Analyse quantitative des effluents de pyrolyse en milieu ouvert et fermé Quantitative Analysis of Pyrolysis Effluents in an Open and Closed System

Directory of Open Access Journals (Sweden)

Behar F.

2006-11-01

Full Text Available Dans la première partie de l'article, nous décrivons une technique de pyrolyse en milieu ouvert qui permet de caractériser les matières organiques complexes comme le kérogène, le charbon, les asphaltènes de roche et d'huiles, les substances humiques et fulviques etc. Les effluents de pyrolyse sont récupérés et fractionnés quantitativement puis analysés par des techniques spécifiques comme la chromatographie en phase gazeuse et le couplage chromatographie/spectrométrie de masse. Dans la deuxième partie, est présentée une technique de pyrolyse en milieu fermé pour simuler au laboratoire l'évolution thermique des kérogènes, asphaltènes ou huiles. Nous nous sommes surtout attachés à dresser des bilans massiques et des bilans de l'hydrogène sur l'ensemble des produits de pyrolyse. Pour cela, nous avons distingué cinq classes de poids moléculaire croissant : C1, C2-C5, C6-C13, C14+ et coke. La récupération quantitative et la séparation de chacune des cinq fractions permet une analyse moléculaire détaillée de chacune d'elles. The first part of this article describes an open pyrolysis system in order to characterize complex organic matter such as kerogen, coal, rock and oil asphaltenes and humic substances, etc. Pyrolysis effluents are recovered, fractionated quantitatively by liquid chromatography, and then they are analyzed by specific techniques such as gas chromatography and chromatography/mass-spectrometry coupling. The second part describes a pyrolysis technique in a closed system, used for the laboratory simulation of the thermal evolution of kerogens, asphaltenes or oils. A special effort has been made to give the mass and hydrogen balances for all pyrolysis products. For this, five classes have been distinguised with increasing molecular weight: C1, C2-C5, C6-C13, C14+ and coke. The quantitative recovery and the separation of each of the five fractions is used to make a detailed molecular analysis of each of

Improving accuracy and precision of ice core δD(CH4 analyses using methane pre-pyrolysis and hydrogen post-pyrolysis trapping and subsequent chromatographic separation

Directory of Open Access Journals (Sweden)

M. Bock

2014-07-01

Full Text Available Firn and polar ice cores offer the only direct palaeoatmospheric archive. Analyses of past greenhouse gas concentrations and their isotopic compositions in air bubbles in the ice can help to constrain changes in global biogeochemical cycles in the past. For the analysis of the hydrogen isotopic composition of methane (δD(CH4 or δ2H(CH4 0.5 to 1.5 kg of ice was hitherto used. Here we present a method to improve precision and reduce the sample amount for δD(CH4 measurements in (ice core air. Pre-concentrated methane is focused in front of a high temperature oven (pre-pyrolysis trapping, and molecular hydrogen formed by pyrolysis is trapped afterwards (post-pyrolysis trapping, both on a carbon-PLOT capillary at −196 °C. Argon, oxygen, nitrogen, carbon monoxide, unpyrolysed methane and krypton are trapped together with H2 and must be separated using a second short, cooled chromatographic column to ensure accurate results. Pre- and post-pyrolysis trapping largely removes the isotopic fractionation induced during chromatographic separation and results in a narrow peak in the mass spectrometer. Air standards can be measured with a precision better than 1‰. For polar ice samples from glacial periods, we estimate a precision of 2.3‰ for 350 g of ice (or roughly 30 mL – at standard temperature and pressure (STP – of air with 350 ppb of methane. This corresponds to recent tropospheric air samples (about 1900 ppb CH4 of about 6 mL (STP or about 500 pmol of pure CH4.

Characterization of some sedimentary sequences from Cambay basin, India, by pyrolysis-GC

Science.gov (United States)

Philp, R. P.; Garg, A. K.

Pyrolysis-gas chromatography of sedimentary sequences from a key exploratory well of the southern Cambay Basin, India, has been performed to characterize the nature of the source material and its maturity. In samples from the Eocene-Paleocene section (2960-3407 m), the pyrolysate is dominated by hydrocarbons in the lower molecular weight region indicating a significant input algal source material. The presence of various xylenes and phenols in the pyrograms is indicative of a significant input from higher plant material. The organic material in this section is interpreted to have been derived from marine-terrestrial source inputs deposited under swampy to marine and reducing environments. Good mature source rocks with type III kerogens which are wet gas/gas condensate-prone have been identified in this region. This paper intends to discuss the characterization of source rocks using the pyrolysis-gas chromatography approach and the significance of the distribution of the pyrolysis product.

