchimiya, Minori; ...
2015-01-30
We report on the first ever use of non-destructive micrometer-scale synchrotron-computed microtomography (CMT) for biochar material characterization as a function of pyrolysis temperature. This innovative approach demonstrated an increase in micron-sized marcropore fraction of the Cotton Hull (CH) sample, resulting in up to 29% sample porosity. We have also found that initial porosity development occurred at low temperatures (below 350°C) of pyrolysis, consistent with chemical composition of CH. This innovative technique can be highly complementary to traditional BET measurements, considering that Barrett–Joyner–Halenda (BJH) analysis of pore size distribution cannot detect these macropores. Such information can be of substantial relevance tomore » environmental applications, given that water retention by biochars added to soils is controlled by macropore characteristic among the other factors. In addition, complementing our data with SEM, EDX, and XRF characterization techniques allowed us to develop a better understanding of evolution of biochar properties during its production, such presence of metals and initial morphological features of biochar before pyrolysis. These results have significant implications for using biochar as a soil additive and for clarifying the mechanisms of biofuel production by pyrolysis.« less
New applications of X-ray tomography in pyrolysis of biomass: Biochar imaging
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jones, Keith; Ramakrishnan, Girish; Uchimiya, Minori
We report on the first ever use of non-destructive micrometer-scale synchrotron-computed microtomography (CMT) for biochar material characterization as a function of pyrolysis temperature. This innovative approach demonstrated an increase in micron-sized marcropore fraction of the Cotton Hull (CH) sample, resulting in up to 29% sample porosity. We have also found that initial porosity development occurred at low temperatures (below 350°C) of pyrolysis, consistent with chemical composition of CH. This innovative technique can be highly complementary to traditional BET measurements, considering that Barrett–Joyner–Halenda (BJH) analysis of pore size distribution cannot detect these macropores. Such information can be of substantial relevance tomore » environmental applications, given that water retention by biochars added to soils is controlled by macropore characteristic among the other factors. In addition, complementing our data with SEM, EDX, and XRF characterization techniques allowed us to develop a better understanding of evolution of biochar properties during its production, such presence of metals and initial morphological features of biochar before pyrolysis. These results have significant implications for using biochar as a soil additive and for clarifying the mechanisms of biofuel production by pyrolysis.« less
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.
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
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
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
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
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bandyopadhyay, S.; Chowdhury, R.; Biswas, G.K.
A mathematical model based on the mechanistic approach to the reaction kinetics of pyrolysis reactions and the realistic analysis of the interaction between simultaneous heat and mass transfer along with the chemical reaction has been developed for the design of smoothly running pyrolyzers. The model of a fixed-bed pyrolysis reactor has been proposed on the basis of the dimensionless parameters with respect to time and radial position. The variation of physical parameters like bed voidage, heat capacity, diffusivity, density, thermal conductivity, etc., on temperature and conversion has been taken into account. A deactivation model has also been incorporated to explainmore » the behavior of pyrolysis reactions at temperatures above 673 K. The simulated results of the model have been explained by comparing them with the experimental results.« less
Analysis of the combustion and pyrolysis of dried sewage sludge by TGA and MS.
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.
Fan, Liangliang; Chen, Paul; Zhang, Yaning; Liu, Shiyu; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Ruan, Roger
2017-02-01
Fast microwave-assisted catalytic co-pyrolysis of lignin and low-density polyethylene (LDPE) with HZSM-5 and MgO was investigated. Effects of pyrolysis temperature, lignin to LDPE ratio, MgO to HZSM-5 ratio, and feedstock to catalyst ratio on the products yields and chemical profiles were examined. 500°C was the optimal co-pyrolysis temperature in terms of the maximum bio-oil yield. The proportion of aromatics increased with increasing LDPE content. In addition, with the addition of LDPE (lignin/LDPE=1/2), methoxyl group in the phenols was completely removed. A synergistic effect was found between lignin and LDPE. The proportion of aromatics increased and alkylated phenols decreased with increasing HZSM-5 to MgO ratio. The bio-oil yield increased with the addition of appropriate amount of catalyst and the proportion of alkylated phenols increased with increasing catalyst to feedstock ratio. Copyright © 2016 Elsevier Ltd. All rights reserved.
Pattiya, Adisak
2011-01-01
Biomass residues from cassava plants, namely cassava stalk and cassava rhizome, were pyrolysed in a fluidised-bed reactor for production of bio-oil. The aims of this work were to investigate the yields and properties of pyrolysis products produced from both feedstocks as well as to identify the optimum pyrolysis temperature for obtaining the highest organic bio-oil yields. Results showed that the maximum yields of the liquid bio-oils derived from the stalk and rhizome were 62 wt.% and 65 wt.% on dry basis, respectively. The pyrolysis temperatures that gave highest bio-oil yields for both feedstocks were in the range of 475-510 °C. According to the analysis of the bio-oils properties, the bio-oil derived from cassava rhizome showed better quality than that derived from cassava stalk as the former had lower oxygen content, higher heating value and better storage stability. Copyright © 2010 Elsevier Ltd. All rights reserved.
Pyrolysis kinetics of algal consortia grown using swine manure wastewater.
Sharara, Mahmoud A; Holeman, Nathan; Sadaka, Sammy S; Costello, Thomas A
2014-10-01
In this study, pyrolysis kinetics of periphytic microalgae consortia grown using swine manure slurry in two seasonal climatic patterns in northwest Arkansas were investigated. Four heating rates (5, 10, 20 and 40 °C min(-1)) were used to determine the pyrolysis kinetics. Differences in proximate, ultimate, and heating value analyses reflected variability in growing substrate conditions, i.e., flocculant use, manure slurry dilution, and differences in diurnal solar radiation and air temperature regimes. Peak decomposition temperature in algal harvests varied with changing the heating rate. Analyzing pyrolysis kinetics using differential and integral isoconversional methods (Friedman, Flynn-Wall-Ozawa, and Kissinger-Akahira-Sunose) showed strong dependency of apparent activation energy on the degree of conversion suggesting parallel reaction scheme. Consequently, the weight loss data in each thermogravimetric test was modeled using independent parallel reactions (IPR). The quality of fit (QOF) for the model ranged between 2.09% and 3.31% indicating a good agreement with the experimental data. Copyright © 2014 Elsevier Ltd. All rights reserved.
Physical and chemical characterizations of biochars derived from different agricultural residues
NASA Astrophysics Data System (ADS)
Jindo, K.; Mizumoto, H.; Sawada, Y.; Sanchez-Monedero, M. A.; Sonoki, T.
2014-08-01
Biochar has received large attention as a strategy to tackle against carbon emission. Not only carbon fixation has been carried out but also other merits for agricultural application due to unique physical and chemical character such as absorption of contaminated compounds in soil, trapping ammonia and methane emission from compost, and enhancement of fertilizer quality. In our study, different local waste feed stocks (rice husk, rice straw, wood chips of apple tree (Malus Pumila) and oak tree (Quercus serrata)), in Aomori, Japan, were utilized for creating biochar with different temperature (400-800 °C). Concerning to the biochar production, the pyrolysis of lower temperature had more biochar yield than higher temperature pyrolysis process. On the contrary, surface areas and adsorption characters have been increased as increasing temperature. The proportions of carbon content in the biochars also increased together with increased temperatures. Infrared-Fourier spectra (FT-IR) and 13C-NMR were used to understand carbon chemical compositions in our biochars, and it was observed that the numbers of the shoulders representing aromatic groups, considered as stable carbon structure appeared as the temperature came closer to 600 °C, as well as in FT-IR. In rice materials, the peak assigned to SiO2, was observed in all biochars (400-800 °C) in FT-IR. We suppose that the pyrolysis at 600 °C creates the most recalcitrant character for carbon sequestration, meanwhile the pyrolysis at 400 °C produces the superior properties as a fertilizer by retaining volatile and easily labile compounds which promotes soil microbial activities.
Temperature & wood source control PyOM turnover in a Northern American forest
NASA Astrophysics Data System (ADS)
Hatton, Pierre-Joseph; Le Moine, James; Auclerc, Apolline; Gormley, Mark; Filley, Tim R.; Nadelhoffer, Knute J.; Bird, Jeff. A.
2016-04-01
Surprisingly little is known about how pyrolysis temperature and wood source affect the stability of forest-fire derived pyrogenic organic matter (PyOM). Here, we show that wood source and temperature affect in situ mineralization rates of PyOM in soils for two co-occurring gymnosperm (jack pine; JP [Pinus banksiana]) and angiosperm (red maple; RM [Acer rubrum])¬ species from North American boreal-temperate ecotones. We assess the effect of pyrolysis temperature on PyOM fates by following the decay of 13C/15N-enriched JP wood (JPwood) and PyOM produced at 300 °C (JP300) and 450 °C (JP450); and assess the effect of PyOM wood source by comparing fates of JP450 and RM450. JPwood mineralized 18× faster than JP300 and 44× faster than JP450 after 2.8y. RM450 mineralized initially faster than JP450 during the first ~2y, but became equivalent afterwards (1.1±0.2% of CO¬2 losses after 2.8y). Modeled turnover times suggest that this can be attributed to ~1% of fast-cycling PyOM (<3y). Slower-cycling pools are 12× faster for JPwood (13±5y) than for JP300 (157±28y) and 55× faster than for JP450 (700±229y). Modeled turnover times of the slow-cycling pools were equivalent for JP450 and RM450. The priming effect was positive for JPwood (0.10±0.05), neutral for JP300 (-0.02±0.04), and negative for JP450 (-0.15±0.03) and RM50 (-0.59±0.03). DOC losses were minimal compared with CO2 losses (DOC:CO2 ratio ≤0.005), but followed the same patterns: JPwood 6× greater than that of JP300 and 39× greater compared with JP450. After 1y, C recoveries were lower for JPwood than for PyOM, with no influence of pyrolysis temperature or wood source (yet); N recoveries did not differ. PLFA-(13)C data reveal that (i) treatments have similar microbial communities after 1y, (ii) JPwood is preferentially utilized by fungi, and (iii) bacteria increasingly utilize PyOM as pyrolysis temperature increases. Estimated carbon use efficiency decreased with increasing pyrolysis temperature (JPwood~JP300>JP450~RM450). Although insignificant, potential phenol oxidase and peroxidase activities decrease with increasing pyrolysis temperature. Neither PyOM nor wood additions (~11% of soil C stock 0-20 cm depth) affected pH or Ec after 1y. We provide the first, field experimental evidence that pyrolysis temperature and wood source affect the turnover of PyOM in soil. We show faster, initial decay for PyOM produced at lesser temperature and RM (angiosperm) compared with JP (gymnosperm). This study offers realistic insights on (i) the controls underlying in situ PyOM turnover, and on (ii) how ongoing/projected changes in tree species composition and fire frequency/intensity/distribution may affect PyOM in soil of North America temperate-boreal ecotones.
Zhang, Hedong; Gao, Zuopeng; Liu, Yang; Ran, Chunmei; Mao, Xiao; Kang, Qinhao; Ao, Wenya; Fu, Jie; Li, Jing; Liu, Guangqing; Dai, Jianjun
2018-05-01
This study investigated the pyrolysis characteristic of textile dyeing sludge (DS) using an auger pyrolyser under microwave irradiation at different pyrolysis temperature. The migration and distribution characteristic of heavy metals and their potential ecological risks were investigated using inductively coupled plasma mass spectrometry (ICP-MS) techniques. Temperature and additives (e.g. Ca-bentonite, kaolin and CaO) significantly affected product distribution and yields. Heavy metals showed different enrichment characteristics during pyrolysis and a great percentage of the heavy metals was retained in the sludge char (SC), depending on different temperatures and additives. CaO had a strong ability for retention of S, Pb and Ni. Ca-bentonite, kaolin and CaO had considerable ability to retain Cr at 650 ℃. Ca-bentonite and CaO had positive effects on Ni retention at 450 °C and 650 °C. As was enriched at 450 °C with addition of Ca-bentonite. Cu and Zn were enriched at 450 °C and 850 °C without additives and the corresponding residue ratios (RRs) were 88.68-100%, which indicated good stability of these heavy metals during microwave pyrolysis of DS. The heavy metal contents in SC were lower than those in the national standards (CJ/T 362-2011, China) and these heavy metals showed slight potential ecological risk to the environment. Copyright © 2018 Elsevier B.V. All rights reserved.
Toxicity of Pyrolysis Gases from Elastomers
NASA Technical Reports Server (NTRS)
Hilado, Carlos J.; Kosola, Kay L.; Solis, Alida N.; Kourtides, Demetrius A.; Parker, John A.
1977-01-01
The toxicity of the pyrolysis gases from six elastomers was investigated. The elastomers were polyisoprene (natural rubber), styrene-butadiene rubber (SBR), ethylene propylene diene terpolymer (EPDM), acrylonitrile rubber, chlorosulfonated polyethylene rubber, and polychloroprene. The rising temperature and fixed temperature programs produced exactly the same rank order of materials based on time to death. Acryltonitrile rubber exhibited the greatest toxicity under these test conditions; carbon monoxide was not found in sufficient concentrations to be the primary cause of death.
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.
Biochar, the carbon-rich material remaining after pyrolysis (low oxygen) of cellulosic feedstocks, has the potential as a soil amendment to sequester carbon, improve soil water-holding capacity, and increase nutrient retention thereby enhancing soil conditions to benefit plant gr...
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...
Low temperature isothermal pyrolysis of cellulose
A. Broido; M. Weinstein
1971-01-01
By providing continuous weight measurement, thermogravimetry, even for isothermal experiments, offers a major advantage over the classical methods of determining weight-change curves in complex pyrolysis reactions. Thus, even minor weight changes, readily detectable on a continuous record, furnish clues concerning the reaction sequences and indicate conditions under...
Catalytic pyrolysis characteristics of scrap printed circuit boards by TG-FTIR.
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.
Smoke Hazards Resulting from the Burning of Shipboard Paints. Part 3.
1987-09-18
pyrolysis begins about 2 mins. after the sample is first exposed to the radiant heat flux. A peak mass loss rate of about 0.4 mg/cm2-s occurs after...the higher local surface tempera- tures associated with the flaming combustion of pyrolysis gases issuing from these cracks. Smoke particle size...combustion in room temperature ventilation air, the mean .’ particle diameters vary between 0.7 and 1.1 /Am during the initial stages of pyrolysis and
NASA Astrophysics Data System (ADS)
Shuai, Yanhua; Douglas, Peter M. J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael D.; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.
2018-02-01
Multiply isotopically substituted molecules ('clumped' isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature-time conditions corresponding to 'low,' 'mature,' and 'over-mature' stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions ('high' to 'over-mature' stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where 'secondary' cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.
NASA Technical Reports Server (NTRS)
Pike, R. W.; Delvalle, E. G.
1974-01-01
The decomposition of ablative composites is described along with the transport phenomena of pyrolysis gases which result from the decomposition of these plastics as they flow through the porous char of char-forming ablators. The pyrolysis products are those formed by the thermal degradation of nylon-phenolic resin and silicone elastomer composites. Emphasis is placed on the nature and extent of chemical reactions of the pyrolysis products and the char, along with the energy absorbed by the combined pyrolysis and char zone. Chemical reactions with thermodynamically consistent kinetic data are determined in order to develop a realistic analysis for predicting the thermal performance of ablative heat shields.
Gong, Xiaomin; Huang, Danlian; Liu, Yunguo; Zeng, Guangming; Wang, Rongzhong; Wei, Jingjing; Huang, Chao; Xu, Piao; Wan, Jia; Zhang, Chen
2018-04-01
This study aimed to investigate the effect of pyrolysis on the stabilization of heavy metals in plant residues obtained after phytoremediation. Ramie residues, being collected after phytoremediation of metal contaminated sediments, were pyrolyzed at different temperatures (300-700 °C). Results indicated that pyrolysis was effective in the stabilization of Cd, Cr, Zn, Cu, and Pb in ramie residues by converting the acid-soluble fraction of metals into residual form and decreasing the TCLP-leachable metal contents. Meanwhile, the reutilization potential of using the pyrolysis products generated from ramie residues obtained after phytoremediation as sorbents was investigated. Adsorption experiments results revealed that the pyrolysis products presented excellent ability to adsorb methylene blue (MB) with a maximum adsorption capacity of 259.27 mg/g. This study demonstrated that pyrolysis could be used as an efficient alternative method for stabilizing heavy metals in plant residues obtained after phytoremediation, and their pyrolysis products could be reutilized for dye adsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.
Flash Vacuum Pyrolysis: Techniques and Reactions.
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.
Zhang, Huiyan; Wang, Yun; Shao, Shanshan; Xiao, Rui
2016-11-21
Lignin is the most difficult to be converted and most easy coking component in biomass catalytic pyrolysis to high-value liquid fuels and chemicals. Catalytic conversion of guaiacol as a lignin model compound was conducted in a fixed-bed reactor over ZSM-5 to investigate its conversion and coking behaviors. The effects of temperature, weight hourly space velocity (WHSV) and partial pressure on product distribution were studied. The results show the maximum aromatic carbon yield of 28.55% was obtained at temperature of 650 °C, WHSV of 8 h -1 and partial pressure of 2.38 kPa, while the coke carbon yield was 19.55%. The reaction pathway was speculated to be removing methoxy group to form phenols with further aromatization to form aromatics. The amount of coke increased with increasing reaction time. The surface area and acidity of catalysts declined as coke formed on the acid sites and blocked the pore channels, which led to the decrease of aromatic yields. Finally, a kinetic model of guaiacol catalytic conversion considering coke deposition was built based on the above reaction pathway to properly predict product distribution. The experimental and model predicting data agreed well. The correlation coefficient of all equations were all higher than 0.90.
Zhang, Huiyan; Wang, Yun; Shao, Shanshan; Xiao, Rui
2016-01-01
Lignin is the most difficult to be converted and most easy coking component in biomass catalytic pyrolysis to high-value liquid fuels and chemicals. Catalytic conversion of guaiacol as a lignin model compound was conducted in a fixed-bed reactor over ZSM-5 to investigate its conversion and coking behaviors. The effects of temperature, weight hourly space velocity (WHSV) and partial pressure on product distribution were studied. The results show the maximum aromatic carbon yield of 28.55% was obtained at temperature of 650 °C, WHSV of 8 h−1 and partial pressure of 2.38 kPa, while the coke carbon yield was 19.55%. The reaction pathway was speculated to be removing methoxy group to form phenols with further aromatization to form aromatics. The amount of coke increased with increasing reaction time. The surface area and acidity of catalysts declined as coke formed on the acid sites and blocked the pore channels, which led to the decrease of aromatic yields. Finally, a kinetic model of guaiacol catalytic conversion considering coke deposition was built based on the above reaction pathway to properly predict product distribution. The experimental and model predicting data agreed well. The correlation coefficient of all equations were all higher than 0.90. PMID:27869228
Xu, Zhiyuan; Shi, Jingjing; Haroone, Muhammad Sohail; Chen, Wenpeng; Zheng, Shufang; Lu, Jun
2018-04-01
Due to the superiority of metal-doped ZnO compared to TiO 2 , the Zn-M (M = Al 3+ , Ga 3+ , Cr 3+ , Ti 4+ , Ce 4+ ) mixed metal oxide solid solutions have been extensively studied for photocatalytic and photovoltaic applications. In this work, a systematic research has proceeded for the preparation of a zinc-aluminum oxide semiconductor as a photoanode for the dye-sensitized solar cells (DSSCs) by a simple pyrolysis route with the Zn-Al layered double hydroxide (LDH) as a precursor. The Zn-Al oxide solid solution has been applied for DSSCs as an electron acceptor, which is used to study the influence of different Al content and sintering temperature on the device efficiency. Finally, the Zn-Al oxide solid solution with calcination temperature 600 °C and Al 27 at.% content exhibits the best performance. The photoelectric efficiency improved 100 times when the Al 3+ content decreased from 44 to 27 at.%. The Zn x Al y O solid solution show a reasonable efficiency as photoanode materials in DSSCs, with the best preliminary performance reported so far, and shows its potential application for the photovoltaic devices. Copyright © 2018 Elsevier Inc. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zacher, Alan H.; Elliott, Douglas C.; Olarte, Mariefel V.
Liquid transportation fuel blend-stocks were produced by pyrolysis and catalytic upgrading of woody residue biomass. Mountain pine beetle killed wood and hog fuel from a saw mill were pyrolyzed in a 1 kg/h fluidized bed reactor and subsequently upgraded to hydrocarbons in a continuous fixed bed hydrotreater. Upgrading was performed by catalytic hydrotreatment in a two-stage bed at 170°C and 405°C with a per bed LHSV between 0.17 and 0.19. The overall yields from biomass to upgraded fuel were similar for both feeds: 24-25% despite the differences in bio-oil (intermediate) mass yield. Pyrolysis bio-oil mass yield was 61% from MPBKmore » wood, and subsequent upgrading of the bio-oil gave an average mass yield of 41% to liquid fuel blend stocks. Hydrogen was consumed at an average of 0.042g/g of bio-oil fed, with final oxygen content in the product fuel ranging from 0.31% to 1.58% over the course of the test. Comparatively for hog fuel, pyrolysis bio-oil mass yield was lower at 54% due to inorganics in the biomass, but subsequent upgrading of that bio-oil had an average mass yield of 45% to liquid fuel, resulting in a similar final mass yield to fuel compared to the cleaner MPBK wood. Hydrogen consumption for the hog fuel upgrading averaged 0.041 g/g of bio-oil fed, and the final oxygen content of the product fuel ranged from 0.09% to 2.4% over the run. While it was confirmed that inorganic laded biomass yields less bio-oil, this work demonstrated that the resultant bio-oil can be upgraded to hydrocarbons at a higher yield than bio-oil from clean wood. Thus the final hydrocarbon yield from clean or residue biomass pyrolysis/upgrading was similar.« less
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.