DEPOSITIONAL ENVIRONMENT AND ORGANIC GEOCHEMICAL CHARACTERISTICS OF LOWER EOCENE BITUMINOUS ROCKS, IN THE KÜRNÜÇ/GÖYNÜK-BOLU AREA

Directory of Open Access Journals (Sweden)

Ali SARI

2016-12-01

Full Text Available In this study, dark gray and dark brown colored, organic-carbon rich bituminous rocks (bituminous marl and bituminous shale exposing around the Kürnüç area (Göynük, Bolu are investigated by means of or- ganic geochemical characteristics. In this respect, rock lithologies, depositional environments, rock source potential, kerogen and organic maturity types and hydrocarbon generation potentials of bituminous rocks were determined. For this reason, pyrolysis (Rock Eval–VI analysis, gas chromatography (GC and gas chromatography-mass spectrometer (GC-MS analyses were carried out. In addition, spore color index (SCI was determined with organic petrographic method and stable carbon analysis (δ13C of the samples were also conducted. Lithology of the studied samples is of clastic source and the depositional environ- ment is a lagoon with a partial connection to the sea. In bituminous rocks with excellent source rock potential TOC values are in the range of 2.52-8.38 wt % (average 6.08 wt %. With the exception of two samples (Type II kerogen type of all samples is Type I. According to pyrolysis, GC and GC-MS organic maturity results, all the samples are in immature stage. Organic geochemical data indicate that bituminous rocks have an excellent oil generation potential and there is no organic contamination.

Geochemistry of Eagle Ford group source rocks and oils from the first shot field area, Texas

Science.gov (United States)

Edman, Janell D.; Pitman, Janet K.; Hammes, Ursula

2010-01-01

Total organic carbon, Rock-Eval pyrolysis, and vitrinite reflectance analyses performed on Eagle Ford Group core and cuttings samples from the First Shot field area, Texas demonstrate these samples have sufficient quantity, quality, and maturity of organic matter to have generated oil. Furthermore, gas chromatography and biomarker analyses performed on Eagle Ford Group oils and source rock extracts as well as weight percent sulfur analyses on the oils indicate the source rock facies for most of the oils are fairly similar. Specifically, these source rock facies vary in lithology from shales to marls, contain elevated levels of sulfur, and were deposited in a marine environment under anoxic conditions. It is these First Shot Eagle Ford source facies that have generated the oils in the First Shot Field. However, in contrast to the generally similar source rock facies and organic matter, maturity varies from early oil window to late oil window in the study area, and these maturity variations have a pronounced effect on both the source rock and oil characteristics. Finally, most of the oils appear to have been generated locally and have not experienced long distance migration. 

Analytical pyrolysis and stable isotope analyses reveal past environmental changes in coralloid speleothems from Easter Island (Chile).

Science.gov (United States)

Miller, Ana Z; De la Rosa, José M; Jiménez-Morillo, Nicasio T; Pereira, Manuel F C; González-Pérez, José A; Calaforra, José M; Saiz-Jimenez, Cesareo

2016-08-26

This study comprises an innovative approach based on the combination of chromatography (analytical pyrolysis and pyrolysis compound-specific isotope analysis (Py-CSIA)), light stable isotopes, microscopy and mineralogy analyses to characterize the internal layering of coralloid speleothems from the Ana Heva lava tube in Easter Island (Chile). This multidisciplinary proxy showed that the speleothems consist of banded siliceous materials of low crystallinity with different mineralogical compositions and a significant contribution of organic carbon. Opal-A constitutes the outermost grey layer of the coralloids, whereas calcite and amorphous Mg hydrate silicate are the major components of the inner whitish and honey-brown layers, respectively. The differences found in the mineralogical, elemental, molecular and isotopic composition of these distinct coloured layers are related to environmental changes during speleothem development. Stable isotopes and analytical pyrolysis suggested alterations in the water regime, pointing to wetter conditions during the formation of the Ca-rich layer and a possible increase in the amount of water dripping into the cave. The trend observed for δ(15)N values suggested an increase in the average temperature over time, which is consistent with the so-called climate warming during the Holocene. The pyrolysis compound-specific isotope analysis of each speleothem layer showed a similar trend with the bulk δ(13)C values pointing to the appropriateness of direct Py-CSIA in paleoenvironmental studies. The δ(13)C values for n-alkanes reinforced the occurrence of a drastic environmental change, indicating that the outermost Opal layer was developed under drier and more arid environmental conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Science.gov (United States)

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

2014-01-01

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

Experimental investigation of the role of rock fabric in gas generation and expulsion during thermal maturation: Anhydrous closed-system pyrolysis of a bitumen-rich Eagle Ford Shale

Science.gov (United States)