Huang, Hua; Wang, Ya-Xiong; Tang, Jing-Chun; Tang, Jing-Chun; Zhu, Wen-Ying
2014-05-01
Biochar was made from maize stalk under three different temperatures of 300, 500 and 700 degreeC. The elemental composition of biochar was measured by elemental analyzer. Scanning electron microscope (SEM) was used to measure the surface morphology. Sorption of naphthalene to biochar was researched by batch sorption experiments. Results showed that, with the increase of temperature, C content increased from 66. 79% to 76. 30% , H and O contents decreased from 4.92% and 19. 25% to 3. 18% and 9.53%, respectively; H/C, O/C, (O + N)/C, aromaticity and hydrophobicity increased, and polarity decreased. SEM results showed that maize stalk biochar was platy particles, and its roughness of surface increased with increasing temperature. The sorption of naphthalene on biochar followed the Lagergren pseudo-second order dynamic sorption model. Initial sorption rate and equilibrium sorption capacity increased as preparation temperatures increased at the same initial concentration of naphthalene. The isotherm sorption behavior can be described by the Freundlich model, which indicated that, as pyrolysis temperature increased, the sorption capacity of biochar increased, and nonlinearity increased first and then decreased. Biochar derived from maize stalk had distinct features when compared with other feedstocks, and its elemental composition, surface features and sorption behaviors were significantly influenced by pyrolysis temperature.
USDA-ARS?s Scientific Manuscript database
Inorganic elements in biomass feedstocks can influence thermochemical reactions as well as the resultant chars elemental, compositional, and thermal characteristics. Chars were produced using slow pyrolysis at less than 400 and at higher than 500 degree Celsius from sugarcane bagasse, peanut hulls,...
New applications of x-ray tomography in pyrolysis of biomass: biochar imaging
USDA-ARS?s Scientific Manuscript database
We report on the first ever use of non-destructive micrometer-scale synchrotron computed microtomography for characterization of biochar materials as a function of pyrolysis temperature. Using this innovative approach we have observed an increase in marcropore fraction of the sample, resulting in 29...
Mathematical model of a smoldering log.
Fernando de Souza Costa; David Sandberg
2004-01-01
A mathematical model is developed describing the natural smoldering of logs. It is considered the steady one dimensional propagation of infinitesimally thin fronts of drying, pyrolysis, and char oxidation in a horizontal semi-infinite log. Expressions for the burn rates, distribution profiles of temperature, and positions of the drying, pyrolysis, and smoldering fronts...
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...
Methods for detecting the mobility of trace elements during medium-temperature pyrolysis
Shiley, R.H.; Konopka, K.L.; Cahill, R.A.; Hinckley, C.C.; Smith, Gerard V.; Twardowska, H.; Saporoschenko, Mykola
1983-01-01
The mobility (volatility) of trace elements in coal during pyrolysis has been studied for distances of up to 40 cm between the coal and the trace element collector, which was graphite or a baffled solvent trap. Nineteen elements not previously recorded as mobile were detected. ?? 1983.
TG-FTIR analysis on pyrolysis and combustion of marine sediment
NASA Astrophysics Data System (ADS)
Oudghiri, Fatiha; Allali, Nabil; Quiroga, José María; Rodríguez-Barroso, María Rocío
2016-09-01
In this paper, the pyrolysis and combustion of sediment have been compared using thermogravimetric analysis (TG) coupled with Fourier transform infrared spectrometry (TG-FTIR) analysis. The TG results showed that both the pyrolysis and combustion of sediment presented four weight loss stages, each. The evolving gaseous products during pyrolysis were H2O, CO2 and hydrocarbons, while combustion yielded considerable amounts of CO2, in addition to H2O, CO, Cdbnd C, Cdbnd O and NH3. Comparing the pyrolysis and combustion TG-FTIR curves, it is possible to evaluate the effect of oxygen presence in the temperature range of 200-600 °C, which increases the volatilisation rate of organic matter in sediment. For the better detection of organic and inorganic matter in sediment by TG-FTIR analysis it is recommended to work in combustion mode of sediment.
Method of increasing anhydrosugars, pyroligneous fractions and esterified bio-oil
Steele, Philip H; Yu, Fei; Li, Qi; Mitchell, Brian
2014-12-30
The device and method are provided to increase anhydrosugars yield during pyrolysis of biomass. This increase is achieved by injection of a liquid or gas into the vapor stream of any pyrolysis reactor prior to the reactor condensers. A second feature of our technology is the utilization of sonication, microwave excitation, or shear mixing of the biomass to increase the acid catalyst rate for demineralization or removal of hemicellulose prior to pyrolysis. The increased reactivity of these treatments reduces reaction time as well as the required amount of catalyst to less than half of that otherwise required. A fractional condensation system employed by our pyrolysis reactor is another feature of our technology. This system condenses bio-oil pyrolysis vapors to various desired fractions by differential temperature manipulation of individual condensers comprising a condenser chain.
Bio-Fuel Production Assisted with High Temperature Steam Electrolysis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Grant Hawkes; James O'Brien; Michael McKellar
2012-06-01
Two hybrid energy processes that enable production of synthetic liquid fuels that are compatible with the existing conventional liquid transportation fuels infrastructure are presented. Using biomass as a renewable carbon source, and supplemental hydrogen from high-temperature steam electrolysis (HTSE), these two hybrid energy processes have the potential to provide a significant alternative petroleum source that could reduce dependence on imported oil. The first process discusses a hydropyrolysis unit with hydrogen addition from HTSE. Non-food biomass is pyrolyzed and converted to pyrolysis oil. The pyrolysis oil is upgraded with hydrogen addition from HTSE. This addition of hydrogen deoxygenates the pyrolysis oilmore » and increases the pH to a tolerable level for transportation. The final product is synthetic crude that could then be transported to a refinery and input into the already used transportation fuel infrastructure. The second process discusses a process named Bio-Syntrolysis. The Bio-Syntrolysis process combines hydrogen from HTSE with CO from an oxygen-blown biomass gasifier that yields syngas to be used as a feedstock for synthesis of liquid synthetic crude. Conversion of syngas to liquid synthetic crude, using a biomass-based carbon source, expands the application of renewable energy beyond the grid to include transportation fuels. It can also contribute to grid stability associated with non-dispatchable power generation. The use of supplemental hydrogen from HTSE enables greater than 90% utilization of the biomass carbon content which is about 2.5 times higher than carbon utilization associated with traditional cellulosic ethanol production. If the electrical power source needed for HTSE is based on nuclear or renewable energy, the process is carbon neutral. INL has demonstrated improved biomass processing prior to gasification. Recyclable biomass in the form of crop residue or energy crops would serve as the feedstock for this process. A process model of syngas production using high temperature electrolysis and biomass gasification is presented. Process heat from the biomass gasifier is used to heat steam for the hydrogen production via the high temperature steam electrolysis process. Oxygen produced form the electrolysis process is used to control the oxidation rate in the oxygen-blown biomass gasifier.« less
Sun, Yu'an; Liu, Baoxia; Wang, Guoqing; Zhang, Rongjie; Xie, Bing
2005-01-01
The thermal behavior of vitamin D3 was studied based on pyrolysis-GC-MS technique. It was pyrolyzed at 600 degrees C, 750 degrees C, 900 degrees C, respectively. The pyrolysis product were separated With an HP-5 column and identified by the NIST mass spectral search program in combination with the correlation of boiling point and retention time (BP-RT). There are totally 50 components, including mono aromatics and polycyclic aromatic hydrocarbons (PAHs), were determined. It is shown that the contents of the PAHs are increasing with the increasing of the pyrolysis temperature. The contents of the determined components vary from 0.04% to 37.08%.
Preparation of pyrolysis reference samples: evaluation of a standard method using a tube furnace.
Sandercock, P Mark L
2012-05-01
A new, simple method for the reproducible creation of pyrolysis products from different materials that may be found at a fire scene is described. A temperature programmable steady-state tube furnace was used to generate pyrolysis products from different substrates, including softwoods, paper, vinyl sheet flooring, and carpet. The temperature profile of the tube furnace was characterized, and the suitability of the method to reproducibly create pyrolysates similar to those found in real fire debris was assessed. The use of this method to create proficiency tests to realistically test an examiner's ability to interpret complex gas chromatograph-mass spectrometric fire debris data, and to create a library of pyrolsates generated from materials commonly found at a fire scene, is demonstrated. © 2011 American Academy of Forensic Sciences.
Kinetic Analysis of the Main Temperature Stage of Fast Pyrolysis
NASA Astrophysics Data System (ADS)
Yang, Xiaoxiao; Zhao, Yuying; Xu, Lanshu; Li, Rui
2017-10-01
Kinetics of the thermal decomposition of eucalyptus chips was evaluated using a high-rate thermogravimetric analyzer (BL-TGA) designed by our research group. The experiments were carried out under non-isothermal condition in order to determine the fast pyrolysis behavior of the main temperature stage (350-540ºC) at heating rates of 60, 120, 180, and 360ºC min-1. The Coats-Redfern integral method and four different reaction mechanism models were adopted to calculate the kinetic parameters including apparent activation energy and pre-exponential factor, and the Flynn-Wall-Ozawa method was employed to testify apparent activation energy. The results showed that estimation value was consistent with the values obtained by linear fitting equations, and the best-fit model for fast pyrolysis was found.
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.
Effects of pyrolysis conditions on yield of bio-chars from pine chips
Qiangu Yan; Hossein Toghiani; Fei Yu; Zhiyong Cai; Jilei Zhang
2011-01-01
The influences of temperature, heating rate, purge gas type, and flow rate on the yield of chars produced from pyrolyzing southern pine chips were investigated. Pyrolysis temperatures were between 450°C and 1,000°C, with heating rates of 0.5°C/min, 1.0°C/min, 10°C/min, 30°C/min, 50°C/min, and 100°C/min. Purge gases, nitrogen (N2), hydrogen (H
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.
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
Calcium-rich biochar from the pyrolysis of crab shell for phosphorus removal.
Dai, Lichun; Tan, Furong; Li, Hong; Zhu, Nengmin; He, Mingxiong; Zhu, Qili; Hu, Guoquan; Wang, Li; Zhao, Jie
2017-08-01
Calcium-rich biochars (CRB) prepared through pyrolysis of crab shell at various temperatures were characterized for physicochemical properties and P removal potential. Elemental analysis showed that CRB was rich in calcium (22.91%-36.14%), while poor in carbon (25.21%-9.08%). FTIR, XRD and TG analyses showed that calcite-based CRB was prepared at temperature ≤600 °C, while lime-based CRB was prepared at temperature ≥700 °C. Phosphorus removal experiment showed that P removal efficiencies in 80 mg P/L phosphate solution and biogas effluent ranged from 26% to 11%, respectively, to about 100% and 63%, respectively, depending on the pyrolysis temperature of the resulting biochar. Specifically, compared to common used CaCO 3 and Ca(OH) 2 , P removal potential of calcite-based CRB was much higher than that of CaCO 3 ; while that of lime-based CRB was close to that of Ca(OH) 2 . These results suggested that CRB was competent for P removal/recovery from wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.
Ji, Ran; Zheng, Ding; Zhou, Chang; Cheng, Jiang; Yu, Junsheng; Li, Lu
2017-07-18
Tungsten oxide (WO₃) is prepared by a low-temperature ultrasonic spray pyrolysis method in air atmosphere, and it is used as an anode buffer layer (ABL) for organic solar cells (OSCs). The properties of the WO₃ transition metal oxide material as well as the mechanism of ultrasonic spray pyrolysis processes are investigated. The results show that the ultrasonic spray pyrolysized WO₃ ABL exhibits low roughness, matched energy level, and high conductivity, which results in high charge transport efficiency and suppressive recombination in OSCs. As a result, compared to the OSCs based on vacuum thermal evaporated WO₃, a higher power conversion efficiency of 3.63% is reached with low-temperature ultrasonic spray pyrolysized WO₃ ABL. Furthermore, the mostly spray-coated OSCs with large area was fabricated, which has a power conversion efficiency of ~1%. This work significantly enhances our understanding of the preparation and application of low temperature-processed WO₃, and highlights the potential of large area, all spray coated OSCs for sustainable commercial fabrication.
Liquid smoke characteristics from the pyrolysis of oil palm fronds
NASA Astrophysics Data System (ADS)
Maulina, S.; Silia, F.
2018-02-01
This study was conducted as means to characterize the pyrolysis of oil palm fronds into more economical products. In particular, this study was focused on pyrolysis of oil palm fronds, which could generate products such as liquid smoke, tar and char. Four characteristics of liquid smoke were examined in this study, namely the yield of liquid smoke, phenolic content, total acid content and pH. These characteristics were examined in a temperature of 150 °C, 200 °C and 250 °C with processing time of 60 minutes, 90 minutes and 120 minutes. This study revealed that the highest yield of liquid smoke was equal to 43.47% at a temperature of 150 °C for approximately 2 hours, while the highest level of phenolic was obtained at a temperature of 250 °C for approximately 1 hour. Moreover, the highest total acid content obtained was 11.23% at a temperature of 150 °C with a time of 1 hour. In addition, all operating conditions has produced liquid smoke with an average pH value of 3.
Ji, Ran; Zheng, Ding; Zhou, Chang; Cheng, Jiang; Yu, Junsheng; Li, Lu
2017-01-01
Tungsten oxide (WO3) is prepared by a low-temperature ultrasonic spray pyrolysis method in air atmosphere, and it is used as an anode buffer layer (ABL) for organic solar cells (OSCs). The properties of the WO3 transition metal oxide material as well as the mechanism of ultrasonic spray pyrolysis processes are investigated. The results show that the ultrasonic spray pyrolysized WO3 ABL exhibits low roughness, matched energy level, and high conductivity, which results in high charge transport efficiency and suppressive recombination in OSCs. As a result, compared to the OSCs based on vacuum thermal evaporated WO3, a higher power conversion efficiency of 3.63% is reached with low-temperature ultrasonic spray pyrolysized WO3 ABL. Furthermore, the mostly spray-coated OSCs with large area was fabricated, which has a power conversion efficiency of ~1%. This work significantly enhances our understanding of the preparation and application of low temperature-processed WO3, and highlights the potential of large area, all spray coated OSCs for sustainable commercial fabrication. PMID:28773177
Eom, In-Yong; Kim, Jae-Young; Lee, Soo-Min; Cho, Tae-Su; Yeo, Hwanmyeong; Choi, Joon-Weon
2013-01-01
The objectives of this study were to investigate the effects of inorganic constituents on the fast pyrolysis of the biomass and to determine the yields as well as physicochemical properties of pyrolytic products. The pyrolytic products were obtained from raw and demineralized rice straw using a fluidized bed type pyrolyzer at different temperatures. As pyrolysis temperature increased, total biooil yield gradually decreased from 46.6 to 29.6 wt.% for the raw-straw, and from 55.4 to 35.3 wt.% for the demineralized rice straw. For demineralized rice straw, higher pyrolysis temperatures promoted gasification reactions but reduced char formations. However, char yield for the raw-straw was relatively unaffected by temperature due to an increase in carbonization reactions that were catalyzed by some inorganics. Certain inorganic constituents in the biomass were distinctively distributed in the biooil, and ICP-ES and GC/MS analysis indicated that some inorganics may be chemically bound to cell wall components. Copyright © 2012 Elsevier Ltd. All rights reserved.
Numerical Study of Pyrolysis of Biomass in Fluidized Beds
NASA Technical Reports Server (NTRS)
Bellan, Josette; Lathouwers, Danny
2003-01-01
A report presents a numerical-simulation study of pyrolysis of biomass in fluidized-bed reactors, performed by use of the mathematical model described in Model of Fluidized Bed Containing Reacting Solids and Gases (NPO-30163), which appears elsewhere in this issue of NASA Tech Briefs. The purpose of the study was to investigate the effect of various operating conditions on the efficiency of production of condensable tar from biomass. The numerical results indicate that for a fixed particle size, the fluidizing-gas temperature is the foremost parameter that affects the tar yield. For the range of fluidizing-gas temperatures investigated, and under the assumption that the pyrolysis rate exceeds the feed rate, the optimum steady-state tar collection was found to occur at 750 K. In cases in which the assumption was not valid, the optimum temperature for tar collection was found to be only slightly higher. Scaling up of the reactor was found to exert a small negative effect on tar collection at the optimal operating temperature. It is also found that slightly better scaling is obtained by use of shallower fluidized beds with greater fluidization velocities.
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
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.
Rafiq, Muhammad Khalid; Joseph, Stephen D; Li, Fei; Bai, Yanfu; Shang, Zhanhuan; Rawal, Aditya; Hook, James M; Munroe, Paul R; Donne, Scott; Taherymoosavi, Sara; Mitchell, David R G; Pace, Ben; Mohammed, Mohanad; Horvat, Joseph; Marjo, Christopher E; Wagner, Avital; Wang, Yanlong; Ye, Jun; Long, Rui-Jun
2017-12-31
Recent studies have shown that the pyrolysis of biomass combined with clay can result in both lower cost and increase in plant yields. One of the major sources of nutrients for pasture growth, as well as fuel and building materials in Tibet is yak dung. This paper reports on the initial field testing in a pasture setting in Tibet using yak dung, biochar, and attapulgite clay/yak dung biochars produced at ratios of 10/90 and 50/50 clay to dung. We found that the treatment with attapulgite clay/yak dung (50/50) biochar resulted in the highest pasture yields and grass nutrition quality. We also measured the properties and yields of mixtures of clay/yak dung biochar used in the field trials produced at 400°C and 500°C to help determine a possible optimum final pyrolysis temperature and dung/clay ratio. It was observed that increasing clay content increased carbon stability, overall biochar yield, pore size, carboxyl and ketone/aldehyde functional groups, hematite and ferrous/ferric sulphate/thiosulphate concentration, surface area and magnetic moment. Decreasing clay content resulted in higher pH, CEC, N content and an enhanced ability to accept and donate electrons. The resulting properties were a complex function of both processing temperature and the percentage of clay for the biochars processed at both 400°C and 500°C. It is possible that the increase in yield and nutrient uptake in the field trial is related to the higher concentration of C/O functional groups, higher surface area and pore volume and higher content of Fe/O/S nanoparticles of multiple oxidation state in the 50/50 clay/dung. These properties have been found to significantly increase the abundance of beneficial microorganisms and hence improve the nutrient cycling and availability in soil. Further field trials are required to determine the optimum pyrolysis production conditions and application rate on the abundance of beneficial microorganisms, yields and nutrient quality. Copyright © 2017 Elsevier B.V. All rights reserved.
Antunes, Elsa; Schumann, James; Brodie, Graham; Jacob, Mohan V; Schneider, Philip A
2017-07-01
The amount of biosolids increases every year, and social and environmental concerns are also rising due to heavy metals and pathogen contamination. Even though biosolids are considered as a waste material, they could be used as a precursor in several applications, especially in agriculture due to the presence of essential nutrients. Microwave assisted pyrolysis (MWAP) is a promising technology to safely manage biosolids, while producing value-added products, such as biochar, that can be used to improve soil fertility. This study examined the impact of pyrolysis temperature between 300 °C and 800 °C on the chemical and physical properties of biochar obtained from biosolids via MWAP. Preliminary phosphorus adsorption tests were carried out with the biochar produced from biosolids. This research demonstrated that pyrolysis temperature affects biochar specific surface area, ash and volatiles content, but does not impact heavily on the pH, chemical composition and crystalline phases of the resultant biochar. Biochar yield decreases as the pyrolysis temperature increases. Phosphorus adsorption capacity of biochar was approximately around 15 mg/g of biochar. Biochar resulting from MWAP is a potential candidate for land application with an important role in water and nutrient retention, due to the high surface area. Copyright © 2017 Elsevier Ltd. All rights reserved.
Conversion of microwave pyrolysed ASR's char using high temperature agents.
Donaj, Pawel; Blasiak, Wlodzimierz; Yang, Weihong; Forsgren, Christer
2011-01-15
Pyrolysis enables to recover metals and organic feedstock from waste conglomerates such as: automotive shredder residue (ASR). ASR as well as its pyrolysis solid products, is a morphologically and chemically varied mixture, containing mineral materials, including hazardous heavy metals. The aim of the work is to generate fundamental knowledge on the conversion of the organic residues of the solid products after ASR's microwave pyrolysis, treated at various temperatures and with two different types of gasifying agent: pure steam or 3% (v/v) of oxygen. The research is conducted using a lab-scale, plug-flow gasifier, with an integrated scale for analysing mass loss changes over time of experiment, serving as macro TG at 950, 850 and 760 °C. The reaction rate of char decomposition was investigated, based on carbon conversion during gasification and pyrolysis stage. It was found in both fractions that char conversion rate decreases with the rise of external gas temperature, regardless of the gasifying agent. No significant differences between the reaction rates undergoing with steam and oxygen for char decomposition has been observed. This abnormal char behaviour might have been caused by the inhibiting effects of ash, especially alkali metals on char activity or due to deformation of char structure during microwave heating. Copyright © 2010 Elsevier B.V. All rights reserved.
Solak, Agnieszka; Rutkowski, Piotr
2014-02-01
Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 - montmorillonite K10, KSF - montmorillonite KSF, B - Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500°C with heating rate of 100°C/s to produce bio-oil with high yield. The pyrolytic oil yield was in the range of 41.3-79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500°C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst. Copyright © 2013 Elsevier Ltd. All rights reserved.
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.