Shao, Deyong; Ellis, Geoffrey S.; Li, Yanfang; Zhang, Tongwei

2018-01-01

Gold-tube pyrolysis experiments were conducted on miniature core plugs and powdered rock from a bitumen-rich sample of Eagle Ford Shale to investigate the role of rock fabric in gas generation and expulsion during thermal maturation. The samples were isothermally heated at 130, 300, 310, 333, 367, 400, and 425 °C for 72 h under a confining pressure of 68.0 MPa, corresponding to six levels of induced thermal maturity: pre-oil generation (130 °C/72 h), incipient oil/bitumen generation (300 and 310 °C/72 h), early oil generation (333 °C/72 h), peak oil generation (367 °C/72 h), early oil cracking (400 °C/72 h), and late oil cracking (425 °C/72 h). Experimental results show that gas retention coupled with compositional fractionation occurs in the core plug experiments and varies as a function of thermal maturity. During the incipient oil/bitumen generation stage, yields of methane through pentane (C1–C5) from core plugs are significantly lower than those from rock powder, and gases from core plugs are enriched in methane. However, the differences in C1–C5 gas yield and composition decrease throughout the oil generation stage, and by the oil cracking stage no obvious compositional difference in C1–C5 gases exists. The decrease in the effect of rock fabric on gas yield and composition with increasing maturity is the result of an increase in gas expulsion efficiency. Pyrolysis of rock powder yields 4–16 times more CO2 compared to miniature core plugs, with δ13CCO2 values ranging from −2.9‰ to −0.6‰, likely due to carbonate decomposition accelerated by reactions with organic acids. Furthermore, lower yields of gaseous alkenes and H2 from core plug experiments sugge

Production, properties and utilisation of pyrolysis oil

Energy Technology Data Exchange (ETDEWEB)

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

1997-12-01

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

Source rock

Directory of Open Access Journals (Sweden)

Abubakr F. Makky

2014-03-01

Full Text Available West Beni Suef Concession is located at the western part of Beni Suef Basin which is a relatively under-explored basin and lies about 150 km south of Cairo. The major goal of this study is to evaluate the source rock by using different techniques as Rock-Eval pyrolysis, Vitrinite reflectance (%Ro, and well log data of some Cretaceous sequences including Abu Roash (E, F and G members, Kharita and Betty formations. The BasinMod 1D program is used in this study to construct the burial history and calculate the levels of thermal maturity of the Fayoum-1X well based on calibration of measured %Ro and Tmax against calculated %Ro model. The calculated Total Organic Carbon (TOC content from well log data compared with the measured TOC from the Rock-Eval pyrolysis in Fayoum-1X well is shown to match against the shale source rock but gives high values against the limestone source rock. For that, a new model is derived from well log data to calculate accurately the TOC content against the limestone source rock in the study area. The organic matter existing in Abu Roash (F member is fair to excellent and capable of generating a significant amount of hydrocarbons (oil prone produced from (mixed type I/II kerogen. The generation potential of kerogen in Abu Roash (E and G members and Betty formations is ranging from poor to fair, and generating hydrocarbons of oil and gas prone (mixed type II/III kerogen. Eventually, kerogen (type III of Kharita Formation has poor to very good generation potential and mainly produces gas. Thermal maturation of the measured %Ro, calculated %Ro model, Tmax and Production index (PI indicates that Abu Roash (F member exciting in the onset of oil generation, whereas Abu Roash (E and G members, Kharita and Betty formations entered the peak of oil generation.

Predicting bi-decadal organic carbon mineralization in northwestern European soils with Rock-Eval pyrolysis

Science.gov (United States)

Soucemarianadin, Laure; Barré, Pierre; Baudin, François; Chenu, Claire; Houot, Sabine; Kätterer, Thomas; Macdonald, Andy; van Oort, Folkert; Plante, Alain F.; Cécillon, Lauric

2017-04-01

The organic carbon reservoir of soils is a key component of climate change, calling for an accurate knowledge of the residence time of soil organic carbon (SOC). Existing proxies of the size of SOC labile pool such as SOC fractionation or respiration tests are time consuming and unable to consistently predict SOC mineralization over years to decades. Similarly, models of SOC dynamics often yield unrealistic values of the size of SOC kinetic pools. Thermal analysis of bulk soil samples has recently been shown to provide useful and cost-effective information regarding the long-term in-situ decomposition of SOC. Barré et al. (2016) analyzed soil samples from long-term bare fallow sites in northwestern Europe using Rock-Eval 6 pyrolysis (RE6), and demonstrated that persistent SOC is thermally more stable and has less hydrogen-rich compounds (low RE6 HI parameter) than labile SOC. The objective of this study was to predict SOC loss over a 20-year period (i.e. the size of the SOC pool with a residence time lower than 20 years) using RE6 indicators. Thirty-six archive soil samples coming from 4 long-term bare fallow chronosequences (Grignon, France; Rothamsted, Great Britain; Ultuna, Sweden; Versailles, France) were used in this study. For each sample, the value of bi-decadal SOC mineralization was obtained from the observed SOC dynamics of its long-term bare fallow plot (approximated by a spline function). Those values ranged from 0.8 to 14.3 gC·kg-1 (concentration data), representing 8.6 to 50.6% of total SOC (proportion data). All samples were analyzed using RE6 and simple linear regression models were used to predict bi-decadal SOC loss (concentration and proportion data) from 4 RE6 parameters: HI, OI, PC/SOC and T50 CO2 oxidation. HI (the amount of hydrogen-rich effluents formed during the pyrolysis phase of RE6; mgCH.g-1SOC) and OI (the CO2 yield during the pyrolysis phase of RE6; mgCO2.g-1SOC) parameters describe SOC bulk chemistry. PC/SOC (the amount of organic

Geochemical investigation of petroleum source rocks by using Rock- Eval data in the Agha-Jari oilfield

Directory of Open Access Journals (Sweden)

Behzad khani

2015-01-01

Full Text Available In this study, 40 drilling cutting of the Pabdeh, Gurpi, kazhdumi and Gadvan Formations from the Agha-Jari Oilfield were analyzed by using Rock-Eval pyrolysis. In order to recognizing sedimentary environmental conditions of studied Formations, they are divided to 4 zones which A (Kazhdumi Formation#187 and C (Kazhdumi Formation#140 zones show reduction conditions by presence of sea organic materials and B (Gadvan Formation #140 and D(Gadvan Formation#187 zones show oxidation conditions by presence of continental organic materials to basin. Based on the Rock-Eval pyrolysis data, the Pabeh, Gurpi, Kazhdumi and Gadvan Formations have variable hydrocarbon generative potential. HI vs. OI plot revealed that the kerogen type in this Formations is a mixed of types II & III. The intensity of matrix effect in the Pabdeh, Gurpi, Kazhdumi and Gadvan Formations was compared by using S2 vs. TOC plot and calculating its regression equation. The results show that the significant amount of S2 adsorption by matrix was happened in the Pabdeh (4.98-6.96 mg HC/gr rock in wells 113 and 121 and Gurpi Formations ‌(4.33 mg HC/gr rock in well 113 which is due to their low thermal maturity‌(Tmax

Geochemical characterization of the hydrous pyrolysis products from a recent cyanobacteria-dominated microbial mat

Energy Technology Data Exchange (ETDEWEB)

Franco, N.; Mendoça-Filho, J.G.; Silva, T.F.; Stojanovic, K.; Fontana, L.F.; Carvalhal-Gomes, S.B.V.; Silva, F.S.; Furukawa, G.G.

2016-07-01

Hydrous pyrolysis experiments were performed on a recent microbial mat sample from Lagoa Vermelha, Brazil, to determine whether crude oil can be generated and expelled during artificial maturation of the Organic Matter (OM). The experiments were conducted at 280ºC, 330ºC and 350ºC during 20h. Two types of liquid pyrolysis products, assigned as free oil and bitumen, were isolated and analyzed. Free oil represents free organic phase released by hydrous pyrolysis, whereas bitumen was obtained by extraction from the solid pyrolysis residue with dichloromethane. Changes in the OM maturity were determined using Rock-Eval parameters and biomarker maturity ratios of original sample and pyrolysis products. Biomarker compositions of original sample extract and liquid pyrolysates were used for determination of dominant bacterial source. The yields of free oil and bitumen showed that a microbial mat OM has a high liquid hydrocarbons generation potential. Rock-Eval maturity parameters, biopolymer and biomarker compositions indicate a significant increase of the OM maturity during hydrous pyrolysis. At 280ºC the release of free, adsorbed and occluded compounds was observed; however, without a cracking of the OM. At 330ºC the generation of bitumen and free oil is mostly related to the OM cracking. The highest yield of free oil was recorded at this temperature. Distribution of biomarkers in the extract of original sample and liquid pyrolysates confirms cyanobacteria-dominated microbial mats, whereas the identification of long chain n-alkane series, with maximum at C26, and prominent C30 hop-17(21)-ene additionally suggest the presence of sulfate reducing bacteria. (Author)

Chemical analysis of minerals in granitic rocks by electron probe micro analyser

International Nuclear Information System (INIS)

Hiraoka, Yoshihiro

1994-01-01

The chemical compositions of minerals in a few granitic rocks were determined by electron probe micro analyser (EPMA). The accurate analytical data for standard feldspar groups were obtained by correcting the low analytical values of sodium and potassium that were arised from the damage in EPMA analysis. Using this method, feldspar groups and biotites in three granitic rocks gathered from Hiei, Hira and Kurama areas respectively, were analyzed. As the results, the local characteristics were observed in the kinds of feldspar groups and the chemical compositions of biotites that were contained in granitic rocks. (author)

Identification and Quantification of Carbonate Species Using Rock-Eval Pyrolysis

Directory of Open Access Journals (Sweden)

Pillot D.