Machado, Cláudia Emanuele; Tartuci, Letícia Gazola; de Fátima Gorgulho, Honória; de Oliveira, Luiz Fernando Cappa; Bettini, Jefferson; Pereira dos Santos, Daniela; Ferrari, Jefferson Luis; Schiavon, Marco Antônio
2016-03-18
This work used L-tartaric acid as a model molecule to evaluate how the use of inert and oxidizing atmospheres during pyrolysis affected the physical and optical properties of the resulting carbon dots (CDs). Pyrolysis revealed to be a simple procedure that afforded CDs in a single step, dismissed the addition of organic solvents, and involved only one extraction stage that employed water. By X-ray diffraction a dependency between the structure of the CDs and the atmosphere (oxidizing or inert) used during the pyrolysis was found. Potentiometric titration demonstrated that the CDs were largely soluble in water; it also aided characterization of the various groups that contained sp(3) -hybridized carbon atoms on the surface of the dots. Raman spectroscopy suggested that different amounts of sp(2)- and sp(3)-hybridized carbon atoms emerged on the CDs depending on the pyrolysis atmosphere. In conclusion, the pyrolysis atmosphere influenced the physical properties, such as the composition and the final structure. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Thermal/Pyrolysis Gas Flow Analysis of Carbon Phenolic Material
NASA Technical Reports Server (NTRS)
Clayton, J. Louie
2001-01-01
Provided in this study are predicted in-depth temperature and pyrolysis gas pressure distributions for carbon phenolic materials that are externally heated with a laser source. Governing equations, numerical techniques and comparisons to measured temperature data are also presented. Surface thermochemical conditions were determined using the Aerotherm Chemical Equilibrium (ACE) program. Surface heating simulation used facility calibrated radiative and convective flux levels. Temperatures and pyrolysis gas pressures are predicted using an upgraded form of the SINDA/CMA program that was developed by NASA during the Solid Propulsion Integrity Program (SPIP). Multispecie mass balance, tracking of condensable vapors, high heat rate kinetics, real gas compressibility and reduced mixture viscosity's have been added to the algorithm. In general, surface and in-depth temperature comparisons are very good. Specie partial pressures calculations show that a saturated water-vapor mixture is the main contributor to peak in-depth total pressure. Further, for most of the cases studied, the water-vapor mixture is driven near the critical point and is believed to significantly increase the local heat capacity of the composite material. This phenomenon if not accounted for in analysis models may lead to an over prediction in temperature response in charring regions of the material.
Putschew, A.; Schaeffer-Reiss, C.; Schaeffer, P.; Koopmans, M.P.; De Leeuw, J. W.; Lewan, M.D.; Sinninghe, Damste J.S.; Maxwell, J.R.
1998-01-01
An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330??C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH2 and HI/LiAIH4) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis-GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260??C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak Carbon-heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220??C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.
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.
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.
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.
Aysu, Tevfik
2015-09-01
Pyrolysis of Alcea pallida stems was performed in a fixed-bed tubular reactor with and without catalyst at three different temperatures. The effects of pyrolysis parameters including temperature and catalyst on the product yields were investigated. It was found that higher temperature resulted in lower liquid (bio-oil) and solid (bio-char) yields and higher gas yields. Catalysts had different effects on product yields and composition of bio-oils. Liquid yields were increased in the presence of zinc chloride and alumina but decreased with calcium hydroxide, tincal and ulexite. The highest bio-oil yield (39.35%) by weight including aqueous phase was produced with alumina catalyst at 500 °C. The yields of bio-char, bio-oil and gas produced, as well as the compositions of the resulting bio-oils were determined by elemental analysis, TGA, FT-IR and GC-MS. 160 different compounds were identified by GC-MS in the bio-oils obtained at 500 °C. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Kumar, A. Madhan; Babu, R. Suresh; Obot, I. B.; Adesina, Akeem Yusuf; Ibrahim, Ahmed; de Barros, A. L. F.
2018-05-01
Protecting the surface of metals and alloys against corrosion and wear is of abundant importance owing to their widespread applications. In the present work, we report the improved anticorrosion and tribo-mechanical performance of copper (Cu) by a hard carbon (HC) coating synthesized in different pyrolysis temperature. Structural and surface characterization with roughness measurements was systematically investigated using various techniques. Effect of pyrolysis temperature on the corrosion behavior of coated Cu substrates in 0.6 M NaCl solution was evaluated via electrochemical impedance spectroscopy, potentiodynamic polarization. Pin-on-disk wear test of coated Cu substrate showed the influence of the pyrolysis temperature on the wear resistance performance of the HC coatings. According to the obtained results, it could be concluded that the HC coatings synthesized at 1100 °C revealed an enhanced comprehensive performance, revealing their possible utilization as a protective coating for Cu substrates in chloride environment. Monte Carlo simulations have been utilized to elucidate the interaction between the Cu surface and HC coatings.
NASA Astrophysics Data System (ADS)
Kumar, A. Madhan; Babu, R. Suresh; Obot, I. B.; Adesina, Akeem Yusuf; Ibrahim, Ahmed; de Barros, A. L. F.
2018-01-01
Protecting the surface of metals and alloys against corrosion and wear is of abundant importance owing to their widespread applications. In the present work, we report the improved anticorrosion and tribo-mechanical performance of copper (Cu) by a hard carbon (HC) coating synthesized in different pyrolysis temperature. Structural and surface characterization with roughness measurements was systematically investigated using various techniques. Effect of pyrolysis temperature on the corrosion behavior of coated Cu substrates in 0.6 M NaCl solution was evaluated via electrochemical impedance spectroscopy, potentiodynamic polarization. Pin-on-disk wear test of coated Cu substrate showed the influence of the pyrolysis temperature on the wear resistance performance of the HC coatings. According to the obtained results, it could be concluded that the HC coatings synthesized at 1100 °C revealed an enhanced comprehensive performance, revealing their possible utilization as a protective coating for Cu substrates in chloride environment. Monte Carlo simulations have been utilized to elucidate the interaction between the Cu surface and HC coatings.
Fast microwave assisted pyrolysis of biomass using microwave absorbent.
Borges, Fernanda Cabral; Du, Zhenyi; Xie, Qinglong; Trierweiler, Jorge Otávio; Cheng, Yanling; Wan, Yiqin; Liu, Yuhuan; Zhu, Rongbi; Lin, Xiangyang; Chen, Paul; Ruan, Roger
2014-03-01
A novel concept of fast microwave assisted pyrolysis (fMAP) in the presence of microwave absorbents was presented and examined. Wood sawdust and corn stover were pyrolyzed by means of microwave heating and silicon carbide (SiC) as microwave absorbent. The bio-oil was characterized, and the effects of temperature, feedstock loading, particle sizes, and vacuum degree were analyzed. For wood sawdust, a temperature of 480°C, 50 grit SiC, with 2g/min of biomass feeding, were the optimal conditions, with a maximum bio-oil yield of 65 wt.%. For corn stover, temperatures ranging from 490°C to 560°C, biomass particle sizes from 0.9mm to 1.9mm, and vacuum degree lower than 100mmHg obtained a maximum bio-oil yield of 64 wt.%. This study shows that the use of microwave absorbents for fMAP is feasible and a promising technology to improve the practical values and commercial application outlook of microwave based pyrolysis. Copyright © 2014 Elsevier Ltd. All rights reserved.
Liu, Xuan; Zhang, Yang; Li, Zifu; Feng, Rui; Zhang, Yaozhong
2014-10-01
In this study, thermal and physicochemical characterization results of corncob (CC) and its derived biochars were analyzed and differentiated from sawdust (SD) and cornstalk (CS). The pyrolysis temperature shows the largest effect on the yield of biochar produced compare with residing time, heating rate, and feedstock particle size. The CC-derived biochars produced at temperatures ranging from 300 to 600°C were analyzed. The CC was thermochemically altered to a stable biochar when the pyrolysis temperature was set to over 500°C. To deduce the reaction mechanism of the CC during the major thermal decomposition stage, 16 mechanisms in solid-state reactions were applied. The reaction order and nucleation mechanisms described the thermal decomposition of the CC. By using the best-fitted mechanisms, the kinetic parameters were calculated. The weight active energy of the CC was 122.42kJ/mol, which was the lowest value compared to those of CS and SD. Copyright © 2014 Elsevier Ltd. All rights reserved.
Thermal Analysis of the Fastrac Chamber/Nozzle
NASA Technical Reports Server (NTRS)
Davis, Darrell
2001-01-01
This paper will describe the thermal analysis techniques used to predict temperatures in the film-cooled ablative rocket nozzle used on the Fastrac 60K rocket engine. A model was developed that predicts char and pyrolysis depths, liner thermal gradients, and temperatures of the bondline between the overwrap and liner. Correlation of the model was accomplished by thermal analog tests performed at Southern Research, and specially instrumented hot fire tests at the Marshall Space Flight Center. Infrared thermography was instrumental in defining nozzle hot wall surface temperatures. In-depth and outboard thermocouple data was used to correlate the kinetic decomposition routine used to predict char and pyrolysis depths. These depths were anchored with measured char and pyrolysis depths from cross-sectioned hot-fire nozzles. For the X-34 flight analysis, the model includes the ablative Thermal Protection System (TPS) material that protects the overwrap from the recirculating plume. Results from model correlation, hot-fire testing, and flight predictions will be discussed.
Thermal Analysis of the MC-1 Chamber/Nozzle
NASA Technical Reports Server (NTRS)
Davis, Darrell W.; Phelps, Lisa H. (Technical Monitor)
2001-01-01
This paper will describe the thermal analysis techniques used to predict temperatures in the film-cooled ablative rocket nozzle used on the MC-1 60K rocket engine. A model was developed that predicts char and pyrolysis depths, liner thermal gradients, and temperatures of the bondline between the overwrap and liner. Correlation of the model was accomplished by thermal analog tests performed at Southern Research, and specially instrumented hot fire tests at the Marshall Space Flight Center. Infrared thermography was instrumental in defining nozzle hot wall surface temperatures. In-depth and outboard thermocouple data was used to correlate the kinetic decomposition routine used to predict char and pyrolysis depths. These depths were anchored with measured char and pyrolysis depths from cross-sectioned hot-fire nozzles. For the X-34 flight analysis, the model includes the ablative Thermal Protection System (TPS) material that protects the overwrap from the recirculating plume. Results from model correlation, hot-fire testing, and flight predictions will be discussed.
Pyrolytic characteristics of biomass acid hydrolysis residue rich in lignin.
Huang, Yanqin; Wei, Zhiguo; Yin, Xiuli; Wu, Chuangzhi
2012-01-01
Pyrolytic characteristics of acid hydrolysis residue (AHR) of corncob and pinewood (CAHR, WAHR) were investigated using a thermo-gravimetric analyzer (TGA) and a self-designed pyrolysis apparatus. Gasification reactivity of CAHR char was then examined using TGA and X-ray diffractometer. Result of TGA showed that thermal degradation curves of AHR descended smoothly along with temperature increasing from 150 °C to 850 °C, while a "sharp mass loss stage" for original biomass feedstock (OBF) was observed. Char yield from AHR (42.64-30.35 wt.%) was found to be much greater than that from OBF (26.4-19.15 wt.%). In addition, gasification reactivity of CAHR char was lower than that of corncob char, and there was big difference in micro-crystallite structure. It was also found that CAHR char reactivity decreased with pyrolysis temperature, but increased with pyrolysis heating rate and gasification temperature at 850-950 °C. Furthermore, CAHR char reactivity performed better under steam atmosphere than under CO2 atmosphere. Copyright © 2011 Elsevier Ltd. All rights reserved.
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.
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
NASA Technical Reports Server (NTRS)
Arnold, William A.; Hartman, Thomas G.; McQuillen, John
2006-01-01
Perfluorohexane (PFH), C6F14, is a perfluorocarbon fluid. Several PFH fluids with different isomer concentrations were evaluated for use in an upcoming NASA space experiment. Samples tested included two commercially obtained high-purity n-perfluorohexane (n-PFH) fluids and a technical grade mixture of C6F14 branched and linear isomers (FC-72(TradeMark)). These fluids were evaluated for exact chemical composition, impurity purity and high temperature degradation behavior (pyrolysis). Our investigation involved simulated thermal stressing studies of PFH fluids under conditions likely to occur in the event of an atmospheric breach within the International Space Station (ISS) and subsequent exposure of the vapors to the high temperature and catalyst present in its Trace Contaminant Control Subsystem (TCCS). Exposure to temperatures in the temperature range of 200-450 C in an inert or oxidizing atmosphere, with and without the presence of catalyst was investigated. The most aggressive conditions studied were exposure of PFH vapors to 450 C in air and in the presence of TCCS (palladium) catalyst. Gas chromatography-mass spectrometry (GC-MS) and gas chromatography (GC) analyses were conducted on the perfluorohexane samples before and after pyrolysis. The FC-72 and n-PFH samples showed no significant degradation following pyrolysis even under the most aggressive study conditions. Some trace level impurities associated with the PFH samples such as linear perfluorocarbon monohydrides or monoiodides were destroyed by pyrolysis at the upper limit. Other trace level impurities such as olefinic or cycloolefinic perfluorocarbons were converted into oxidation products by pyrolysis. The purity of PFH following pyrolysis actually increased slightly as a consequence since these trace contaminants were effectively scrubbed from the samples. However, since the initial concentrations of the thermally-impacted impurities were so low, the net effect was trivial. A potential byproduct of exposure of perfluorohexane fluids to high temperatures is the production of perfluoroisobutene (PFiB), which is extremely toxic. An ultra-high sensitivity PFiB-specific analysis based on GC-MS with negative ion chemical ionization (NICI) detection was used to evaluate the samples following thermal stressing. The perfluorohexanes examined here under conditions reflective of the ISS TCCS environment showed no signs of PFiB production with an analytical detection limit of 10 part per billion (ppb v/v).
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...
USDA-ARS?s Scientific Manuscript database
It is known that properties of activated biochars are tightly associated with those of the original feedstock as well as pyrolysis and activation conditions. This study examined two feedstock types, pine wood shavings and chicken litter, to produce biochars at two different pyrolysis temperatures a...
USDA-ARS?s Scientific Manuscript database
Birch wood was slowly pyrolyzed to produce bio-oil and biochar. Slow pyrolysis conditions including reaction temperature, residence time, and particle size of the feed were optimized to maximize bio-oil yield. Particle size had an insignificant effect, whereas yields of up to 56% were achieved using...
On-Line Analysis and Kinetic Behavior of Arsenic Release during Coal Combustion and Pyrolysis.
Shen, Fenghua; Liu, Jing; Zhang, Zhen; Dai, Jinxin
2015-11-17
The kinetic behavior of arsenic (As) release during coal combustion and pyrolysis in a fluidized bed was investigated by applying an on-line analysis system of trace elements in flue gas. This system, based on inductively coupled plasma optical emission spectroscopy (ICP-OES), was developed to measure trace elements concentrations in flue gas quantitatively and continuously. Obvious variations of arsenic concentration in flue gas were observed during coal combustion and pyrolysis, indicating strong influences of atmosphere and temperature on arsenic release behavior. Kinetic laws governing the arsenic release during coal combustion and pyrolysis were determined based on the results of instantaneous arsenic concentration in flue gas. A second-order kinetic law was determined for arsenic release during coal combustion, and the arsenic release during coal pyrolysis followed a fourth-order kinetic law. The results showed that the arsenic release rate during coal pyrolysis was faster than that during coal combustion. Thermodynamic calculations were carried out to identify the forms of arsenic in vapor and solid phases during coal combustion and pyrolysis, respectively. Ca3(AsO4)2 and Ca(AsO2)2 are the possible species resulting from As-Ca interaction during coal combustion. Ca(AsO2)2 is the most probable species during coal pyrolysis.
Efficiency of biochar produced from malt spent rootlets to remove mercury and dyes
NASA Astrophysics Data System (ADS)
Kamenidou, Charoula; Manariotis, Ioannis; Karapanagioti, Hrissi
2017-04-01
Considerable research effort has been focused on the production of biochar from carbon-rich biomass under oxygen-limited conditions as a mitigation measure for global warming once it is used as a soil amendment. Furthermore, the use of biochar as an added value product, such as sorbent or catalyst, is desirable and could be more profitable. Biochar is obtained from the incomplete combustion of carbon-rich biomass under oxygen-limited conditions. Various organic-rich wastes including wood chips, animal manure, and crop residues have been used for biochar production. The present study presents the findings of an experimental work, which investigated the use of biochar produced from malt spent rootlets (MSR), which is a beer production by-product, to remove Hg(II) and methylene blue (MB) from aqueous solutions. MSR was pyrolyzed at temperatures of 300, 400, 500, 600, 750, 850, and 900oC, under limited oxygen conditions. The increase of temperature resulted in significantly increased BET surface areas. The mercury sorption capacity was affected by pyrolysis temperature, and was increased by increasing the pyrolysis temperature. The maximum sorption capacity was 100-110 mg Hg(II)/g biochar at a temperature range of 750-850oC. The MB sorption capacity of biochar was also affected by pyrolysis temperature.
Kim, Jang Won; Lee, Albert S; Yu, Seunggun; Han, Jeong Whan
2018-01-15
This paper reports the recycling of flexible printed circuit board (FPCB) waste through carbonization of polyimide by dual pyrolysis processes. The organic matter was recovered as pyrolyzed oil at low temperatures, while valuable metals and polyimide-derived carbon were effectively recovered through secondary high temperature pyrolysis. The major component of organics extracted from FPCB waste comprised of epoxy resins were identified as pyrolysis oils containing bisphenol-A. The valuable metals (Cu, Ni, Ag, Sn, Au, Pd) in waste FPCB were recovered as granular shape and quantitatively analyzed via ICP-OES. In attempt to produce carbonaceous material with increased degree of graphitization at low heat-treatment conditions, the catalytic effect of transition metals within FPCB waste was investigated for the efficient carbonization of polyimide films. The morphology of the carbon powder was observed by scanning electron microscopy and graphitic carbonization was investigated with X-ray analysis. The protocols outlined in this study may allow for propitious opportunities to salvage both organic and inorganic materials from FPCB waste products for a sustainable future. Copyright © 2017 Elsevier B.V. All rights reserved.
Nannochloropsis algae pyrolysis with ceria-based catalysts for production of high-quality bio-oils.
Aysu, Tevfik; Sanna, Aimaro
2015-10-01
Pyrolysis of Nannochloropsis was carried out in a fixed-bed reactor with newly prepared ceria based catalysts. The effects of pyrolysis parameters such as temperature and catalysts on product yields were investigated. The amount of bio-char, bio-oil and gas products, as well as the compositions of the resulting bio-oils was determined. The results showed that both temperature and catalyst had significant effects on conversion of Nannochloropsis into solid, liquid and gas products. The highest bio-oil yield (23.28 wt%) and deoxygenation effect was obtained in the presence of Ni-Ce/Al2O3 as catalyst at 500°C. Ni-Ce/Al2O3 was able to retain 59% of the alga starting energy in the bio-oil, compared to only 41% in absence of catalyst. Lower content of acids and oxygen in the bio-oil, higher aliphatics (62%), combined with HHV show promise for production of high-quality bio-oil from Nannochloropsis via Ni-Ce/Al2O3 catalytic pyrolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.
Pyrolysis of cassava rhizome in a counter-rotating twin screw reactor unit.
Sirijanusorn, Somsak; Sriprateep, Keartisak; Pattiya, Adisak
2013-07-01
A counter-rotating twin screw reactor unit was investigated for its behaviour in the pyrolysis of cassava rhizome biomass. Several parameters such as pyrolysis temperature in the range of 500-700°C, biomass particle size of <0.6mm, the use of sand as heat transfer medium, nitrogen flow rate of 4-10 L/min and nitrogen pressure of 1-3 bar were thoroughly examined. It was found that the pyrolysis temperature of 550°C could maximise the bio-oil yield (50 wt.%). The other optimum parameters for maximising the bio-oil yield were the biomass particle size of 0.250-0.425 mm, the nitrogen flow rate of 4 L/min and the nitrogen pressure of 2 bar. The use of the heat transfer medium could increase the bio-oil yield to a certain extent. Moreover, the water content of bio-oil produced with the counter-rotating twin screw reactor was relatively low, whereas the solids content was relatively high, compared to some other reactor configurations. Copyright © 2013 Elsevier Ltd. All rights reserved.
Liu, Shiyu; Xie, Qinglong; Zhang, Bo; Cheng, Yanling; Liu, Yuhuan; Chen, Paul; Ruan, Roger
2016-03-01
This study investigated fast microwave-assisted catalytic co-pyrolysis of corn stover and scum for bio-oil production with CaO and HZSM-5 as the catalyst. Effects of reaction temperature, CaO/HZSM-5 ratio, and corn stover/scum ratio on co-pyrolysis product fractional yields and selectivity were investigated. Results showed that co-pyrolysis temperature was selected as 550°C, which provides the maximum bio-oil and aromatic yields. Mixed CaO and HZSM-5 catalyst with the weight ratio of 1:4 increased the aromatic yield to 35.77 wt.% of feedstock, which was 17% higher than that with HZSM-5 alone. Scum as the hydrogen donor, had a significant synergistic effect with corn stover to promote the production of bio-oil and aromatic hydrocarbons when the H/C(eff) value exceeded 1. The maximum yield of aromatic hydrocarbons (29.3 wt.%) were obtained when the optimal corn stover to scum ratio was 1:2. Copyright © 2016 Elsevier Ltd. All rights reserved.
Thermogravimetric analysis and fast pyrolysis of Milkweed.
Kim, Seung-Soo; Agblevor, Foster A
2014-10-01
Pyrolysis of Milkweed was carried out in a thermogravimetric analyzer and a bubbling fluidized bed reactor. Total liquid yield of Milkweed pyrolysis was between 40.74% and 44.19 wt% between 425 °C and 550 °C. The gas yield increased from 27.90 wt% to 33.33 wt% with increasing reaction temperature. The higher heating values (HHV) of the Milkweed bio-oil were relatively high (30.33-32.87 MJ/kg) and varied with reaction temperature, feeding rate and fluidization velocity. The selectivity for CO2 was highest within non-condensable gases, and the molar ratio of CO2/CO was about 3 at the different reaction conditions. The (13)C NMR analysis, of the bio-oil showed that the relative concentration carboxylic group and its derivatives was higher at 425 °C than 475 °C, which resulted in slightly higher oxygen content in bio-oil. The pH of aqueous phase obtained at 475 °C was 7.37 which is the highest reported for any lignocellulosic biomass pyrolysis oils. Copyright © 2014 Elsevier Ltd. All rights reserved.
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.
A comparative study on pyrolysis characteristic Indonesia biomassa and low grade coal
NASA Astrophysics Data System (ADS)
Adhityatama, G. I.; Hanif, F.; Cahyono, R. B.; Hidayat, M.; Akiyama, T.
2017-05-01
A comparative study on pyrolysis of biomass and low grade coal was conducted using a thermogravimetric analyzer. Each kind of biomass and coal has a characteristic pyrolysis behavior which is explained based on its individual component characteristics. All fuels experienced a small weight loss as temperatures approached 450K because of moisture evaporation. The coal had smallest total weight loss compared to biomass due to its high content of fixed carbon, suggesting that coal would produce high amounts of char and small amounts of volatile matter (e.g., tar and gas). The biomass exhibits similar tendency regarding the decomposition process which is the hemicelluloses break down first at temperatures of 470 to 530K, cellulose follows in the temperature range 510 to 620K, and lignin is the last component to pyrolyzer at temperatures of 550 to 770K. The thermal decomposition of biomass consisted of two predominant peaks corresponding first to the decomposition of cellulose and, second, to the decomposition of lignin. Meanwhile, the coal exhibited only single peak because these fuels were predominantly composed of carbon. Based on the kinetic analysis, coal have the smaller activation energy (55.32kJ/mol) compared to biomass (range from 89.80-172.86 kJ/mol). Pyrolysis process also created more pore material in the solid product. These results were important for the optimization of energy conversion from those solid fuels. Biomass resulted lower solid product and higher tar product, thus would be suitable for liquid and gas energy production.
Effect of temperature and heating rate on apparent lethal concentrations of pyrolysis products
NASA Technical Reports Server (NTRS)
Hilado, C. J.; Solis, A. N.; Marcussen, W. H.; Furst, A.
1976-01-01
The apparent lethal concentrations for 50 percent of the test animals of the pyrolysis products from twelve polymeric materials were studied as a function of temperature and heating rate. The materials were polyethylene, nylon 6, ABS, polycarbonate, polyether sulfone, polyaryl sulfone, wool fabric, aromatic polyamide fabric, polychloroprene foam, polyvinyl fluoride film, Douglas fir, and red oak. The apparent lethal concentration values of most materials vary significantly with temperature and heating rate. The apparent lethal concentration values, based on weight of sample charged, appears to effectively integrate the thermophysical, thermochemical, and physiological responses from a known quantity of material under specified imposed conditions.
Wood source and pyrolysis temperature interact to control PyOM degradation rates
NASA Astrophysics Data System (ADS)
Bird, J. A.; Hatton, P. J.; Filley, T. R.; Chatterjee, S.; Auclerc, A.; Gormley, M.; Dastmalchi, K.; Stark, R. E.; Nadelhoffer, K. J.
2015-12-01
Surprisingly little is known about how shifts in tree species composition and increased forest fire frequency and intensity will affect one of the most stable pools of soil organic matter, i.e. the pyrogenic organic matter (PyOM or char). In a previous study, we showed that wood source and pyrolysis temperature interact to control PyOM structure and potential reactivity for two tree species common in high-latitude forests, jack pine (JP) and red maple (RM). Here, we investigate whether these differences affect PyOM turnover by examining the fates of 13C/15N-enriched JP wood and PyOM pyrolyzed at 300 (JP300) and 450 °C (JP450) and RM pyrolyzed at 450 °C (RM450). The substrates were applied 1-3 cm below the O/A interface of a well-drained Spodosol in a long-term forest fire study located at the University of Michigan Biological Station (Pellston, MI, USA). 13C-CO2effluxes from the first 996 days of decay showed a significant wood source by pyrolysis temperature interaction on PyOM field mineralisation rates, with RM450 mineralising twice faster than JP450 during the first 90 days. Increasing pyrolysis temperature substantially decreased field mineralization rates during the first 996 days, with mineralisation rates 24 and 80 times slower for JP300 and JP450 compared with JP wood. After 1 year, (i) bacterial groups were large sinks for PyOM-derived C as pyrolysis temperature increased and as substrate use efficiency decreased; (ii) potential phenol oxidase and net peroxidase activities were unaffected by the PyOM addition, although net peroxidase activities measured tended to lesser for soils amended with JP450 and RM450; and (iii) Collembola detritivores appeared less likely to be found for soils amended with JP450 and RM450. PyOM-derived C and N recoveries did not differ after 1 year; we will present 3-y recovery data. Our results suggest that the composition of angiosperms (e.g. RM) and gymnosperms (e.g. JP) in high-latitude forests is an underappreciated but essential determinant of soil PyOM stocks and reactivity, with angiosperms yielding more degradable PyOM. Considering the wood source by pyrolysis temperature interaction on PyOM will help providing more comprehensive large-scale assessments of PyOM stocks and reactivity potentials under current and future climate conditions.
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.
Performance of rotary kiln reactor for the elephant grass pyrolysis.
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.
Styrene recovery from polystyrene by flash pyrolysis in a conical spouted bed reactor.
Artetxe, Maite; Lopez, Gartzen; Amutio, Maider; Barbarias, Itsaso; Arregi, Aitor; Aguado, Roberto; Bilbao, Javier; Olazar, Martin
2015-11-01
Continuous pyrolysis of polystyrene has been studied in a conical spouted bed reactor with the main aim of enhancing styrene monomer recovery. Thermal degradation in a thermogravimetric analyser was conducted as a preliminary study in order to apply this information in the pyrolysis in the conical spouted bed reactor. The effects of temperature and gas flow rate in the conical spouted bed reactor on product yield and composition have been determined in the 450-600°C range by using a spouting velocity from 1.25 to 3.5 times the minimum one. Styrene yield is strongly influenced by both temperature and gas flow rate, with the maximum yield being 70.6 wt% at 500°C and a gas velocity twice the minimum one. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Jourabchi, S. A.; Ng, H. K.; Gan, S.; Yap, Z. Y.
2016-06-01
A high-impact poly-styrene (HIPS) was mixed with dried and ground coconut shell (CS) at equal weight percentage. Fast pyrolysis was carried out on the mixture in a fixed bed reactor over a temperature range of 573 K to 1073 K, and a nitrogen (N2) linear velocity range of 7.8x10-5 m/s to 6.7x10-2 m/s to produce bio-oil. Heat transfer and fluid dynamics of the pyrolysis process inside the reactor was visualised by using Computational Fluid Dynamics (CFD). The CFD modelling was validated by experimental results and they both indicated that at temperature of 923 K and N2 linear velocity of 7.8x10-5 m/s, the maximum bio-oil yield of 52.02 wt% is achieved.
Tire traces - discrimination and classification of pyrolysis-GC/MS profiles.
Gueissaz, Line; Massonnet, Geneviève
2013-07-10
Tire traces can be observed on several crime scenes as vehicles are often used by criminals. The tread abrasion on the road, while braking or skidding, leads to the production of small rubber particles which can be collected for comparison purposes. This research focused on the statistical comparison of Py-GC/MS profiles of tire traces and tire treads. The optimisation of the analytical method was carried out using experimental designs. The aim was to determine the best pyrolysis parameters regarding the repeatability of the results. Thus, the pyrolysis factor effect could also be calculated. The pyrolysis temperature was found to be five time more important than time. Finally, a pyrolysis at 650°C during 15s was selected. Ten tires of different manufacturers and models were used for this study. Several samples were collected on each tire, and several replicates were carried out to study the variability within each tire (intravariability). More than eighty compounds were integrated for each analysis and the variability study showed that more than 75% presented a relative standard deviation (RSD) below 5% for the ten tires, thus supporting a low intravariability. The variability between the ten tires (intervariability) presented higher values and the ten most variant compounds had a RSD value above 13%, supporting their high potential of discrimination between the tires tested. Principal Component Analysis (PCA) was able to fully discriminate the ten tires with the help of the first three principal components. The ten tires were finally used to perform braking tests on a racetrack with a vehicle equipped with an anti-lock braking system. The resulting tire traces were adequately collected using sheets of white gelatine. As for tires, the intravariability for the traces was found to be lower than the intervariability. Clustering methods were carried out and the Ward's method based on the squared Euclidean distance was able to correctly group all of the tire traces replicates in the same cluster than the replicates of their corresponding tire. Blind tests on traces were performed and were correctly assigned to their tire source. These results support the hypothesis that the tested tires, of different manufacturers and models, can be discriminated by a statistical comparison of their chemical profiles. The traces were found to be not differentiable from their source but differentiable from all the other tires present in the subset. The results are promising and will be extended on a larger sample set. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.
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.
Ceramic fibers for matrix composites in high-temperature engine applications
Baldus; Jansen; Sporn
1999-07-30
High-temperature engine applications have been limited by the performance of metal alloys and carbide fiber composites at elevated temperatures. Random inorganic networks composed of silicon, boron, nitrogen, and carbon represent a novel class of ceramics with outstanding durability at elevated temperatures. SiBN(3)C was synthesized by pyrolysis of a preceramic N-methylpolyborosilazane made from the single-source precursor Cl(3)Si-NH-BCl(2). The polymer can be processed to a green fiber by melt-spinning, which then undergoes an intermediate curing step and successive pyrolysis. The ceramic fibers, which are presently produced on a semitechnical scale, combine several desired properties relevant for an application in fiber-reinforced ceramic composites: thermal stability, mechanical strength, high-temperature creep resistivity, low density, and stability against oxidation or molten silicon.
Biomass Pyrolysis Solids as Reducing Agents: Comparison with Commercial Reducing Agents.
Adrados, Aitziber; De Marco, Isabel; López-Urionabarrenechea, Alexander; Solar, Jon; Caballero, Blanca M; Gastelu, Naia
2015-12-23
Biomass is one of the most suitable options to be used as renewable energy source due to its extensive availability and its contribution to reduce greenhouse gas emissions. Pyrolysis of lignocellulosic biomass under appropriate conditions (slow heating rate and high temperatures) can produce a quality solid product, which could be applicable to several metallurgical processes as reducing agent (biocoke or bioreducer). Two woody biomass samples (olives and eucalyptus) were pyrolyzed to produce biocoke. These biocokes were characterized by means of proximate and ultimate analysis, real density, specific surface area, and porosity and were compared with three commercial reducing agents. Finally, reactivity tests were performed both with the biocokes and with the commercial reducing agents. Bioreducers have lower ash and sulfur contents than commercial reducers, higher surface area and porosity, and consequently, much higher reactivity. Bioreducers are not appropriate to be used as top burden in blast furnaces, but they can be used as fuel and reducing agent either tuyére injected at the lower part of the blast furnace or in non-ferrous metallurgical processes where no mechanical strength is needed as, for example, in rotary kilns.
Zhao, Song; Zhou, Xiehong; Wang, Chuanyi; Jia, Hanzhong
2017-08-24
Pyrolysis is potentially an effective treatment of waste oil residues for recovery of petroleum hydrocarbons, and the addition of biomass is expected to improve its dewatering and pyrolysis behavior. In this study, the dewatering and low-temperature co-pyrolysis of oil-containing sludge in the presence of various agricultural biomasses, such as rice husk, walnut shell, sawdust, and apricot shell, were explored. As a result, the water content gradually decreases with the increase of biomass addition within 0-1.0 wt % in original oily sludge. Comparatively, the dewatering efficiency of sludge in the presence of four types of biomasses follows the order of apricot shell > walnut shell > rice husk > sawdust. On the other hand, rice husk and sawdust are relatively more efficient in the recovery of petroleum hydrocarbons compared with walnut shell and apricot shell. The recovery efficiency generally increased with the increase in the biomass content in the range of 0-0.2 wt %, then exhibited a gradually decreasing trend with the increase in the biomass content from 0.2 to 1.0 wt %. The results suggest that optimum amount of biomass plays an important role in the recovery efficiency. In addition, the addition of biomass (such as rice husk) also promotes the formation of C x H y and CO, increasing the calorific value of pyrolysis residue, and controlled the pollution components of the exhaust gas discharged from residue incineration. The present work implies that biomass as addictive holds great potential in the industrial dewatering and pyrolysis of oil-containing sludge.
Effect of heating rate on toxicity of pyrolysis gases from some elastomers
NASA Technical Reports Server (NTRS)
Hilado, C. J.; Kosola, K. L.; Solis, A. N.
1977-01-01
The effect of heating rate on the toxicity of the pyrolysis gases from six elastomers was investigated, using a screening test method. The elastomers were polyisoprene (natural rubber), styrene-butadiene rubber (SBR), ethylene propylene diene terpolymer (EPDM), acrylonitrile rubber, chlorosulfonated polyethylene rubber, and polychloroprene. The rising temperature and fixed temperature programs produced exactly the same rank order of materials based on time to death. Acrylonitrile rubber exhibited the greatest toxicity under these test conditions, and carbon monoxide was not found in sufficient concentrations to be the primary cause of death.
Photoactive lead oxide thin films by spray pyrolysis
NASA Astrophysics Data System (ADS)
Bhagat, Dharini; Waldiya, Manmohansingh; Mukhopadhyay, Indrajit
2018-05-01
We report the synthesis of photoactive lead monoxide thin films on fluorine doped tin oxide substrate by cost effective spray pyrolysis technique using aqueous solution of lead acetate trihydrate. Influence of substrate temperature on the structural and optical properties of thin films was studied. Polymorph of lead monoxide, litharge (α-PbO), was obtained when the substrate temperature was kept constant at 360 °C. XRD analysis revealed that the deposits were tetragonal structured with preferred orientation along 002 plane. Band gap value was found to be 1.93ev from diffuse reflectance spectra.
NASA Astrophysics Data System (ADS)
Rahaman, Sabina; Sunil, M. Anantha; Shaik, Habibuddin; Ghosh, Kaustab
2018-05-01
Deposition of Cu2SnS3 (CTS) thin films is successfully carried out on soda lime glass substrate using low cost ultrasonic spray pyrolysis technique. Vacuum annealing of CTS films is carried out at different temperatures 350°C, 400°C and 450°C. The present work is to study the effect of annealing temperature on the crystal structure, surface morphology and optical properties of CTS thin films. Structural studies confirm the formation of CTS phase. Raman analysis is carried out to study presence of defects with annealing temperature. Optical studies confirm that film prepared at 450°C temperature is suitable as absorber material for photovoltaic applications.
Catalytic hydroprocessing of fast pyrolysis oils: Impact of biomass feedstock on process efficiency
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
Lewan, M.D.; Ruble, T.E.
2002-01-01
This study compares kinetic parameters determined by open-system pyrolysis and hydrous pyrolysis using aliquots of source rocks containing different kerogen types. Kinetic parameters derived from these two pyrolysis methods not only differ in the conditions employed and products generated, but also in the derivation of the kinetic parameters (i.e., isothermal linear regression and non-isothermal nonlinear regression). Results of this comparative study show that there is no correlation between kinetic parameters derived from hydrous pyrolysis and open-system pyrolysis. Hydrous-pyrolysis kinetic parameters determine narrow oil windows that occur over a wide range of temperatures and depths depending in part on the organic-sulfur content of the original kerogen. Conversely, open-system kinetic parameters determine broad oil windows that show no significant differences with kerogen types or their organic-sulfur contents. Comparisons of the kinetic parameters in a hypothetical thermal-burial history (2.5 ??C/my) show open-system kinetic parameters significantly underestimate the extent and timing of oil generation for Type-US kerogen and significantly overestimate the extent and timing of petroleum formation for Type-I kerogen compared to hydrous pyrolysis kinetic parameters. These hypothetical differences determined by the kinetic parameters are supported by natural thermal-burial histories for the Naokelekan source rock (Type-IIS kerogen) in the Zagros basin of Iraq and for the Green River Formation (Type-I kerogen) in the Uinta basin of Utah. Differences in extent and timing of oil generation determined by open-system pyrolysis and hydrous pyrolysis can be attributed to the former not adequately simulating natural oil generation conditions, products, and mechanisms.
Speculations on the nature of cellulose pyrolysis
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...
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.
Duan, Dengle; Ruan, Roger; Lei, Hanwu; Liu, Yuhuan; Wang, Yunpu; Zhang, Yayun; Zhao, Yunfeng; Dai, Leilei; Wu, Qiuhao; Zhang, Shumei
2018-06-01
The co-pyrolysis of pretreated lignin and soapstock was carried out to upgrade vapors under microwave irradiation. Results showed that the yield of 29.92-42.21 wt% of upgraded liquid oil was achieved under varied pretreatment conditions. Char yield decreased from 32.44 wt% for untreated control to 24.35 wt% for the 150 °C pretreated samples. The increased temperature, irradiation time and acid concentration were conducive to decrease the relative contents of phenols and oxygenates in liquid oils. The main components of the liquid oil were gasoline fraction (mono-aromatics and C5-C12 aliphatics), which ranged from 57.38 to 71.98% under various pretreatment conditions. Meanwhile, the diesel fraction (C12+ aliphatics) ranged from 13.16 to 22.62% from co-pyrolysis of pretreated lignin and soapstock, comparing with 10.18% of C12+ aliphatics from co-pyrolysis of non-pretreated lignin and soapstock. A possible mechanism was proposed for co-pyrolysis of pretreated lignin and soapstock for upgraded liquid oils. Copyright © 2018 Elsevier Ltd. All rights reserved.
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.
Zhao, Bing; Xu, Xinyang; Li, Haibo; Chen, Xi; Zeng, Fanqiang
2018-01-01
Hazelnut shell, as novel biomass, has lower ash content and abundant hydrocarbon, which can be utilized resourcefully with municipal sewage sludge (MSS) by co-pyrolyisis to decrease total content of pollution. The co-pyrolysis of MSS and hazelnut shell blend was analyzed by a method of multi-heating rates and different blend ratios with TG-DTG-MS under N 2 atmosphere. The apparent activation energy of co-pyrolysis was calculated by three iso-conversional methods. Satava-Sestak method was used to determine mechanism function G(α) of co-pyrolysis, and Lorentzian function was used to simulate multi-peaks curves. The results showed there were four thermal decomposition stages, and the biomass were cracked and evolved at different temperature ranges. The apparent activation energy increased from 123.99 to 608.15kJ/mol. The reaction mechanism of co-pyrolysis is random nucleation and nuclei growth. The apparent activation energy and mechanism function afford a theoretical groundwork for co-pyrolysis technology. Copyright © 2017 Elsevier Ltd. All rights reserved.
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.
Tinwala, Farha; Mohanty, Pravakar; Parmar, Snehal; Patel, Anant; Pant, Kamal K
2015-01-01
Pyrolysis of woody biomass, agro-residues and seed was carried out at 500 ± 10 °C in a fixed bed pyrolyser. Bio-oil yield was found varying from 20.5% to 47.5%, whereas the biochar and pyrolysis gas ranged from 27.5% to 40% and 24.5% to 40.5%, respectively. Pyrolysis gas was measured for flame temperature along with CO, CO2, H2, CH4 and other gases composition. HHV of biochar (29.4 MJ/kg) and pyrolitic gas (8.6 MJ/kg) of woody biomass was higher analogous to sub-bituminous coal and steam gasification based producer gas respectively, whereas HHV of bio-oil obtained from seed (25.6 MJ/kg) was significantly more than husks, shells and straws. TGA-DTG studies showed the husks as potential source for the pyrolysis. Bio-oils as a major by-product of intermediate pyrolysis have several applications like substitute of furnace oil, extraction of fine chemicals, whereas biochar as a soil amendment for enhancing soil fertility and gases for thermal application. Copyright © 2015 Elsevier Ltd. All rights reserved.
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.