2013-03-01

Full Text Available This paper presents a new reliable and rapid method to characterise and quantify carbonates in solid samples based on monitoring the CO2 flux emitted by progressive thermal decomposition of carbonates during a programmed heating. The different peaks of destabilisation allow determining the different types of carbonates present in the analysed sample. The quantification of each peak gives the respective proportions of these different types of carbonates in the sample. In addition to the chosen procedure presented in this paper, using a standard Rock-Eval 6 pyrolyser, calibration characteristic profiles are also presented for the most common carbonates in nature. This method should allow different types of application for different disciplines, either academic or industrial.

Organic Geochemistry of the Cenomanian-Turonian Bahloul Formation Petroleum Source Rock, Central and Northern Tunisia

OpenAIRE

Affouri , Hassene; Montacer , Mabrouk; Disnar , Jean-Robert

2013-01-01

International audience; Total organic carbon (TOC) determination, Rock-Eval pyrolysis, extractable organic matter content (EOM) fractionation, gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) analyses, were carried out on 79 samples from eleven outcrop cross sections of the Bahloul Formation in central and northern Tunisia. The TOC content varied between 0.23 to 35.6%, the highest average values (18.73%, 8.46% and 4.02%) being at the east of the study area (at Ain Zakk...

PETROS - Worldwide Databank of Major Element Chemical Analyses of Igneous Rocks

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — PETROS is a worldwide data bank of major element chemical analyses of igneous rocks compiled for research and teaching purposes by Dr. Felix Mutschler and Staff at...

Chemical analyses of rocks, minerals, and detritus, Yucca Mountain--Preliminary report, special report No. 11

International Nuclear Information System (INIS)

Hill, C.A.; Livingston, D.E.

1993-09-01

This chemical analysis study is part of the research program of the Yucca Mountain Project intended to provide the State of Nevada with a detailed assessment of the geology and geochemistry of Yucca Mountain and adjacent regions. This report is preliminary in the sense that more chemical analyses may be needed in the future and also in the sense that these chemical analyses should be considered as a small part of a much larger geological data base. The interpretations discussed herein may be modified as that larger data base is examined and established. All of the chemical analyses performed to date are shown in Table 1. There are three parts to this table: (1) trace element analyses on rocks (limestone and tuff) and minerals (calcite/opal), (2) rare earth analyses on rocks (tuff) and minerals (calcite/opal), and (3) major element analyses + CO 2 on rocks (tuff) and detritus sand. In this report, for each of the three parts of the table, the data and its possible significance will be discussed first, then some overall conclusions will be made, and finally some recommendations for future work will be offered

Evolution of sulfur speciation in bitumen through hydrous pyrolysis induced thermal maturation of Jordanian Ghareb Formation oil shale

Science.gov (United States)

Birdwell, Justin E.; Lewan, Michael; Bake, Kyle D.; Bolin, Trudy B.; Craddock, Paul R.; Forsythe, Julia C.; Pomerantz, Andrew E.

2018-01-01

Previous studies on the distribution of bulk sulfur species in bitumen before and after artificial thermal maturation using various pyrolysis methods have indicated that the quantities of reactive (sulfide, sulfoxide) and thermally stable (thiophene) sulfur moieties change following consistent trends under increasing thermal stress. These trends show that sulfur distributions change during maturation in ways that are similar to those of carbon, most clearly illustrated by the increase in aromatic sulfur (thiophenic) as a function of thermal maturity. In this study, we have examined the sulfur moiety distributions of retained bitumen from a set of pre- and post-pyrolysis rock samples in an organic sulfur-rich, calcareous oil shale from the Upper Cretaceous Ghareb Formation. Samples collected from outcrop in Jordan were subjected to hydrous pyrolysis (HP). Sulfur speciation in extracted bitumens was examined using K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The most substantial changes in sulfur distribution occurred at temperatures up to the point of maximum bitumen generation (∼300 °C) as determined from comparison of the total organic carbon content for samples before and after extraction. Organic sulfide in bitumen decreased with increasing temperature at relatively low thermal stress (200–300 °C) and was not detected in extracts from rocks subjected to HP at temperatures above around 300 °C. Sulfoxide content increased between 200 and 280 °C, but decreased at higher temperatures. The concentration of thiophenic sulfur increased up to 300 °C, and remained essentially stable under increasing thermal stress (mg-S/g-bitumen basis). The ratio of stable-to-reactive+stable sulfur moieties ([thiophene/(sulfide+sulfoxide+thiophene)], T/SST) followed a sigmoidal trend with HP temperature, increasing slightly up to 240 °C, followed by a substantial increase between 240 and 320 °C, and approaching a constant value (∼0.95) at