Hossain, Mohammad M; Scott, Ian M; Berruti, Franco; Briens, Cedric
2016-12-01
Valuable chemicals can be separated from agricultural residues by chemical or thermochemical processes. The application of pyrolysis has already been demonstrated as an efficient means to produce a liquid with a high concentration of desired product. The objective of this study was to apply an insect and microorganism bioassay-guided approach to separate and isolate pesticidal compounds from bio-oil produced through biomass pyrolysis. Tobacco leaf (Nicotianata bacum), tomato plant (Solanum lycopersicum), and spent coffee (Coffea arabica) grounds were pyrolyzed at 10°C/min from ambient to 565°C using the mechanically fluidized reactor (MFR). With one-dimensional (1D) MFR pyrolysis, the composition of the product vapors varied as the reactor temperature was raised allowing for the selection of the temperature range that corresponds to vapors with a high concentration of pesticidal properties. Further product separation was performed in a fractional condensation train, or 2D MFR pyrolysis, thus allowing for the separation of vapor components according to their condensation temperature. The 300-400°C tobacco and tomato bio-oil cuts from the 1D MFR showed the highest insecticidal and anti-microbial activity compared to the other bio-oil cuts. The 300-350 and 350-400°C bio-oil cuts produced by 2D MFR had the highest insecticidal activity when the bio-oil was collected from the 210°C condenser. The tobacco and tomato bio-oil had similar insecticidal activity (LC 50 of 2.1 and 2.2 mg/mL) when the bio-oil was collected in the 210°C condenser from the 300-350°C reactor temperature gases. The 2D MFR does concentrate the pesticidal products compared to the 1D MFR and thus can reduce the need for further separation steps such as solvent extraction.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Carpenter, Daniel; Westover, Tyler; Howe, Daniel
Here, we report here on an experimental study to produce refinery-ready fuel blendstocks via catalytic hydrodeoxygenation (upgrading) of pyrolysis oil using several biomass feedstocks and various blends. Blends were tested along with the pure materials to determine the effect of blending on product yields and qualities. Within experimental error, oil yields from fast pyrolysis and upgrading are shown to be linear functions of the blend components. Switchgrass exhibited lower fast pyrolysis and upgrading yields than the woody samples, which included clean pine, oriented strand board (OSB), and a mix of pinon and juniper (PJ). The notable exception was PJ, formore » which the poor upgrading yield of 18% was likely associated with the very high viscosity of the PJ fast pyrolysis oil (947 cp). The highest fast pyrolysis yield (54% dry basis) was obtained from clean pine, while the highest upgrading yield (50%) was obtained from a blend of 80% clean pine and 20% OSB (CP 8OSB 2). For switchgrass, reducing the fast pyrolysis temperature to 450 degrees C resulted in a significant increase to the pyrolysis oil yield and reduced hydrogen consumption during hydrotreating, but did not directly affect the hydrotreating oil yield. The water content of fast pyrolysis oils was also observed to increase linearly with the summed content of potassium and sodium, ranging from 21% for clean pine to 37% for switchgrass. Multiple linear regression models demonstrate that fast pyrolysis is strongly dependent upon the contents lignin and volatile matter as well as the sum of potassium and sodium.« less
Han, Yitong; Cao, Xi; Ouyang, Xin; Sohi, Saran P; Chen, Jiawei
2016-02-01
Magnetic biochar was made from peanut hull biomass using iron chloride in a simplified aqueous phase approach and pyrolysis at alternative peak temperatures (450-650 °C). Magnetic biochar showed an extreme capacity for adsorption of hexavalent chromium Cr (VI) from aqueous solution, which was 1-2 orders of magnitude higher compared to standard (non-magnetic) biochar from the same feedstock. Adsorption increased with pyrolysis temperature peaking at 77,542 mg kg(-1) in the sample pyrolysed at 650 °C. In contrast to magnetic biochar, the low adsorption capacity of standard biochar decreased with increasing pyrolysis temperature. The fine particle size of magnetic biochar and low aqueous pH were also important for adsorption. Surfaces of products from batch adsorption experiments were characterized by scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, X-ray photoelectron spectroscopy and vibrating sample magnetometer. This revealed that γ-Fe2O3 was crucial to the properties (adsorbance and magnetism) of magnetic biochar. The removal mechanism was the Cr (VI) electrostatic attracted on protonated -OH on γ-Fe2O3 surface and it could be desorbed by alkaline solution. Findings suggest that pyrolysis has potential to create effective, magnetically recoverable adsorbents relevant to environmental application. Copyright © 2015 Elsevier Ltd. All rights reserved.
Chou, I.-Ming; Lake, M.A.; Griffin, R.A.
1988-01-01
A Pyroprobe flash pyrolysis-gas chromatograph equipped with a flame photometric detector was used to study volatile sulfur compounds produced during the thermal decomposition of Illinois coal, coal macerals and coal-derived pyrite. Maximum evolution of volatile organic sulfur compounds from all coal samples occurred at a temperature of approximately 700??C. At this temperature, the evolution of thiophene, its alkyl isomers, and short-chain dialkyl sulfide compounds relative to the evolution of benzothiophene and dibenzothiophene compounds was greater from coal high in organic sulfur than from coal low in organic sulfur. The variation in the evolution of sulfur compounds observed for three separate coal macerals (exinite, vitrinite, and inertinite) was similar to that observed for whole coal samples. However, the variation trend for the macerals was much more pronounced. Decomposition of coal-derived pyrite with the evolution of elemental sulfur was detected at a temperature greater than 700??C. The results of this study indicated that the gas chromotographic profile of the volatile sulfur compounds produced during flash pyrolysis of coals and coal macerals varied as a function of the amount of organic sulfur that occurred in the samples. Characterization of these volatile sulfur compounds provides a better understanding of the behavior of sulfur in coal during the thermolysis process, which could be incorporated in the design for coal cleaning using flash pyrolysis techniques. ?? 1988.
NASA Astrophysics Data System (ADS)
Taylor, Nathan John
In the liquid-feed flame spray pyrolysis (LF-FSP) process, alcohol solutions of metalloorganic precursors are aerosolized by O2 and combusted. The metal oxide combustion products are rapidly quenched (< 10 ms) from flame temperatures of 1500°C to temperatures < 400° C, limiting particle growth. The resulting nanopowders are typically agglomerated but unaggregated. Here, we demonstrate two processing approaches to dense materials: nanopowders with the exact composition, and mixed single metal oxide nanopowders. The effect of the initial degree of phase separation on the final microstructures was determined by sintering studies. Our first studies included the production of yttrium aluminum garnet, Y3Al5O12 (YAG), tubes which we extruded from a thermoplastic/ceramic blend. At equivalent final densities, we found finer grain sizes in the from the mixed Y2O3 and Al2 O3 nanopowders, which was attributed to densification occurring before full transformation to the YAG phase. The enhanced densification in production of pure YAG from the reactive sintering process led us to produce composites in the YAG/alpha-Al 2O3 system. Finally, a third Y2O3 stabilized ZrO2 (YSZ) phase was added to further refine grain sizes using the same two processing approaches. In a separate study, single-phase metastable Al2O3 rich spinels with the composition MO•3Al 2O3 where M = Mg, Ni, and Co were sintered to produce dense MAl2O4/alpha-Al2O3 composites. All of these studies provide a test of the bottom-up approach; that is, how the initial length scale of mixing affects the final composite microstructure. Overall, the length scale of mixing is highly dependent upon the specific oxide composites studied. This work provides a processing framework to be adopted by other researchers to further refine microstructural size. LF-FSP flame temperatures were mapped using different alcohols with different heats of combustion: methanol, ethanol, 1-propanol, and n-butanol. The effect of different alcohols on particle size and phase was determined through studies on Al2O3, Y2O3 and TiO2 nanopowders. The final studies describe the morphology of composite nanopowders produced in the WO3-TiO2 and CuO-TiO2 systems. The composite nanopowders have novel morphology, and may offer novel electronic, optical, or catalytic properties.
Relative toxicity of pyrolysis products of some foams and fabrics
NASA Technical Reports Server (NTRS)
Hilado, C. J.
1976-01-01
A limited number of foams and fabrics was evaluated in the course of developing test procedures for determining the relative toxicity of materials. The principal variable studied, heating rate, did not affect the relative ranking of the materials tested. Two pyrolysis test procedures using the same basic approach but employing different sample weights, chamber volumes, laboratory animals, heating rates, and upper temperature limits, resulted in identical rankings of relative toxicity. The data obtained show that modification of conventional flexible polyurethane foams with flame retardants to comply with California upholstered furniture flammability regulations seems to consistently reduce toxicity under pyrolysis conditions.
Maliutina, Kristina; Tahmasebi, Arash; Yu, Jianglong
2018-06-01
The present dataset describes the entrained-flow pyrolysis of Microalgae Chlorella vulgaris and the results obtained during bio-char characterization. The dataset includes a brief explanation of the experimental procedure, experimental conditions and the influence of pyrolysis conditions on bio-chars morphology and carbon structure. The data show an increase in sphericity and surface smoothness of bio-chars at higher pressures and temperatures. Data confirmed that the swelling ratio of bio-chars increased with pressure up to 2.0 MPa. Consequently, changes in carbon structure of bio-chars were investigated using Raman spectroscopy. The data showed the increase in carbon order of chars at elevated pressures. Changes in the chemical structure of bio-char as a function of pyrolysis conditions were investigated using FTIR analysis.
Molecular Analysis of Primary Vapor and Char Products during Stepwise Pyrolysis of Poplar Biomass
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jones, Roger W.; Reinot, Tonu; McClelland, John F.
2010-08-03
Pyrolysis of biomass produces both pyrolysis oil and solid char. In this study, poplar has been pyrolyzed in a stepwise fashion over a series of temperatures from 200 to 500°C, and both the primary products contributing to pyrolysis oil and the changes in the pyrolyzing poplar surface leading toward char have been characterized at each step. The primary products were identified by direct analysis in real time (DART) mass spectrometry, and the changes in the poplar surface were monitored using Fourier transform infrared (FTIR) photoacoustic spectroscopy, with a sampling depth of a few micrometers. The primary products from pyrolyzing cellulose,more » xylan, and lignin under similar conditions were also characterized to identify the sources of the poplar products.« less
Molecular Analysis of Primary Vapor and Char Products during Stepwise Pyrolysis of Poplar Biomass
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jones, Roger W.; Reinot, Tonu; McClelland, John F.
2010-08-30
Pyrolysis of biomass produces both pyrolysis oil and solid char. In this study, poplar has been pyrolyzed in a stepwise fashion over a series of temperatures from 200 to 500 C, and both the primary products contributing to pyrolysis oil and the changes in the pyrolyzing poplar surface leading toward char have been characterized at each step. The primary products were identified by direct analysis in real time (DART) mass spectrometry, and the changes in the poplar surface were monitored using Fourier transform infrared (FTIR) photoacoustic spectroscopy, with a sampling depth of a few micrometers. The primary products from pyrolyzingmore » cellulose, xylan, and lignin under similar conditions were also characterized to identify the sources of the poplar products.« less
Khachatryan, Lavrent; Xu, Meng-xia; Wu, Ang-jian; Pechagin, Mikhail; Asatryan, Rubik
2016-01-01
The experimental results on detection and identification of intermediate radicals and molecular products from gas-phase pyrolysis of cinnamyl alcohol (CnA), the simplest non-phenolic lignin model compound, over the temperature range of 400–800 °C are reported. The low temperature matrix isolation – electron paramagnetic resonance (LTMI-EPR) experiments along with the theoretical calculations, provided evidences on the generation of the intermediate carbon and oxygen centered as well as oxygen-linked, conjugated radicals. A mechanistic analysis is performed based on density functional theory to explain formation of the major products from CnA pyrolysis; cinnamaldehyde, indene, styrene, benzaldehyde, 1-propynyl benzene, and 2-propenyl benzene. The evaluated bond dissociation patterns and unimolecular decomposition pathways involve dehydrogenation, dehydration, 1,3-sigmatropic H-migration, 1,2-hydrogen shift, C—O and C—C bond cleavage processes. PMID:28344372
Hwang, Hyewon; Oh, Shinyoung; Cho, Tae-Su; Choi, In-Gyu; Choi, Joon Weon
2013-12-01
TGA results indicated that the maximum decomposition temperature of the biomass decreased from 373.9 to 359.0°C with increasing potassium concentration. For fast pyrolysis, char yield of potassium impregnated biomass doubled regardless of pyrolysis temperature compared to demineralized one. The presence of potassium also affected bio-oil properties. Water content increased from 14.4 to 19.7 wt% and viscosity decreased from 34 to 16.2 cSt, but the pH value of the bio-oil remained stable. Gas chromatography/mass spectroscopy (GC/MS) analysis revealed that potassium promoted thermochemical reactions, thus causing a decrease of levoglucosan and an increase of small molecules and lignin-derived phenols in bio-oil. Additionally, various forms of aromatic hydrocarbons, probably derived from lignins, were detected in non-condensed pyrolytic gas fractions. Copyright © 2013 Elsevier Ltd. All rights reserved.
Co-pyrolysis of microwave-assisted acid pretreated bamboo sawdust and soapstock.
Wang, Yunpu; Wu, Qiuhao; Duan, Dengle; Zhang, Yayun; Ruan, Roger; Liu, Yuhuan; Fu, Guiming; Zhang, Shumei; Zhao, Yunfeng; Dai, Leilei; Fan, Liangliang
2018-05-30
Fast microwave-assisted co-pyrolysis of pretreated bamboo sawdust and soapstock was conducted. The pretreatment process was carried out under microwave irradiation. The effects of microwave irradiation temperature, irradiation time, and concentration of hydrochloric acid on product distribution from co-pyrolysis and the relative contents of the major components in bio-oil were investigated. A maximum bio-oil yield of 40.00 wt.% was obtained at 200 °C for 60 min with 0.5 M hydrochloric acid. As pretreatment temperature, reaction time and acid concentration increased, respectively, the relative contents of phenols, diesel fraction (C12 + aliphatics), and other oxygenates decreased. The gasoline fraction (including C5-C12 aliphatics and aromatics) ranged from 55.77% to 73.30% under various pretreatment conditions. Therefore, excessive reaction time and concentration of acid are not beneficial to upgrading bio-oil. Copyright © 2018 Elsevier Ltd. All rights reserved.
Total recovery of nitrogen and phosphorus from three wetland plants by fast pyrolysis technology.
Liu, Wu-Jun; Zeng, Fan-Xin; Jiang, Hong; Yu, Han-Qing
2011-02-01
Fast pyrolysis of three wetland plants (Alligator weed, Oenanthe javanica and Typha angustifolia) in a vertical drop fixed bed reactor was investigated in this study. The experiments were carried out at different pyrolysis temperatures, and the maximum bio-oil yields achieved were 42.3%, 40.2% and 43.6% for Alligator weed, Oenanthe javanica and Typha angustifolia, respectively. The elemental composition of the bio-oil and char were analyzed, and the results show that a low temperature was appropriate for the nitrogen and phosphorus enrichment in char. GC-MS analysis shows that nitrogenous compounds, phenols and oxygenates were the main categories in the bio-oil. A series of leaching tests were carried out to examine the recovery of the nitrogen and phosphorus in the char, and the results indicate that significant fractions of nitrogen and phosphorus could be recovered by leaching process. Copyright © 2010 Elsevier Ltd. All rights reserved.
Fast pyrolysis of oil palm shell (OPS)
NASA Astrophysics Data System (ADS)
Abdullah, Nurhayati; Sulaiman, Fauziah; Aliasak, Zalila
2015-04-01
Biomass is an important renewable source of energy. Residues that are obtained from harvesting and agricultural products can be utilised as fuel for energy generation by conducting any thermal energy conversion technology. The conversion of biomass to bio oil is one of the prospective alternative energy resources. Therefore, in this study fast pyrolysis of oil palm shell was conducted. The main objective of this study was to find the optimum condition for high yield bio-oil production. The experiment was conducted using fixed-bed fluidizing pyrolysis system. The biomass sample was pyrolysed at variation temperature of 450°C - 650°C and at variation residence time of 0.9s - 1.35s. The results obtained were further discussed in this paper. The basic characteristic of the biomass sample was also presented here. The experiment shows that the optimum bio-oil yield was obtained at temperature of 500°C at residence time 1.15s.
Pyrolysis responses of kevlar/epoxy composite materials on laser irradiating
NASA Astrophysics Data System (ADS)
Liu, Wei-ping; Wei, Cheng-hua; Zhou, Meng-lian; Ma, Zhi-liang; Song, Ming-ying; Wu, Li-xiong
2017-05-01
The pyrolysis responses of kevlar/epoxy composite materials are valuable to study in a case of high temperature rising rate for its widely application. Distinguishing from the Thermal Gravimetric Analysis method, an apparatus is built to research the pyrolysis responses of kevlar/epoxy composite materials irradiated by laser in order to offer a high temperature rising rate of the sample. By deploying the apparatus, a near real-time gas pressure response can be obtained. The sample mass is weighted before laser irradiating and after an experiment finished. Then, the gas products molecular weight and the sample mass loss evolution are derived. It is found that the pressure and mass of the gas products increase with the laser power if it is less than 240W, while the molecular weight varies inversely. The variation tendency is confusing while the laser power is bigger than 240W. It needs more deeper investigations to bring it to light.
Effect of pulsation on black liquor gasification. Final report
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zinn, B.T.; Jagoda, J.; Jeong, H.
1998-12-01
Pyrolysis is an endothermic process. The heat of reaction is provided either by partial combustion of the waste or by heat transfer from an external combustion process. In one proposed system black liquor is pyrolized in a fluidized bed to which heat is added through a series of pulse combustor tail pipes submerged in the bed material. This system appears promising because of the relatively high heat transfer in pulse combustors and in fluidized beds. Other advantages of pulse combustors are discussed elsewhere. The process is, however, only economically viable if a part of the pyrolysis products can be usedmore » to fire the pulse combustors. The overall goals of this study were to determine: (1) which is the limiting heat transfer rate in the process of transferring heat from the hot combustion products to the pipe, through the pipe, from the tail pipe to the bed and through the bed; i.e., whether increased heat transfer within the pulse combustor will significantly increase the overall heat transfer rate; (2) whether the heat transfer benefits of the pulse combustor can be utilized while maintaining the temperature in the bed within the narrow temperature range required by the process without generating hot spots in the bed; and (3) whether the fuel gas produced during the gasification process can be used to efficiently fire the pulse combustor.« less
NASA Astrophysics Data System (ADS)
Morisson, Marietta; Buch, Arnaud; Szopa, Cyril; Raulin, François; Stambouli, Moncef
2017-04-01
Martian surface is exposed to harsh radiative and oxidative conditions which are destructive for organic molecules. That is why the future ExoMars rover will examine the molecular composition of samples acquired from depths down to two meters below the Martian surface, where organics may have been protected from radiative and oxidative degradation. The samples will then be analyzed by the Pyrolysis-Gas Chromatography-Mass Spectrometry (Pyr-GC-MS) operational mode of the Mars Organic Molecule Analyzer (MOMA) instrument. To prevent thermal alteration of organic molecules during pyrolysis, thermochemolysis with tetramethylammonium hydroxide (TMAH) will extract the organics from the mineral matrix and methylate the polar functional groups, allowing the volatilization of molecules at lower temperatures and protecting the most labile chemical groups from thermal degradation. This study has been carried out on a Martian regolith analogue (JSC-Mars-1) with a high organic content with the aim of optimizing the thermochemolysis temperature within operating conditions similar to the MOMA experiment ones. We also performed Pyrolysis-GC-MS analysis as a comparison. The results show that, unlike pyrolysis alone - which mainly produces aromatics, namely thermally altered molecules - thermochemolysis allows the extraction and identification of numerous organic molecules of astrobiological interest. They also show that the main compounds start to be detectable at low thermochemolysis temperatures ranging from 400°C to 600°C. However, we noticed that the more the temperature increases, the more the chromatograms are saturated with thermally evolved molecules leading to many coelutions and making identification difficult.
Chiang, Hung-Lung; Lin, Kuo-Hsiung
2014-01-15
The printed circuit board (PCB) is an important part of electrical and electronic equipment, and its disposal and the recovery of useful materials from waste PCBs (WPCBs) are key issues for waste electrical and electronic equipment. Waste PCB compositions and their pyrolysis characteristics were analyzed in this study. In addition, the volatile organic compound (VOC) exhaust was controlled by an iron-impregnated alumina oxide catalyst. Results indicated that carbon and oxygen were the dominant components (hundreds mg/g) of the raw materials, and other elements such as nitrogen, bromine, and copper were several decades mg/g. Exhaust constituents of CO, H2, CH4, CO2, and NOx, were 60-115, 0.4-4.0, 1.1-10, 30-95, and 0-0.7mg/g, corresponding to temperatures ranging from 200 to 500°C. When the pyrolysis temperature was lower than 300°C, aromatics and paraffins were the major species, contributing 90% of ozone precursor VOCs, and an increase in the pyrolysis temperature corresponded to a decrease in the fraction of aromatic emission factors. Methanol, ethylacetate, acetone, dichloromethane, tetrachloromethane and acrylonitrile were the main species of oxygenated and chlorinated VOCs. The emission factors of some brominated compounds, i.e., bromoform, bromophenol, and dibromophenol, were higher at temperatures over 400°C. When VOC exhaust was flowed through the bed of Fe-impregnated Al2O3, the emission of ozone precursor VOCs could be reduced by 70-80%. Copyright © 2013 Elsevier B.V. All rights reserved.
Simulation of Oil Palm Shell Pyrolysis to Produce Bio-Oil with Self-Pyrolysis Reactor
NASA Astrophysics Data System (ADS)
Fika, R.; Nelwan, L. O.; Yulianto, M.
2018-05-01
A new self-pyrolysis reactor was designed to reduce the utilization of electric heater due to the energy saving for the production of bio-oil from oil palm shell. The yield of the bio- oil was then evaluated with the developed mathematical model by Sharma [1] with the characteristic of oil palm shell [2]. During the simulation, the temperature on the combustion chamber on the release of the bio-oil was utilized to determine the volatile composition from the combustion of the oil palm shell as fuel. The mass flow was assumed constant for three experiments. The model resulted in a significant difference between the simulated bio-oil and experiments. The bio-oil yields from the simulation were 22.01, 16.36, and 21.89 % (d.b.) meanwhile the experimental yields were 10.23, 9.82, and 8.41% (d.b.). The char yield varied from 30.7 % (d.b.) from the simulation to 40.9 % (d.b.) from the experiment. This phenomenon was due to the development of process temperature over time which was not considered as one of the influential factors in producing volatile matters on the simulation model. Meanwhile the real experiments highly relied on the process conditions (reactor type, temperature over time, gas flow). There was also possibilities of the occurrence of the gasification inside the reactor which caused the liquid yield was not as high as simulated. Further simulation model research on producing the bio-oil yield will be needed to predict the optimum condition and temperature development on the newly self-pyrolysis reactor.