Coal pyrolysis. VII. Economic viability of pyrolysis. Pirolisis del carbon. VII. Viabilidad economica de la pirolisis

Energy Technology Data Exchange (ETDEWEB)

Molinar, R.; Adanez, J.; Miranda, J.L.; Ibarra, J.V. (Instituto de Carboquimica, Zaragoza (Spain))

1989-04-01

Analyses the most important economic parameters of the main pyrolysis processes. Considers the markets available for semi-coke and tars. Concludes that no single technology or process has clear advantages over the others because all depends on the type of coal being used and the purpose for which the end product is to be used. Refers to studies carried out in Canada and the USA on the same subject and reports their findings. Concludes optimistically that coal pyrolysis shows promise of being economically viable in the future because although initially, costs reflect the high financial outlay necessary to begin operations, after a certain period, these costs fall and the end product can be sold at a lower price. A further point in favour of pyrolysis is that coal prices are likely to rise more slowly than oil prices. 5 refs., 8 tabs.

Pore Scale Analysis of Oil Shale/Sands Pyrolysis

Energy Technology Data Exchange (ETDEWEB)

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

2011-03-01

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

Measured sections and analyses of uranium host rocks of the Dockum Group, New Mexico and Texas

International Nuclear Information System (INIS)

Dickson, R.E.; Drake, D.P.; Reese, T.J.

1977-02-01

This report presents 27 measured sections from the Dockum Group of Late Triassic age, in the southern High Plains of eastern New Mexico and northwestern Texas. Many of the measured sections are only partial; the intent in those cases was to measure the parts of sections that had prominent sandstone/conglomerate beds or that had uranium deposits. No attempt was made to relate rock color to a rock color chart; rock colors are therefore approximate. Modal analyses (by thin-section examination) of sandstone and conglomerate samples and gamma-ray spectrometric analyses of the samples are presented in appendices

Lead isotope analyses of standard rock samples

International Nuclear Information System (INIS)

Koide, Yoshiyuki; Nakamura, Eizo

1990-01-01

New results on lead isotope compositions of standard rock samples and their analytical procedures are reported. Bromide form anion exchange chromatography technique was adopted for the chemical separation lead from rock samples. The lead contamination during whole analytical procedure was low enough to determine lead isotope composition of common natural rocks. Silica-gel activator method was applied for emission of lead ions in the mass spectrometer. Using the data reduction of 'unfractionated ratios', we obtained good reproducibility, precision and accuracy on lead isotope compositions of NBS SRM. Here we present new reliable lead isotope compositions of GSJ standard rock samples and USGS standard rock, BCR-1. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

1995-12-31

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1996-12-31

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

Hydrocarbon Source Rock Potential of the Sinamar Formation, Muara Bungo, Jambi

Directory of Open Access Journals (Sweden)

Moh. Heri Hermiyanto Zajuli

2014-07-01

Full Text Available DOI: 10.17014/ijog.v1i1.175The Oligocene Sinamar Formation consists of shale, claystone, mudstone, sandstone, conglomeratic sandstone, and intercalation of coal seams. The objective of study was to identify the hydrocarbon source rock potential of the Sinamar Formation based on geochemichal characteristics. The analyses were focused on fine sediments of the Sinamar Formation comprising shale, claystone, and mudstone. Primary data collected from the Sinamar Formation well and outcrops were analyzed according to TOC, pyrolisis analysis, and gas chromatography - mass spectometry of normal alkanes that include isoprenoids and sterane. The TOC value indicates a very well category. Based on TOC versus Pyrolysis Yields (PY diagram, the shales of Sinamar Formation are included into oil prone source rock potential with good to excellent categories. Fine sediments of the Sinamar Formation tend to produce oil and gas originated from kerogen types I and III. The shales tend to generate oil than claystone and mudstone and therefore they are included into a potential source rock. 