Demonstration of the waste tire pyrolysis process on pilot scale in a continuous auger reactor.
Martínez, Juan Daniel; Murillo, Ramón; García, Tomás; Veses, Alberto
2013-10-15
This work shows the technical feasibility for valorizing waste tires by pyrolysis using a pilot scale facility with a nominal capacity of 150 kWth. A continuous auger reactor was operated to perform thirteen independent experiments that conducted to the processing of more than 500 kg of shredded waste tires in 100 h of operation. The reaction temperature was 550°C and the pressure was 1 bar in all the runs. Under these conditions, yields to solid, liquid and gas were 40.5 ± 0.3, 42.6 ± 0.1 and 16.9 ± 0.3 wt.% respectively. Ultimate and proximate analyses as well as heating value analysis were conducted for both the solid and liquid fraction. pH, water content, total acid number (TAN), viscosity and density were also assessed for the liquid and compared to the specifications of marine fuels (standard ISO 8217). Gas chromatography was used to calculate the composition of the gaseous fraction. It was observed that all these properties remained practically invariable along the experiments without any significant technical problem. In addition, the reaction enthalpy necessary to perform the waste tire pyrolysis process (907.1 ± 40.0 kJ/kg) was determined from the combustion and formation enthalpies of waste tire and conversion products. Finally, a mass balance closure was performed showing an excellent reliability of the data obtained from the experimental campaign. Copyright © 2013 Elsevier B.V. All rights reserved.
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.
Structural evolution of maize stalk/char particles during pyrolysis.
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.
Study on Thermal and Mechanical Properties of EPDM Insulation
NASA Astrophysics Data System (ADS)
Zhang, Zhong-Shui; Xu, Jin-Sheng; Chen, Xiong; Jiang, Jing
As the most common insulation material of solid rocket motors, thermal and mechanical properties of ethylene propylene diene monomer (EPDM) composite are inspected in the study. Referring to the results of thermogravimetric analysis (TGA), composition and morphology of EPDM composite in different thermal degradation degree are investigated by scanning electron microscope (SEM) to inspect the mechanism of thermal insulation. Mechanical properties of EPDM composite in the state of pyrolysis are investigated by uniaxial tensile tests. At the state of initial pyrolysis, composite belongs to the category of hyperelastic-viscoelastic material. The tendency of tensile strength increased and elongation decreased with increasing of heating temperature. Composite behaves as the linear rule at the state of late pyrolysis, which belongs to the category of bittle. The elasticity modulus of curves are almost the same while the heating temperature ranges from 200°C to 300°C, and then gradually go down. The tensile strength of pyrolytic material reach the highest at the heating temperature of 300°C, and the virgin material has the largest elongation.
Zhang, Jun; Tian, Yu; Cui, Yanni; Zuo, Wei; Tan, Tao
2013-03-01
The nitrogen transformations with attention to NH3 and HCN were investigated at temperatures of 300-800°C during microwave pyrolysis of a protein model compound. The evolution of nitrogenated compounds in the char, tar and gas products were conducted. The amine-N, heterocyclic-N and nitrile-N compounds were identified as three important intermediates during the pyrolysis. NH3 and HCN were formed with comparable activation energies competed to consume the same reactive substances at temperatures of 300-800°C. The deamination and dehydrogenation of amine-N compounds from protein cracking contributed to the formation of NH3 (about 8.9% of Soy-N) and HCN (6.6%) from 300 to 500°C. The cracking of nitrile-N and heterocyclic-N compounds from the dehydrogenation and polymerization of amine-N generated HCN (13.4%) and NH3 (31.3%) between 500 and 800°C. It might be able to reduce the HCN and NH3 emissions through controlling the intermediates production at temperatures of 500-800°C. Copyright © 2013 Elsevier Ltd. All rights reserved.
Removal of hexavalent Cr by coconut coir and derived chars--the effect of surface functionality.
Shen, Ying-Shuian; Wang, Shan-Li; Tzou, Yu-Min; Yan, Ya-Yi; Kuan, Wen-Hui
2012-01-01
The Cr(VI) removal by coconut coir (CC) and chars obtained at various pyrolysis temperatures were evaluated. Increasing the pyrolysis temperature resulted in an increased surface area of the chars, while the corresponding content of oxygen-containing functional groups of the chars decreased. The Cr(VI) removal by CC and CC-derived chars was primarily attributed to the reduction of Cr(VI) to Cr(III) by the materials and the extent and rate of the Cr(VI) reduction were determined by the oxygen-containing functional groups in the materials. The contribution of pure Cr(VI) adsorption to the overall Cr(VI) removal became relatively significant for the chars obtained at higher temperatures. Accordingly, to develop a cost-effective method for removing Cr(VI) from water, the original CC is more advantageous than the carbonaceous counterparts because no pyrolysis is required for the application and CC has a higher content of functional groups for reducing Cr(VI) to less toxic Cr(III). Copyright © 2011 Elsevier Ltd. All rights reserved.
Organic emissions from coal pyrolysis: mutagenic effects.
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
Bio-oil and bio-char from low temperature pyrolysis of spent grains using activated alumina.
Sanna, Aimaro; Li, Sujing; Linforth, Rob; Smart, Katherine A; Andrésen, John M
2011-11-01
The pyrolysis of wheat and barley spent grains resulting from bio-ethanol and beer production respectively was investigated at temperatures between 460 and 540 °C using an activated alumina bed. The results showed that the bio-oil yield and quality depend principally on the applied temperature where pyrolysis at 460 °C leaves a bio-oil with lower nitrogen content in comparison with the original spent grains and low oxygen content. The viscosity profile of the spent grains indicated that activated alumina could promote liquefaction and prevent charring of the structure between 400 and 460 °C. The biochar contains about 10-12% of original carbon and 13-20% of starting nitrogen resulting very attractive as a soil amendment and for carbon sequestration. Overall, value can be added to the spent grains opening a new market in bio-fuel production without the needs of external energy. The bio-oil from spent grains could meet about 9% of the renewable obligation in the UK. Copyright © 2011 Elsevier Ltd. All rights reserved.
Valorisation of waste tyre by pyrolysis in a moving bed reactor.
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
Comparison of non-catalytic and catalytic fast pyrolysis of corncob in a fluidized bed reactor.
Zhang, Huiyan; Xiao, Rui; Huang, He; Xiao, Gang
2009-02-01
Fast pyrolysis of corncob with and without catalyst was investigated in a fluidized bed to determine the effects of pyrolysis parameters (temperature, gas flow rate, static bed height and particle size) and a HZSM-5 zeolite catalyst on the product yields and the qualities of the liquid products. The result showed that the optimal conditions for liquid yield (56.8%) were a pyrolysis temperature of 550 degrees C, gas flow rate of 3.4 L/min, static bed height of 10 cm and particle size of 1.0-2.0mm. The presence of the catalyst increased the yields of non-condensable gas, water and coke, while decreased the liquid and char yields. The elemental analysis showed that more than 25% decrease in oxygen content of the collected liquid in the second condenser with HZSM-5 was observed compared with that without catalyst. The H/C, O/C molar ratios and the higher heating value of the oil fraction in the collected liquid with the catalyst were 1.511, 0.149 and 34.6 MJ/kg, respectively. It was indicated that the collected liquid in the second condenser had high qualities and might be used as transport oil.
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.
Ex-situ catalytic pyrolysis of wastewater sewage sludge - A micro-pyrolysis study.
Wang, Kaige; Zheng, Yan; Zhu, Xifeng; Brewer, Catherine E; Brown, Robert C
2017-05-01
Concerns over increasing amounts of sewage sludge and unsustainability of current disposal methods have led to development of alternative routes for sludge management. The large amount of organics in sewage sludge makes it potential feedstock for energy or fuel production via thermochemical pathways. In this study, ex-situ catalytic pyrolysis using HZSM-5 catalyst was explored for the production of olefinic and aromatic hydrocarbons and nutrient-rich char from sewage sludge. The optimal pyrolysis and catalysis temperatures were found to be 500°C and 600°C, respectively. Carbon yields of hydrocarbons from sewage sludge were higher than for lignocellulose; yield differences were attributed to the high extractives content in the sludge. Full recovery of most inorganic elements were found in the char, which suggests that catalyst deactivation maybe alleviated through ex-situ catalytic pyrolysis. Most of the nitrogen was retained in the char while 31.80% was released as ammonia, which suggests a potential for nitrogen recycling. Copyright © 2017 Elsevier Ltd. All rights reserved.
Li, Dongbing; Briens, Cedric; Berruti, Franco
2015-01-01
Lignin pyrolysis was studied in a bubbling fluidized bed reactor equipped with a fractional condensation train, using nitrogen as the fluidization gas. The effect of different bed materials (silica sand, lignin char, activated lignin char, birch bark char, and foamed glass beads) on bio-oil yield and quality was investigated for a pyrolysis temperature of 550 °C. Results how that a bed of activated lignin char is preferable to the commonly used silica sand: pyrolysis of Kraft lignin with a bed of activated lignin char not only provides a pure char product, but also a higher dry bio-oil yield (with a relative increase of 43%), lower pyrolytic water production, and better bio-oil quality. The bio-oil obtained from Kraft lignin pyrolysis with a bed of activated lignin char has a lower average molecular weight, less tar, more phenolics, and less acidity than when sand is used as bed material. Copyright © 2015 Elsevier Ltd. All rights reserved.
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.
Han, Hengda; Hu, Song; Syed-Hassan, Syed Shatir A; Xiao, Yiming; Wang, Yi; Xu, Jun; Jiang, Long; Su, Sheng; Xiang, Jun
2017-07-01
Sewage sludge is an important class of bioresources whose energy content could be exploited using pyrolysis technology. However, some harmful trace elements in sewage sludge can escape easily to the gas phase during pyrolysis, increasing the potential of carcinogenic material emissions to the atmosphere. This study investigates emission characteristics of arsenic, cadmium and lead under different pyrolysis conditions for three different sewage sludge samples. The increased temperature (within 723-1123K) significantly promoted the cadmium and lead emissions, but its influence on arsenic emission was not pronounced. The releasing rate order of the three trace elements is volatile arsenic compounds>cadmium>lead in the beginning of pyrolysis. Fast heating rates promoted the emission of trace elements for the sludge containing the highest amount of ash, but exhibited an opposite effect for other studied samples. Overall, the high ash sludge released the least trace elements almost under all reaction conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.
Thermal pyrolysis characteristics of macroalgae Cladophora glomerata.
Gao, Wenhua; Chen, Kefu; Zeng, Jinsong; Xu, Jun; Wang, Bin
2017-11-01
The Cladophora glomerata (C. glomerata) is a kind of widely distributed macroalgae in the freshwater ecosystems. It primarily consists of carbohydrates that can be converted into biofuel by pyrolysis. In this study, thermogravimetric analysis (TGA) was used to investigate the thermal behavior and kinetics of C. glomerata during the pyrolysis process. The results showed that heating rates slightly affect the decomposition properties of C. glomerata; with the heating rates increasing, the maximum peak of weight loss rate shifted to higher temperatures. The activation energies of C. glomerata pyrolysis reaction were 244.25 and 238.07kJ/mol, respectively, as calculated by Friedman and Kissinger-Akahira-Sunose (KAS) methods. The pre-exponential factor and reaction order were determined by Coats-Redfern model, and applied to simulate the pyrolysis process of C. glomerata. The model calculated data and experimental data were consistent. This study could provide theoretical supports for designing C. glomerata conversion processes. Copyright © 2017 Elsevier Ltd. All rights reserved.
Kinetic study of solid waste pyrolysis using distributed activation energy model.
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.
Understanding the stability of pyrolysis tars from biomass in a view point of free radicals.
He, Wenjing; Liu, Qingya; Shi, Lei; Liu, Zhenyu; Ci, Donghui; Lievens, Caroline; Guo, Xiaofen; Liu, Muxin
2014-03-01
Fast pyrolysis of biomass has attracted increasing attention worldwide to produce bio-tars that can be upgraded into liquid fuels and chemicals. However, the bio-tars are usually poor in quality and stability and are difficult to be upgraded. To better understand the nature of the bio-tars, this work reveals radical concentration of tars derived from pyrolysis of two kinds of biomass. The tars were obtained by condensing the pyrolysis volatiles in 3s. It shows that the tars contain large amounts of radicals, at a level of 10(16)spins/g, and are able to generate more radicals at temperatures of 573K or higher, reaching a level of 10(19)spins/g at 673K in less than 30min. The radical generation in the tar samples is attributed to the formation of THF insoluble matters (coke), which also contain radicals. The radical concentrations of the aqueous liquids obtained in pyrolysis are also studied. Copyright © 2014 Elsevier Ltd. All rights reserved.
Thermogravimetric and kinetic study of Pinyon pine in the various gases.
Kim, Seung-Soo; Shenoy, Alok; Agblevor, Foster A
2014-03-01
As a renewable resource, Pinyon pine can be converted into bio-oil, gas, and char through pyrolysis. It is known that recycling of the non-condensable gases, which are produced by fast pyrolysis, can increase liquid yield and decrease char yield. In this study, pyrolysis characteristics and kinetics of Pinyon pine were investigated in TGA using simulated non-condensable gases (N2, H2/N2, H2/CO2, and He/CO/H2). The apparent activation energy of Pinyon pine increased from 43.9 to 160.3kJ mol(-1) with increasing pyrolysis conversion from 5% to 95% in pure nitrogen, and reaction order was 1.35. When hydrogen (H2) and carbon monoxide (CO) mixtures were used as simulated gases, the maximum degradation temperature and activation energy decreased by 4-11°C and 6.1-10.2kJ/mol, respectively. The results show that recycling of non-condensable gases could positively influence the fast pyrolysis of biomass. Copyright © 2014 Elsevier Ltd. All rights reserved.
Rates and Mechanisms of Oil Shale Pyrolysis: A Chemical Structure Approach
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fletcher, Thomas; Pugmire, Ronald
2015-01-01
Three pristine Utah Green River oil shale samples were obtained and used for analysis by the combined research groups at the University of Utah and Brigham Young University. Oil shale samples were first demineralized and the separated kerogen and extracted bitumen samples were then studied by a host of techniques including high resolution liquid-state carbon-13 NMR, solid-state magic angle sample spinning 13C NMR, GC/MS, FTIR, and pyrolysis. Bitumen was extracted from the shale using methanol/dichloromethane and analyzed using high resolution 13C NMR liquid state spectroscopy, showing carbon aromaticities of 7 to 11%. The three parent shales and the demineralized kerogensmore » were each analyzed with solid-state 13C NMR spectroscopy. Carbon aromaticity of the kerogen was 23-24%, with 10-12 aromatic carbons per cluster. Crushed samples of Green River oil shale and its kerogen extract were pyrolyzed at heating rates from 1 to 10 K/min at pressures of 1 and 40 bar and temperatures up to 1000°C. The transient pyrolysis data were fit with a first-order model and a Distributed Activation Energy Model (DAEM). The demineralized kerogen was pyrolyzed at 10 K/min in nitrogen at atmospheric pressure at temperatures up to 525°C, and the pyrolysis products (light gas, tar, and char) were analyzed using 13C NMR, GC/MS, and FTIR. Details of the kerogen pyrolysis have been modeled by a modified version of the chemical percolation devolatilization (CPD) model that has been widely used to model coal combustion/pyrolysis. This refined CPD model has been successful in predicting the char, tar, and gas yields of the three shale samples during pyrolysis. This set of experiments and associated modeling represents the most sophisticated and complete analysis available for a given set of oil shale samples.« less
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.
Growth and characterization of V2O5 nanorods deposited by spray pyrolysis at low temperatures
NASA Astrophysics Data System (ADS)
Abd-Alghafour, N. M.; Ahmed, Naser M.; Hassan, Zai.; Mohammad, Sabah M.; Bououdina, M.
2016-07-01
Vanadium pentoxide (V2O5) nanorods were deposited by spray pyrolysis on preheated glass substrates at low temperatures. The influence of substrate temperature on the crystallization of V2O5 has been investigated. X-ray diffraction analysis (XRD) revealed that the films deposited at Tsub = 300°C were orthorhombic structures with preferential along (001) direction. Formation of nanorods from substrate surface which led to the formation of films with small-sized and rod-shaped nanostructure is observed by field scanning electron microscopy. Optical transmittance in the visible range increases to reach a maximum value of about 80% for a substrate temperature of 350°C. PL spectra reveal one main broad peak centered around 540 nm with high intensity.
A Systems Approach to Bio-Oil Stabilization - Final Technical Report
DOE Office of Scientific and Technical Information (OSTI.GOV)
Brown, Robert C; Meyer, Terrence; Fox, Rodney
2011-12-23
The objective of this project is to develop practical, cost effective methods for stabilizing biomass-derived fast pyrolysis oil for at least six months of storage under ambient conditions. The U.S. Department of Energy has targeted three strategies for stabilizing bio-oils: (1) reducing the oxygen content of the organic compounds comprising pyrolysis oil; (2) removal of carboxylic acid groups such that the total acid number (TAN) of the pyrolysis oil is dramatically reduced; and (3) reducing the charcoal content, which contains alkali metals known to catalyze reactions that increase the viscosity of bio-oil. Alkali and alkaline earth metals (AAEM), are knownmore » to catalyze decomposition reactions of biomass carbohydrates to produce light oxygenates that destabilize the resulting bio-oil. Methods envisioned to prevent the AAEM from reaction with the biomass carbohydrates include washing the AAEM out of the biomass with water or dilute acid or infusing an acid catalyst to passivate the AAEM. Infusion of acids into the feedstock to convert all of the AAEM to salts which are stable at pyrolysis temperatures proved to be a much more economically feasible process. Our results from pyrolyzing acid infused biomass showed increases in the yield of anhydrosugars by greater than 300% while greatly reducing the yield of light oxygenates that are known to destabilize bio-oil. Particulate matter can interfere with combustion or catalytic processing of either syngas or bio-oil. It also is thought to catalyze the polymerization of bio-oil, which increases the viscosity of bio-oil over time. High temperature bag houses, ceramic candle filters, and moving bed granular filters have been variously suggested for syngas cleaning at elevated temperatures. High temperature filtration of bio-oil vapors has also been suggested by the National Renewable Energy Laboratory although there remain technical challenges to this approach. The fast pyrolysis of biomass yields three main organic products: condensable vapors, non-condensable gases, and liquid aerosols. Traditionally these are recovered by a spray quencher or a conventional shell and tube condenser. The spray quencher or condenser is typically followed by an electrostatic precipitator to yield 1 or 2 distinct fractions of bio-oil. The pyrolyzer system developed at Iowa State University incorporates a proprietary fractionating condenser train. The system collects the bio-oil into five unique fractions. For conditions typical of fluidized bed pyrolyzers, stage fractions have been collected that are carbohydrate-rich (anhydrosugars), lignin-rich, and an aqueous solution of carboxylic acids and aldehydes. One important feature is that most of the water normally found in bio-oil appears in the last stage fraction along with several water-soluble components that are thought to be responsible for bio-oil aging (low molecular weight carboxylic acids and aldehydes). Research work on laser diagnostics for hot-vapor filtration and bio-oil recovery centered on development of analytical techniques for in situ measurements during fast pyrolysis, hot-vapor filtration, and fractionation relative to bio-oil stabilization. The methods developed in this work include laser-induced breakdown spectroscopy (LIBS), laser-induced incandescence (LII), and laser scattering for elemental analysis (N, O, H, C), detection of particulates, and detection of aerosols, respectively. These techniques were utilized in simulated pyrolysis environments and applied to a small-scale pyrolysis unit. Stability of Bio-oils is adversely affected by the presence of particulates that are formed as a consequence of thermal pyrolysis, improving the CFD simulations of moving bed granular filter (MBGF) is useful for improving the design of MBGF for bio-oil production. The current work uses fully resolved direct numerical simulation (where the flow past each granule is accurately represented) to calculate the filter efficiency that is used in the CFD model at all flow speeds. This study shows that fully-resolved direct numerical simulation (DNS) is successful in calculating the filter efficiency at all speeds. Aldehydes and acids are thought to play key roles in the stability of bio-oils, so the catalytic stabilization of bio-oils was focused on whether a reaction approach could be employed that simultaneously addressed these two types of molecules in bio-oil. Our approach to post treatment was simultaneous hydrogenation and esterification using bifunctional metal/acidic heterogeneous catalyst in which reactive aldehydes were reduced to alcohols, creating a high enough alcohol concentration so that the carboxylic acids could be esterified.« less
Thiophenic Sulfur Compounds Released During Coal Pyrolysis
Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan
2013-01-01
Abstract Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography–mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis. PMID:23781126
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.
Shuai, Yanhua; Douglas, Peter M.J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.
2018-01-01
Multiply isotopically substituted molecules (‘clumped’ isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature–time conditions corresponding to ‘low,’ ‘mature,’ and ‘over-mature’ stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions (‘high’ to ‘over-mature’ stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where ‘secondary’ cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl precursor. Other interpretations are also explored. These findings provide new insights into the chemistry of thermogenic methane generation, and may provide an explanation of the elevated apparent temperatures recorded by the methane clumped-isotope thermometer in some natural gases. However, it remains unknown if the laboratory experiments capture the processes that occur at the longer time and lower temperatures of natural gas formation.
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.
Matsuoka, Seiji; Kawamoto, Haruo; Saka, Shiro
2011-02-01
Thermal glycosylation and degradation reactions of cellulose (Avicel PH-101) were studied in the presence or absence of alcohols (glycerol, mannitol, 1,2,6-hexanetriol, 3-phenoxy-1,2-propanediol, and 1-tetradecanol) under N(2) at 60-280°C. In the presence of glycerol (heating time, 10 min), the reducing ends were converted into glycosides when the temperature of the glycerol was >140°C without the addition of any catalysts. A temperature of 140°C is close to that required for the initiation of thermal polymerization (glycosylation). Although the conversion was only around 20% in the range of 140-180°C, the reactivity increased above 200-240°C where the thermal expansion of cellulose crystals is reported to become significant. Finally, all reducing ends were converted into glycosides at 260°C. Such heterogeneous reactivity likely arose from the lower reactivities of the reducing ends in the crystalline region due to their lower accessibility to glycerol, although the reactivity in the non-crystalline region was similar to that of glucose. Alcohols that have a lower OH/C ratio did not react with the reducing ends, suggesting that the hydrophilicity of the alcohol was critical for the glycosylation reaction to proceed. The glycosylated cellulose samples were found to be significantly stabilized against pyrolytic coloration. The results of neat cellulose pyrolysis indicated that two competitive reactions, thermal glycosylation and degradation, formed a dark-colored substance at the reducing ends while the internal glucose units in the cellulose were comparatively stable. 2010 Elsevier Ltd. All rights reserved.
Method for making carbon super capacitor electrode materials
Firsich, D.W.; Ingersoll, D.; Delnick, F.M.
1998-07-07
A method is described for making near-net-shape, monolithic carbon electrodes for energy storage devices. The method includes the controlled pyrolysis and activation of a pressed shape of methyl cellulose powder with pyrolysis being carried out in two stages; pre-oxidation, preferably in air at a temperature between 200--250 C, followed by carbonization under an inert atmosphere. An activation step to adjust the surface area of the carbon shape to a value desirable for the application being considered, including heating the carbon shape in an oxidizing atmosphere to a temperature of at least 300 C, follows carbonization. 1 fig.
Toxicity of pyrolysis gases from wood
NASA Technical Reports Server (NTRS)
Hilado, C. J.; Huttlinger, N. V.; Oneill, B. A.; Kourtides, D. A.; Parker, J. A.
1977-01-01
The toxicity of the pyrolysis gases from nine wood samples was investigated. The samples of hardwoods were aspen poplar, beech, yellow birch, and red oak. The samples of softwoods were western red cedar, Douglas fir, western hemlock, eastern white pine, and southern yellow pine. There was no significant difference between the wood samples under rising temperature conditions, which are intended to simulate a developing fire, or under fixed temperature conditions, which are intended to simulate a fully developed fire. This test method is used to determine whether a material is significantly more toxic than wood under the preflashover conditions of a developing fire.
Method for making carbon super capacitor electrode materials
Firsich, David W.; Ingersoll, David; Delnick, Frank M.
1998-01-01
A method for making near-net-shape, monolithic carbon electrodes for energy storage devices. The method includes the controlled pyrolysis and activation of a pressed shape of methyl cellulose powder with pyrolysis being carried out in two stages; pre-oxidation, preferably in air at a temperature between 200.degree.-250.degree. C., followed by carbonization under an inert atmosphere. An activation step to adjust the surface area of the carbon shape to a value desirable for the application being considered, including heating the carbon shape in an oxidizing atmosphere to a temperature of at least 300.degree. C., follows carbonization.
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.
The sensitivity of relative toxicity rankings by the USF/NASA test method to some test variables
NASA Technical Reports Server (NTRS)
Hilado, C. J.; Labossiere, L. A.; Leon, H. A.; Kourtides, D. A.; Parker, J. A.; Hsu, M.-T. S.
1976-01-01
Pyrolysis temperature and the distance between the source and sensor of effluents are two important variables in tests for relative toxicity. Modifications of the USF/NASA toxicity screening test method to increase the upper temperature limit of pyrolysis, reduce the distance between the sample and the test animals, and increase the chamber volume available for animal occupancy, did not significantly alter rankings of relative toxicity of four representative materials. The changes rendered some differences no longer significant, but did not reverse any rankings. The materials studied were cotton, wool, aromatic polyamide, and polybenzimidazole.
Oil residue contamination of continental shelf sediments of the Gulf of Mexico.
Harding, V; Camp, J; Morgan, L J; Gryko, J
2016-12-15
We have investigated the distribution of a heavy oil residue in the coastal sediments of the Gulf of Mexico. The amount of the contamination was determined by high-temperature pyrolysis coupled with the Gas Chromatography-Mass Spectrometry (GCMS) of air-dried sediments. The pyrolysis products contain straight-chain saturated and unsaturated hydrocarbons, such as dodecane and 1-dodecene, resulting in a very characteristic pattern of double peaks in the GCMS. Hydrocarbons containing 8 to 23 carbon atoms were detected in the pyrolysis products. Using thermal pyrolysis we have found that the sediment samples collected along Texas, Louisiana, and Mississippi shores contain no detectable traces of oil residue, but most of the samples collected along Alabama and Florida shores contain ~200ppm of heavy oil residue. Copyright © 2016 Elsevier Ltd. All rights reserved.
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
Diffusion of biomass pyrolysis products in H-ZSM-5 by molecular dynamics simulations
Bu, Lintao; Nimlos, Mark R.; Robichaud, David J.; ...
2016-12-13
Diffusion of biomass pyrolysis vapors and their upgraded products is an essential catalytic property of zeolites during catalytic fast pyrolysis and likely plays a critical role in the selectivity of these catalysts. Characterizing the diffusivities of representative biofuel molecules is critical to understand shape selectivity and interpret product distribution. Yet, experimental measurements on the diffusivities of oxygenated biofuel molecules at pyrolysis temperatures are very limited in the literature. As an alternative approach, we conducted MD simulations to measure the diffusion coefficients of several selected molecules that are representative of biomass pyrolysis vapors, namely water, methanol, glycolaldehyde, and toluene in H-ZSM-5more » zeolite. The results show the diffusion coefficients calculated via MD simulations are consistent with available NMR measurements at room temperature. The effect of molecular weight and molecular critical diameter on the diffusivity among the chosen model compounds is also examined. Furthermore, we have characterized the diffusivities of representative biofuel molecules, namely xylene isomers, in H-ZSM-5. Our calculations determined that the ratio of the diffusion coefficients for xylene isomers is p-xylene: o-xylene: m-xylene ≈ 83:3:1 at 700 K. Furthermore, our results also demonstrate the different diffusivity between p-xylene and toluene is due to the molecular orientations when the molecules diffuse along the channels in H-ZSM-5 and provide deep insight into the effect of molecular orientation on its diffusivity.« less
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.
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.
Characterization of biochar prepared from biogas digestate.
Hung, Chao-Yi; Tsai, Wen-Tien; Chen, Jie-Wei; Lin, Yu-Quan; Chang, Yuan-Ming
2017-08-01
In the study, the biogas digestate was evaluated as a potential feedstock for preparing biochars at a broad temperature range of 300-900°C. The physico-chemical and pore properties of the resulting biochars (denoted as SDBC, solid digestate biochar), including calorific value (higher heating value), surface area/pore volume/pore size distribution, true density, scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray powder diffraction (XRD), were studied. It was found that the higher heating values of the SDBC products were on a decreasing trend as pyrolysis temperature increased, but they indicated an increase in true density. The results are probably associated with the active pyrolysis of the lignocellulosic fragments and the calcination (or shrinkage) processes, thus resulting in the increased contents of aromatic carbon clusters and main mineral constituents remained. Based on the pore properties, pyrolysis temperature at around 800°C seemed to be the optimal condition for producing SDBC, where its Brunauer-Emmet-Teller (BET) surface area (>100m 2 /g) largely increased as compared to that of the digestate feedstock (<1m 2 /g). Furthermore, the main compositions of mineral ash in the resulting biochar could exist as phosphates, carbonates, or oxides of calcium and other alkali/alkaline earth elements. According to the data on EDS and XRD, more pores could be significantly generated under severe pyrolysis (>700°C) due to the high aromaticity via the thermal decomposition of lignocelluloses and the volatilization of inorganic minerals. Copyright © 2017 Elsevier Ltd. All rights reserved.
Pyrolysis conditions and ozone oxidation effects on ammonia adsorption in biomass generated chars.
Kastner, James R; Miller, Joby; Das, K C
2009-05-30
Ammonia adsorbents were generated via pyrolysis of biomass (peanut hulls and palm oil shells) over a range of temperatures and compared to a commercially available activated carbon (AC) and solid biomass residuals (wood and poultry litter fly ash). Dynamic ammonia adsorption studies (i.e., breakthrough curves) were performed using these adsorbents at 23 degrees C from 6 to 17 ppmv NH(3). Of the biomass chars, palm oil char generated at 500 degrees C had the highest NH(3) adsorption capacity (0.70 mg/g, 6 ppmv, 10% relative humidity (RH)), was similar to the AC, and contrasted to the other adsorbents (including the AC), the NH(3) adsorption capacity significantly increased if the relative humidity was increased (4 mg/g, 7 ppmv, 73% RH). Room temperature ozone treatment of the chars and activated carbon significantly increased the NH(3) adsorption capacity (10% RH); resultant adsorption capacity, q (mg/g) increased by approximately 2, 6, and 10 times for palm oil char, peanut hull char (pyrolysis only), and activated carbon, respectively. However, water vapor (73% RH at 23 degrees C) significantly reduced NH(3) adsorption capacity in the steam and ozone treated biomass, yet had no effect on the palm shell char generated at 500 degrees C. These results indicate the feasibility of using a low temperature (and thus low energy input) pyrolysis and activation process for the generation of NH(3) adsorbents from biomass residuals.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schmidt, P.W.; Cutter, B.E.; Kalliat, M.
1984-04-01
In order to learn about the effects of higher preparation temperatures, we recently examined a series of charcoals from black cherry (Prunus serotina Ehrh.) wood heated to temperatures from 600/sup 0/ to 2000/sup 0/C. The results are summarized in this report. In addition to obtaining some information about the pore structure of black cherry charcoal, we have developed a general picture of how the charcoal porosity depends on the temperature to which the wood was heated during pyrolysis. These results have led us to propose that the macropores in charcoals are similar to those in wood and that the mainmore » effect which pyrolysis at temperatures above 400/sup 0/C exerts on the pore structure is to cause the micropores and transitional pores to grow, while leaving the macropores almost unchanged.« less
Nakamura, S; Takino, M; Daishima, S
2001-04-06
Gas chromatography-mass spectrometry (GC-MS) with a temperature-programmable pyrolyzer was used for the analysis of waterborne paints. Evolved gas analysis (EGA) profiles of the waterborne paints were obtained by this temperature-programmed pyrolysis directly coupled with MS via a deactivated metal capillary tube. The EGA profile suggested the optimal thermal desorption conditions for solvents and additives and the subsequent optimal pyrolysis temperature for the remaining polymeric material. Polymers were identified from pyrograms with the assistance of a new polymer library. The solvents were identified from the electron ionization mass spectra with the corresponding chemical ionization mass spectra. The additive was identified as zinc pyrithione by comparison with authentic standard. Zinc pyrithione cannot be analyzed by GC-MS as it is. However, the thermal decomposition products of zinc pyrithione could be detected. The information on the decomposition temperature and products was useful for the identification of the original compound.
Kinetic modeling of ethane pyrolysis at high conversion.
Xu, Chen; Al Shoaibi, Ahmed Sultan; Wang, Chenguang; Carstensen, Hans-Heinrich; Dean, Anthony M
2011-09-29
The primary objective of this study is to develop an improved first-principle-based mechanism that describes the molecular weight growth kinetics observed during ethane pyrolysis. A proper characterization of the kinetics of ethane pyrolysis is a prerequisite for any analysis of hydrocarbon pyrolysis and oxidation. Flow reactor experiments were performed with ~50/50 ethane/nitrogen mixtures with temperatures ranging from 550 to 850 °C at an absolute pressure of ~0.8 atm and a residence time of ~5 s. These conditions result in ethane conversions ranging from virtually no reaction to ~90%. Comparisons of predictions using our original mechanism to these data yielded very satisfactory results in terms of the temperature dependence of ethane conversion and prediction of the major products ethylene and hydrogen. However, there were discrepancies in some of the minor species concentrations that are involved in the molecular weight growth kinetics. We performed a series of CBS-QB3 analyses for the C(3)H(7), C(4)H(7), and C(4)H(9) potential energy surfaces to better characterize the radical addition reactions that lead to molecular weight growth. We also extended a published C(6)H(9) PES to include addition of vinyl to butadiene. The results were then used to calculate pressure-dependent rate constants for the multiple reaction pathways of these addition reactions. Inclusion of the unadjusted rate constants resulting from these analyses in the mechanism significantly improved the description of several of the species involved in molecular weight growth kinetics. We compare the predictions of this improved model to those obtained with a consensus model recently published as well as to ethane steam cracking data. We find that a particularly important reaction is that of vinyl addition to butadiene. Another important observation is that several radical addition reactions are partially equilibrated. Not only does this mean that reliable thermodynamic parameters are essential for an accurate model, but also that the reaction set describing molecular weight growth chemistry must include a final product that is sufficiently stable to shift the equilibrium toward this product despite the decrease in entropy that accompanies molecular weight growth. Another reaction, H addition to olefins, was found to inhibit molecular weight growth by leading to the production of a lower olefin plus methyl radicals.
Ngatia, L W; Hsieh, Y P; Nemours, D; Fu, R; Taylor, R W
2017-08-01
Phosphorus (P) eutrophication is a major pollution problem globally, with unprecedented amount of P emanating from agricultural sources. But little is known about the optimization of soil-biochar P sorption capacity. The study objective was to determine how biochar feedstocks and pyrolysis conditions influences carbon (C) thermal stability, C composition and pH and in turn influence the phosphorus sorption optimization. Biochar was produced from switchgrass, kudzu and Chinese tallow at 200, 300, 400, 500, 550, 650,750 °C. Carbon thermal stability was determined by multi-element scanning thermal analysis (MESTA), C composition was determined using solid state 13 C NMR. Phosphorus sorption was determined using a mixture of 10% biochar and 90% sandy soil after incubation. Results indicate increased P sorption (P < 0.0001) and decreased P availability (P < 0.0001) with increasing biochar pyrolysis temperature. However, optimum P sorption was feedstock specific with switchgrass indicating P desorption between 200 and 550 °C. Phosphorus sorption was in the order of kudzu > switchgrass > Chinese tallow. Total C, C thermal stability, aromatic C and alkalinity increased with elevated pyrolysis temperature. Biochar alkalinity favored P sorption. There was a positive relationship between high thermal stable C and P sorption for Kudzu (r = 0.62; P = 0.0346) and Chinese tallow (r = 0.73; P = 0.0138). In conclusion, biochar has potential for P eutrophication mitigation, however, optimum biochar pyrolysis temperature for P sorption is feedstock specific and in some cases might be out of 300-500 °C temperature range commonly used for agronomic application. High thermal stable C dominated by aromatic C and alkaline pH seem to favor P sorption. Copyright © 2017 Elsevier Ltd. All rights reserved.
Mo, Yu; Zhao, Lei; Wang, Zhonghui; Chen, Chia-Lung; Tan, Giin-Yu Amy; Wang, Jing-Yuan
2014-04-01
A work applied response surface methodology coupled with Box-Behnken design (RSM-BBD) has been developed to enhance styrene recovery from waste polystyrene (WPS) through pyrolysis. The relationship between styrene yield and three selected operating parameters (i.e., temperature, heating rate, and carrier gas flow rate) was investigated. A second order polynomial equation was successfully built to describe the process and predict styrene yield under the study conditions. The factors identified as statistically significant to styrene production were: temperature, with a quadratic effect; heating rate, with a linear effect; carrier gas flow rate, with a quadratic effect; interaction between temperature and carrier gas flow rate; and interaction between heating rate and carrier gas flow rate. The optimum conditions for the current system were determined to be at a temperature range of 470-505°C, a heating rate of 40°C/min, and a carrier gas flow rate range of 115-140mL/min. Under such conditions, 64.52% WPS was recovered as styrene, which was 12% more than the highest reported yield for reactors of similar size. It is concluded that RSM-BBD is an effective approach for yield optimization of styrene recovery from WPS pyrolysis. Copyright © 2014 Elsevier Ltd. All rights reserved.
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.
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
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.
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.
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.
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.
Lee, Hyung Won; Choi, Suek Joo; Park, Sung Hoon; Jeon, Jong-Ki; Jung, Sang-Chul; Kim, Sang Chai; Park, Young-Kwon
2014-01-01
The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N2 adsorption-desorption isotherms, and NH3 temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H2O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro-d-galactitol and 1,5-anhydro-d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H2O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis.
NASA Astrophysics Data System (ADS)
Lee, Hyung Won; Choi, Suek Joo; Park, Sung Hoon; Jeon, Jong-Ki; Jung, Sang-Chul; Kim, Sang Chai; Park, Young-Kwon
2014-08-01
The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N2 adsorption-desorption isotherms, and NH3 temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H2O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro- d-galactitol and 1,5-anhydro- d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H2O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis.
2014-01-01
The catalytic co-pyrolysis of a seaweed biomass, Laminaria japonica, and a typical polymer material, polypropylene, was studied for the first time. A mesoporous material Al-SBA-15 was used as a catalyst. Pyrolysis experiments were conducted using a fixed-bed reactor and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). BET surface area, N2 adsorption-desorption isotherms, and NH3 temperature programmed desorption were measured to examine the catalyst characteristics. When only L. japonica was pyrolyzed, catalytic reforming slightly increased the gas yield and decreased the oil yield. The H2O content in bio-oil was increased by catalytic reforming from 42.03 to 50.32 wt% due to the dehydration reaction occurring on the acid sites inside the large pores of Al-SBA-15. Acids, oxygenates, mono-aromatics, poly aromatic hydrocarbons, and phenolics were the main components of the bio-oil obtained from the pyrolysis of L. japonica. Upon catalytic reforming over Al-SBA-15, the main oxygenate species 1,4-anhydro-d-galactitol and 1,5-anhydro-d-manitol were completely removed. When L. japonica was co-pyrolyzed with polypropylene, the H2O content in bio-oil was decreased dramatically (8.93 wt% in the case of catalytic co-pyrolysis), contributing to the improvement of the oil quality. A huge increase in the content of gasoline-range and diesel-range hydrocarbons in bio-oil was the most remarkable change that resulted from the co-pyrolysis with polypropylene, suggesting its potential as a transport fuel. The content of mono-aromatics with high economic value was also increased significantly by catalytic co-pyrolysis. PMID:25136282
NASA Astrophysics Data System (ADS)
Gibson, C. D.; Filley, T. R.; Bird, J. A.; Hatton, P. J.; Stark, R. E.; Nadelhoffer, K. J.
2017-12-01
Pyrogenic organic matter (PyOM) produced during forest fires is considered a large sink of stable soil organic matter (SOM) in boreal-temperate forest ecotones, where fire frequency and intensity is growing with changing climate. Understanding how changes in fire regime and predicted shifts in plant taxa will interact to affect PyOM dynamics in soil is imperative to assessing the impact of climate change on SOM maintenance. The stability of PyOM in soil may be co-determined by the physiochemical structure imparted on PyOM during pyrolysis and by its initial taxa-dependent wood chemistry and anatomy. To determine PyOM-C turnover rates in soil, we followed the fate of 13C-enriched wood or PyOM (200, 300, 450, or 600°C) derived from red maple (RM) or jack pine (JP) wood in soil from a recently burned forest in northern Michigan, USA. We found that pyrolysis temperature-controlled physiochemical changes influenced, with threshold dynamics, PyOM stability resulting in mean residence times of 2 (PyOM 200°C) to 450 years for both taxa, confirming that most PyOM (<600°C) turns over on the century, not millennial time scale. Water leachable C, carbohydrate and non-lignin phenol content correlated positively with early PyOM-C mineralization for both JP and RM, but the pyrolysis temperature at which this interaction was strongest differed with taxa reflecting the difference in thermal transition in which carbonization begins (300°C for JP and 450°C for RM). In contrast to previous studies, the addition of sucrose suggests that a co-metabolism mechanism of PyOM decomposition is minor in this soil. Our results show that while the first order control on PyOM stability in this soil is pyrolysis temperature, wood taxa did affect PyOM C MRT, in part due to differences in the amount of water soluble C released by PyOM during the initial decomposition dynamics in soil.
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
Thermokinetic analysis and product characterization of Medium Density Fiberboard pyrolysis.
Aslan, Dilan Irmak; Özoğul, Buğçe; Ceylan, Selim; Geyikçi, Feza
2018-06-01
This study investigates the pyrolysis of Medium Density Fiberboard (MDF) as a potential waste management solution. Thermal behaviour of MDF was analysed via TG/DSC. The primary decomposition step occurred between 190 °C and 425 °C. Evolved gaseous products over this step were evaluated by a FTIR spectrometer coupled with TGA. Peaks for phenolic, alcohols and aldehydes were detected at the maximum decomposition temperature. Py-GC/MS analysis revealed phenols, ketones and cyclic compounds as the primary non-condensable pyrolysis products. The kinetics of pyrolysis were investigated by the widely applied Distributed Activation Energy Model, resulting in an average activation energy and pre-exponential factor of 127.40 kJ mol -1 and 8.4E+11. The results of this study suggest that pyrolyzing MDF could potentially provide renewable fuels and prevent environmental problems related with MDF disposal. Copyright © 2018 Elsevier Ltd. All rights reserved.
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.
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.
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
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
Thermogravimetric characteristics of typical municipal solid waste fractions during co-pyrolysis.