Kinetics of Pyrolysis and Gasification Using Thermogravimetric and Thermovolumetric Analyses

Directory of Open Access Journals (Sweden)

Czerski Grzegorz

2016-03-01

Full Text Available The carbon dioxide gasification process of Miscanthus giganteus biomass was examined using two methods. First an isothermal thermovolumetric method was applied. The measurement was conducted at 950°C and pressure of 0.1 MPa. Based on the continuous analysis of different kinds of gases formed during the gasification process, the thermovolumetric method allowed the determination of yields and composition of the resulting gas as well as the rate constant of CO formation. Then a non-isothermal thermogravimetric method was applied, during which the loss of weight of a sample as a function of temperature was recorded. In the course of the measurement, the temperature was raised from ambient to 950°C and the pressure was 0.1 MPa. As a result, a change in the carbon conversion degree was obtained. Moreover, TGA methods allow distinguishing various stages of the gasification process such as primary pyrolysis, secondary pyrolysis and gasification, and determining kinetic parameters for each stage. The presented methods differs from each other as they are based either on the analysis of changes in the resulting product or on the analysis of changes in the supplied feedstock, but both can be successfully used to the effective examination of kinetics of the gasification process. In addition, an important advantage of both methods is the possibility to carry out the gasification process for different solid fuels as coal, biomass, or solid waste in the atmosphere of a variety of gasification agents.

Depositional environment and source rock potential of Cenomanian and Turonian sedimentary rocks of the Tarfaya Basin, Southwest Morocco

Energy Technology Data Exchange (ETDEWEB)

Ghassal, B.I.; Littke, R.; Sachse, V.; Sindern, S.; Schwarzbauer, J.

2016-07-01

Detailed organic and inorganic geochemical analyses were used to assess the depositional environment and source rock potential of the Cenomanian and Turonian oil shale deposits in the Tarfaya Basin. This study is based on core samples from the Tarfaya Sondage-4 well that penetrated over 300m of Mid Cretaceous organic matter-rich deposits. A total of 242 samples were analyzed for total organic and inorganic carbon and selected samples for total sulfur and major elements as well as for organic petrology, Rock-Eval pyrolysis, Curie-Point-pyrolysis-gaschromatography-Mass-Spectrometry and molecular geochemistry of solvent extracts. Based on major elements the lower Cenomanian differs from the other intervals by higher silicate and lower carbonate contents. Moreover, the molecular geochemistry suggests anoxic bottom marine water conditions during the Cenomanian-Turonian Boundary Event (CTBE; Oceanic Anoxic Event 2: OAE2). As a proxy for the Sorg/Corg ratio, the ratio total thiophenes/total benzenes compounds was calculated from pyrolysate compositions. The results suggest that Sorg/ Corg is low in the lower Cenomanian, moderate in the upper Cenomanian, very high in the CTBE (CenomanianTuronian Boundary Event) and high in the Turonian samples. Rock-Eval data reveal that the lower Cenomanian is a moderately organic carbon-rich source rock with good potential to generate oil and gas upon thermal maturation. On the other hand, the samples from the upper Cenomanian to Turonian exhibit higher organic carbon content and can be classified as oil-prone source rocks. Based on Tmax data, all rocks are thermally immature. The microscopic investigations suggest dominance of submicroscopic organic matter in all samples and different contents of bituminite and alginite. The lower Cenomanian samples have little visible organic matter and no bituminite. The upper Cenomanian and CTBE samples are poor in bituminite and have rare visible organic matter, whereas the Turonian samples change

A steady state model of agricultural waste pyrolysis: A mini review.

Science.gov (United States)

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.

Pyrolysis and oxidative pyrolysis experiments with organization exchange resin

International Nuclear Information System (INIS)

Chun, Ung Kyung

1997-01-01

Pyrolysis may be an important pretreatment step before vitrification in a cold crucible melter (CCM). During vitrification of organic resin the carbon or other remaining residues may harm the performance of the cold crucible melter of the eventual stability of the final glass product. Hence, it is important to reduce or prevent such harmful waste from entry into the cold crucible melter. Pretreatment with pyrolysis will generally provide volume reduction resulting in less amount of solid waste that needs to be handled by the CCM; in addition, the pyrolytic processes may breakdown much of the complex organics causing release through volatilization resulting in less carbon and other harmful substances. Hence, KEPRI has undertaken studies on the pyrolysis and oxidative pyrolysis of organic ion exchange resin. Pyrolysis and oxidative pyrolysis were examined with TGA and a tube furnace. TGA results for pyrolysis with the flow of nitrogen indicate that even after pyrolyzing from room temperature to about 900 deg C, a significant mass fraction of the original cationic resin remains, approximately 46 %. The anionic resin when pyrolytically heated in a flow of nitrogen only, from room temperature to about 900 deg C, produced a final residue mass fraction of about 8 percent. Oxidation at a ratio of air to nitrogen, 1:2, reduced the cationic resin to 5.3% when heated at 5 C/min. Oxidation of anionic resin at the same ratio and same heating rate left almost no solid residue. Pyrolysis (e.g. nitrogen-only environment) in the tube furnace of larger samples relative to the TGA produced very similar results to the TGA. The differences may be attributed to the scale effects such as surface area exposure to the gas stream, temperature distributions throughout the resin, etc. (author) 7 refs., 7 figs