Zhou, Hui; Long, YanQiu; Meng, AiHong; Li, QingHai; Zhang, YanGuo
2015-04-01
The interactions of nine typical municipal solid waste (MSW) fractions during pyrolysis were investigated using the thermogravimetric analyzer (TGA). To compare the mixture results with the calculation results of superposition of single fractions quantitatively, TG overlap ratio was introduced. There were strong interactions between orange peel and rice (overlap ratio 0.9736), and rice and poplar wood (overlap ratio 0.9774). The interactions of mixture experiments postponed the peak and lowered the peak value. Intense interactions between PVC and rice, poplar wood, tissue paper, wool, terylene, and rubber powder during co-pyrolysis were observed, and the pyrolysis at low temperature was usually promoted. The residue yield was increased when PVC was blended with rice, poplar wood, tissue paper, or rubber powder; while the residue yield was decreased when PVC was blended with wool. Copyright © 2014 Elsevier Ltd. All rights reserved.
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.
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
Park, Y K; Kang, Hyeon Koo; Jang, Hansaem; Suh, Dong Jin; Park, Sung Hoon
2016-05-01
Catalytic pyrolysis of lignin, a major constituent of biomass, was performed. A nanoporous molecular sieve silicoaluminophosphate-11 (SAPO-11) was selected as catalyst. Thermogravimetric analysis showed that 500 degrees C was the optimal pyrolysis temperature. Pyrolyzer-gas chromatography/mass spectroscopy was used to investigate the pyrolysis product distribution. Production of phenolics, the dominant product from the pyrolysis of lignin, was promoted by the increase in the catalyst dose. In particular, low-molecular-mass phenolics were produced more over SAPO-11, while high-molecular-mass phenolics and double-bond-containing phenolics were produced less. The fraction of aromatic compounds, including benzene, toluene, xylene, and ethylbenzene, was also increased by catalytic reforming. The catalytic effects were more pronounced when the catalyst/biomass ratio was increased. The enhanced production of aromatic compounds by an acidic catalyst obtained in this study is in good agreement with the results of previous studies.
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
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.
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 %.
Santín, Cristina; Doerr, Stefan H; Merino, Agustin; Bucheli, Thomas D; Bryant, Rob; Ascough, Philippa; Gao, Xiaodong; Masiello, Caroline A
2017-09-11
Pyrogenic carbon (PyC), produced naturally (wildfire charcoal) and anthropogenically (biochar), is extensively studied due to its importance in several disciplines, including global climate dynamics, agronomy and paleosciences. Charcoal and biochar are commonly used as analogues for each other to infer respective carbon sequestration potentials, production conditions, and environmental roles and fates. The direct comparability of corresponding natural and anthropogenic PyC, however, has never been tested. Here we compared key physicochemical properties (elemental composition, δ 13 C and PAHs signatures, chemical recalcitrance, density and porosity) and carbon sequestration potentials of PyC materials formed from two identical feedstocks (pine forest floor and wood) under wildfire charring- and slow-pyrolysis conditions. Wildfire charcoals were formed under higher maximum temperatures and oxygen availabilities, but much shorter heating durations than slow-pyrolysis biochars, resulting in differing physicochemical properties. These differences are particularly relevant regarding their respective roles as carbon sinks, as even the wildfire charcoals formed at the highest temperatures had lower carbon sequestration potentials than most slow-pyrolysis biochars. Our results challenge the common notion that natural charcoal and biochar are well suited as proxies for each other, and suggest that biochar's environmental residence time may be underestimated when based on natural charcoal as a proxy, and vice versa.
Yin, Yichao; Liu, Xiaofang; Wei, Xiaojun; Yu, Ronghai; Shui, Jianglan
2016-12-21
Porous carbon nanotubes/cobalt nanoparticles (CNTs/Co) composite with dodecahedron morphology was synthesized by in situ pyrolysis of the Co-based zeolitic imidazolate framework in a reducing atmosphere. The morphology and microstructure of the composite can be well tuned by controlling the pyrolysis conditions. At lower pyrolysis temperature, the CNTs/Co composite is composed of well-dispersed Co nanoparticles and short CNT clusters with low graphitic degree. The increase of pyrolysis temperature/time promotes the growth and graphitization of CNTs and leads to the aggregation of Co nanoparticles. The optimized CNTs/Co composite exhibits strong dielectric and magnetic losses as well as a good impedance matching property. Interestingly, the CNTs/Co composite displays extremely strong electromagnetic wave absorption with a maximum reflection loss of -60.4 dB. More importantly, the matching thickness of the absorber is as thin as 1.81 mm, and the filler loading of composite in the matrix is only 20 wt %. The highly efficient absorption is closely related to the well-designed structure and the synergistic effect between CNTs and Co nanoparticles. The excellent absorbing performance together with lightweight and ultrathin thickness endows the CNTs/Co composite with the potential for application in the electromagnetic wave absorbing field.
Effect of self-purging pyrolysis on yield of biochar from maize cobs, husks and leaves.
Intani, Kiatkamjon; Latif, Sajid; Kabir, A K M Rafayatul; Müller, Joachim
2016-10-01
In this study, biochar was produced from maize residues (cobs, husks, leaves) in a lab-scale pyrolysis reactor without using a purging gas. The physicochemical properties of biomass and biochar were analysed. Box-Behnken design was used to optimise operational conditions for biochar yields. Multivariate correlations of biochar yields were established using reduced quadratic models with R(2)=0.9949, 0.9801 and 0.9876 for cobs, husks and leaves, respectively. Biochar yields were negatively correlated with the temperature, which was significantly influenced by the exothermic reactions during the pyrolysis of maize residues. The heating rate was found to have the least effect on biochar yields. Under optimal conditions, the maximum biochar yields from cobs, husks and leaves were 33.42, 30.69 and 37.91%, respectively. The highest biochar yield from maize leaves was obtained at a temperature of 300°C, a heating rate of 15°C/min and a holding time of 30min. Copyright © 2016 Elsevier Ltd. All rights reserved.
Devi, Parmila; Saroha, Anil K
2015-09-01
The polycyclic aromatic hydrocarbons (PAHs) toxicity and sorption behaviour of biochars prepared from pyrolysis of paper mill effluent treatment plant (ETP) sludge in temperature range 200-700 °C was studied. The sorption behaviour was found to depend on the degree of carbonization where the fractions of carbonized and uncarbonized organic content in the biochar act as an adsorption media and partition media, respectively. The sorption and partition fractions were quantified by isotherm separation method and isotherm parameters were correlated with biochar properties (aromaticity, polarity, surface area, pore volume and ash content). The risk assessment for the 16 priority EPA PAHs present in the biochar matrix was performed and it was found that the concentrations of the PAHs in the biochar were within the permissible limits prescribed by US EPA (except BC400 and BC500 for high molecular weight PAHs). Copyright © 2015 Elsevier Ltd. All rights reserved.
Mechanical Behavior of a Hi-Nicalon(tm)/SiC Composite Having a Polycarbosilane Derived Matrix
NASA Technical Reports Server (NTRS)
Hurwitz, Frances I.; Calomino, Anthony M.; McCue, Terry R.
1999-01-01
Polymer infiltration of a rigidized preform, followed by pyrolysis to convert the polymer to a ceramic, potentially offers a lower cost alternative to CVD. It also offers more moderate temperature requirements than melt infiltration approaches, which should minimize potential fiber damage during processing. However, polymer infiltration and pyrolysis results in a more microcracked matrix. Preliminary mechanical property characterization, including elevated temperature (1204 C) tensile, 500 h stress rupture behavior and low cycle fatigue, was conducted on Hi-Nicalon (TM)/Si-C-(O) composites having a dual layer BN/SiC interface and a matrix derived by impregnation and pyrolysis of allylhydridopolycarbosilane (AHPCS). Microstructural evaluation of failure surfaces and of polished transverse and longitudinal cross sections of the failed specimens was used to identify predominant failure mechanisms. In stress rupture testing at 1093 C, the failure was interface dominated, while at 1204 C in both stress rupture and two hour hold/fatigue tests failure was matrix dominated, resulting in specimen delamination.
Pyrolysis of Date palm waste in a fixed-bed reactor: Characterization of pyrolytic products.
Bensidhom, Gmar; Ben Hassen-Trabelsi, Aïda; Alper, Koray; Sghairoun, Maher; Zaafouri, Kaouther; Trabelsi, Ismail
2018-01-01
The pyrolysis of several Tunisian Date Palm Wastes (DPW): Date Palm Rachis (DPR), Date Palm Leaflets (DPL), Empty Fruit Bunches (EFB) and Date Palm Glaich (DPG) was run using a fixed-bed reactor, from room temperature to 500°C, with 15°C/min as heating rate and -5°C as condensation temperature, in order to produce bio-oil, biochar and syngas. In these conditions, the bio-oil yield ranges from 17.03wt% for DPL to 25.99wt% for EFB. For the biochar, the highest yield (36.66wt%) was obtained for DPL and the lowest one (31.66wt%) was obtained from DPG while the syngas production varies from 39.10wt% for DPR to 46.31wt% DPL. The raw material and pyrolysis products have been characterized using elemental analysis thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM). The syngas composition has been characterized using gas analyzer. Copyright © 2017 Elsevier Ltd. All rights reserved.
Biomass-based pyrolytic polygeneration system on cotton stalk pyrolysis: influence of temperature.
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.
An analysis of a charring ablator with thermal nonequilibrium, chemical kinetics, and mass transfer
NASA Technical Reports Server (NTRS)
Clark, R. K.
1973-01-01
The differential equations governing the transient response of a one-dimensional ablative thermal protection system are presented for thermal nonequilibrium between the pyrolysis gases and the char layer and with finite rate chemical reactions occurring. The system consists of three layers (the char layer, the uncharred layer, and an optical insulation layer) with concentrated heat sinks at the back surface and between the second and third layers. The equations are solved numerically by using a modified implicit finite difference scheme to obtain solutions for the thickness of the charred and uncharred layers, surface recession and pyrolysis rates, solid temperatures, porosity profiles, and profiles of pyrolysis-gas temperature, pressure, composition, and flow rate. Good agreement is obtained between numerical results and exact solutions for a number of simplified cases. The complete numerical analysis is used to obtain solutions for an ablative system subjected to a constant heating environment. Effects of thermal, chemical, and mass transfer processes are shown.
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.
Low temperature pyrolysis of coal or oil shale in the presence of calcium compounds
Khan, M. Rashid
1988-01-01
A coal pyrolysis technique or process is described in which particulate coal is pyrolyzed in the presence of about 5 to 21 wt. % of a calcium compound selected from calcium oxide, calcined (hydrate) dolomite, or calcined calcium hydrate to produce a high quality hydrocarbon liquid and a combustible product gas which are characterized by low sulfur content. The pyrolysis is achieved by heating the coal-calcium compound mixture at a relatively slow rate at a temperature of about 450.degree. to 700.degree. C. over a duration of about 10 to 60 minutes in a fixed or moving bed reactor. The gas exhibits an increased yield in hydrogen and C.sub.1 -C.sub.8 hydrocarbons and a reduction in H.sub.2 S over gas obtainable by pyrolyzing cola without the calcium compound. The liquid product obtained is of a sufficient quality to permit its use directly as a fuel and has a reduced sulfur and oxygen content which inhibits polymerization during storage.
Duan, Dengle; Ruan, Roger; Wang, Yunpu; Liu, Yuhuan; Dai, Leilei; Zhao, Yunfeng; Zhou, Yue; Wu, Qiuhao
2018-03-01
This study performed microwave-assisted acid pretreatment on pure lignin. The effects of microwave temperature, microwave time, and hydrochloric acid concentration on characteristics and pyrolysis behavior of lignin were examined. Results of ultimate analysis revealed better properties of all pretreated samples than those of raw lignin. Fourier transform infrared spectroscopy analysis showed breakage of βO4 bond and aliphatic side chain, decrease in OH groups, and formation of CO groups in pretreatment. Microwave temperature exerted more significant influence on lignin structure. Thermal stability of treated lignin was improved and insensitive to short microwave time and acid concentration under mild conditions. Resulting from improved alkyl-phenols and decreased alkoxy-phenols, microwave-assisted acid pretreatment of lignin yielded bio-oil with excellent quality. Total yield of phenols in pyrolysis vapors (200 °C) improved to 14.15%, whereas that of guaiacols decreased to 22.36%. This study shows that microwave-assisted acid pretreatment is a promising technology for lignin conversion. Copyright © 2017 Elsevier Ltd. All rights reserved.
Biomass Pyrolysis Solids as Reducing Agents: Comparison with Commercial Reducing Agents
Adrados, Aitziber; De Marco, Isabel; López-Urionabarrenechea, Alexander; Solar, Jon; Caballero, Blanca M.; Gastelu, Naia
2015-01-01
Biomass is one of the most suitable options to be used as renewable energy source due to its extensive availability and its contribution to reduce greenhouse gas emissions. Pyrolysis of lignocellulosic biomass under appropriate conditions (slow heating rate and high temperatures) can produce a quality solid product, which could be applicable to several metallurgical processes as reducing agent (biocoke or bioreducer). Two woody biomass samples (olives and eucalyptus) were pyrolyzed to produce biocoke. These biocokes were characterized by means of proximate and ultimate analysis, real density, specific surface area, and porosity and were compared with three commercial reducing agents. Finally, reactivity tests were performed both with the biocokes and with the commercial reducing agents. Bioreducers have lower ash and sulfur contents than commercial reducers, higher surface area and porosity, and consequently, much higher reactivity. Bioreducers are not appropriate to be used as top burden in blast furnaces, but they can be used as fuel and reducing agent either tuyére injected at the lower part of the blast furnace or in non-ferrous metallurgical processes where no mechanical strength is needed as, for example, in rotary kilns. PMID:28787805
Vertically Aligned Carbon Nanotubes at Different Temperatures by Spray Pyrolysis Techniques
NASA Astrophysics Data System (ADS)
Afre, Rakesh A.; Soga, T.; Jimbo, T.; Kumar, Mukul; Ando, Y.; Sharon, M.
Vertically aligned arrays of multi-walled carbon nanotubes (VACNTs) were grown by spray pyrolysis of turpentine oil and ferrocene mixture at temperatures higher than 700°C. Using this simple method, we report the successful growth of vertically aligned nanotubes of ~300μm length and diameter in the range of ?20-80nm on Si(100) substrate. The ferrocene acts as an in situ Fe catalyst precursor, forming the nano-sized metallic iron particles for formation of VACNTs on the Si substrate. The morphological characteristics of VACNTs are confirmed by SEM, TEM and Raman spectroscopy and growth mechanism is discussed in short.
Predicting properties of gas and solid streams by intrinsic kinetics of fast pyrolysis of wood
Klinger, Jordan; Bar-Ziv, Ezra; Shonnard, David; ...
2015-12-12
Pyrolysis has the potential to create a biocrude oil from biomass sources that can be used as fuel or as feedstock for subsequent upgrading to hydrocarbon fuels or other chemicals. The product distribution/composition, however, is linked to the biomass source. This work investigates the products formed from pyrolysis of woody biomass with a previously developed chemical kinetics model. Different woody feedstocks reported in prior literature are placed on a common basis (moisture, ash, fixed carbon free) and normalized by initial elemental composition through ultimate analysis. Observed product distributions over the full devolatilization range are explored, reconstructed by the model, andmore » verified with independent experimental data collected with a microwave-assisted pyrolysis system. These trends include production of permanent gas (CO, CO 2), char, and condensable (oil, water) species. Elementary compositions of these streams are also investigated. As a result, close agreement between literature data, model predictions, and independent experimental data indicate that the proposed model/method is able to predict the ideal distribution from fast pyrolysis given reaction temperature, residence time, and feedstock composition.« less
Zhang, Chao; Shan, Baoqing; Tang, Wenzhong; Zhu, Yaoyao
2017-08-01
Phyllostachys pubescens (PP) biochars produced under a low oxygen pyrolysis atmosphere (oxygen content 1-4%) were prepared as sorbents for investigating the mechanisms of cadmium and lead sorption. A low-oxygen pyrolysis atmosphere increased biochar ash and specific surface area, promoting heavy metal precipitation and complexation. The maximum sorption capacity (Q m ) of Pb 2+ obtained from the Langmuir model was 67.4mg·g -1 , while Q m of Cd 2+ was 14.7mg·g -1 . The contribution of each mechanism varied with increasing oxygen content at a low pyrolysis temperature. Mineral precipitation with Pb 2+ was the predominant mechanism for Pb 2+ removal and the contribution proportion significantly increased from 17.2% to 71.7% as pyrolysis oxygen atmosphere increased from 0% to 4%. The results showed that cadmium sorption primarily involved coordination with π electrons, at 54.1-82.6% of the total adsorption capacity. The PP biochar shows potential for application in removing heavy metal contaminants, especially Pb 2+ . Copyright © 2017 Elsevier Ltd. All rights reserved.
Microwave pyrolysis of distillers dried grain with solubles (DDGS) for biofuel production.
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.
Agrawal, Ankit; Chakraborty, Saikat
2013-01-01
This work uses thermo-gravimetric, differential thermo-gravimetric and differential thermal analyses to evaluate the kinetics of pyrolysis (in inert/N(2) atmosphere) and (oxidative) combustion of microalgae Chlorella vulgaris by heating from 50 to 800 °C at heating rates of 5-40 °C/min. This study shows that combustion produces higher biomass conversion than pyrolysis, and that three stages of decomposition occur in both cases, of which, the second one--consisting of two temperature zones--is the main stage of devolatization. Proteins and carbohydrates are decomposed in the first of the two zones at activation energies of 51 and 45 kJ/mol for pyrolysis and combustion, respectively, while lipids are decomposed in its second zone at higher activation energies of 64 and 63 kJ/mol, respectively. The kinetic expressions of the reaction rates in the two zones for pyrolysis and combustion have been obtained and it has been shown that increased heating rates result in faster and higher conversion. Copyright © 2012 Elsevier Ltd. All rights reserved.
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
Oh, Seung-Jin; Jung, Su-Hwa; Kim, Joo-Sik
2013-09-01
Corncob was pyrolyzed using ZnCl2 in a pyrolysis plant equipped with a fluidized bed reactor to co-produce furfural and acetic acid. The effects of reaction conditions, the ZnCl2 content and contacting method of ZnCl2 with corncob on the yields of furfural and acetic acid were investigated. The pyrolysis was performed within the temperature range between 310 and 410°C, and the bio-oil yield were 30-60 wt% of the product. The furfural yield increased up to 8.2 wt%. The acetic acid yield was maximized with a value of 13.1 wt%. A lower feed rate in the presence of ZnCl2 was advantageous for the production of acetic acid. The fast pyrolysis of a smaller corncob sample mechanically mixed with 20 wt% of ZnCl2 gave rise to a distinct increase in furfural. A high selectivity for furfural and acetic acid in bio-oil would make the pyrolysis of corncob with ZnCl2 very economically attractive. Copyright © 2013 Elsevier Ltd. All rights reserved.
Hu, Yuyan; Yang, Fan; Chen, Fangfang; Feng, Yuheng; Chen, Dezhen; Dai, Xiaohu
2018-05-01
Co-pyrolysis with sewage sludge was proved to be an efficient pre-treatment for sanitary landfill of municipal solid waste incineration (MSWI) fly ash (FA). In this study, to improve the stabilization effect of heavy metals, mixed ferrous/ferric sulfate was added into the FA/SS mixture before pyrolysis. To examine the feasibility of the landfill of co-pyrolysis char, toxicity characteristic leaching procedure (HJ/T300) was conducted. In addition, physio-chemical characteristics of char were also tested to explain the stability of heavy metals, including the speciation, mineralogical composition and the morphological features of them. The results indicated that within the range that the obtained char could meet the standard for landfill (GB16889-2008), the appropriate addition of mixed ferrous/ferric sulfates benefit to raising the FA ratio in the FA/SS mixture. The maximum ratio of 67 wt% is achieved when the additive was 1.5 wt% of dried SS (based on iron element) and the pyrolysis temperature was 500 °C. Copyright © 2018 Elsevier Ltd. All rights reserved.
Apparatus for fixed bed coal gasification
Sadowski, Richard S.
1992-01-01
An apparatus for fixed-bed coal gasification is described in which coal such as caking coal is continuously pyrolyzed with clump formation inhibited, by combining the coal with a combustible gas and an oxidant, and then continually feeding the pyrolyzed coal under pressure and elevated temperature into the gasification region of a pressure vessel. The materials in the pressure vessel are allowed to react with the gasifying agents in order to allow the carbon contents of the pyrolyzed coal to be completely oxidized. 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.
Physical and chemical characterization of biochars derived from different agricultural residues
NASA Astrophysics Data System (ADS)
Jindo, K.; Mizumoto, H.; Sawada, Y.; Sanchez-Monedero, M. A.; Sonoki, T.
2014-12-01
Biochar is widely recognized as an efficient tool for carbon sequestration and soil fertility. The understanding of its chemical and physical properties, which are strongly related to the type of the initial material used and pyrolysis conditions, is crucial to identify the most suitable application of biochar in soil. A selection of organic wastes with different characteristics (e.g., rice husk (RH), rice straw (RS), wood chips of apple tree (Malus pumila) (AB), and oak tree (Quercus serrata) (OB)) were pyrolyzed at different temperatures (400, 500, 600, 700, and 800 °C) in order to optimize the physicochemical properties of biochar as a soil amendment. Low-temperature pyrolysis produced high biochar yields; in contrast, high-temperature pyrolysis led to biochars with a high C content, large surface area, and high adsorption characteristics. Biochar obtained at 600 °C leads to a high recalcitrant character, whereas that obtained at 400 °C retains volatile and easily labile compounds. The biochar obtained from rice materials (RH and RS) showed a high yield and unique chemical properties because of the incorporation of silica elements into its chemical structure. The biochar obtained from wood materials (AB and OB) showed high carbon content and a high absorption character.