Pyrolysis and oxidative pyrolysis experiments with organization exchange resin

Energy Technology Data Exchange (ETDEWEB)

Chun, Ung Kyung [Korea Electric Power Research Insititute, Taejon (Korea, Republic of)

1997-12-31

Pyrolysis may be an important pretreatment step before vitrification in a cold crucible melter (CCM). During vitrification of organic resin the carbon or other remaining residues may harm the performance of the cold crucible melter of the eventual stability of the final glass product. Hence, it is important to reduce or prevent such harmful waste from entry into the cold crucible melter. Pretreatment with pyrolysis will generally provide volume reduction resulting in less amount of solid waste that needs to be handled by the CCM; in addition, the pyrolytic processes may breakdown much of the complex organics causing release through volatilization resulting in less carbon and other harmful substances. Hence, KEPRI has undertaken studies on the pyrolysis and oxidative pyrolysis of organic ion exchange resin. Pyrolysis and oxidative pyrolysis were examined with TGA and a tube furnace. TGA results for pyrolysis with the flow of nitrogen indicate that even after pyrolyzing from room temperature to about 900 deg C, a significant mass fraction of the original cationic resin remains, approximately 46 %. The anionic resin when pyrolytically heated in a flow of nitrogen only, from room temperature to about 900 deg C, produced a final residue mass fraction of about 8 percent. Oxidation at a ratio of air to nitrogen, 1:2, reduced the cationic resin to 5.3% when heated at 5 C/min. Oxidation of anionic resin at the same ratio and same heating rate left almost no solid residue. Pyrolysis (e.g. nitrogen-only environment) in the tube furnace of larger samples relative to the TGA produced very similar results to the TGA. The differences may be attributed to the scale effects such as surface area exposure to the gas stream, temperature distributions throughout the resin, etc. (author) 7 refs., 7 figs.

EFFECT OF AQUEOUS PRETREATMENT ON PYROLYSIS CHARACTERISTICS OF NAPIER GRASS

Directory of Open Access Journals (Sweden)

ISAH YAKUB MOHAMMED

2015-11-01

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

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

Science.gov (United States)

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

2018-04-01

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

Extent of pyrolysis impacts on fast pyrolysis biochar properties.

Science.gov (United States)

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

2012-01-01

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

The Study of Kinetic Properties and Analytical Pyrolysis of Coconut Shells

Directory of Open Access Journals (Sweden)

Mahir Said

2015-01-01

Full Text Available The kinetic properties of coconut shells during pyrolysis were studied to determine its reactivity in ground form. The kinetic parameters were determined by using thermogravimetric analyser. The activation energy was 122.780 kJ/mol. The pyrolysis products were analyzed using pyrolysis gas chromatography/mass spectrometry (Py-GC/MS. The effects of pyrolysis temperature on the distribution of the pyrolytic products were assessed in a temperature range between 673 K and 1073 K. The set time for pyrolysis was 2 s. Several compounds were observed; they were grouped into alkanes, acids, ethers and alcohols, esters, aldehydes and ketones, furans and pyrans, aromatic compounds, and nitrogen containing compounds. The product compositions varied with temperature in that range. The highest gas proportion was observed at high temperature while the acid proportion was observed to be highest in coconut shells, thus lowering the quality of bio-oil. It has been concluded that higher pyrolysis temperature increases the amount of pyrolysis products to a maximum value. It has been recommended to use coconut shell for production of gas, instead of production of bio-oil due to its high proportion of acetic acid.

Validation Results for Core-Scale Oil Shale Pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Staten, Josh; Tiwari, Pankaj

2015-03-01

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

Recent Advances in Analytical Pyrolysis to Investigate Organic Materials in Heritage Science.

Science.gov (United States)

Degano, Ilaria; Modugno, Francesca; Bonaduce, Ilaria; Ribechini, Erika; Colombini, Maria Perla

2018-06-18

The molecular characterization of organic materials in samples from artworks and historical objects traditionally entailed qualitative and quantitative analyses by HPLC and GC. Today innovative approaches based on analytical pyrolysis enable samples to be analysed without any chemical pre-treatment. Pyrolysis, which is often considered as a screening technique, shows previously unexplored potential thanks to recent instrumental developments. Organic materials that are macromolecular in nature, or undergo polymerization upon curing and ageing can now be better investigated. Most constituents of paint layers and archaeological organic substances contain major insoluble and chemically non-hydrolysable fractions that are inaccessible to GC or HPLC. To date, molecular scientific investigations of the organic constituents of artworks and historical objects have mostly focused on the minor constituents of the sample. This review presents recent advances in the qualitative and semi-quantitative analyses of organic materials in heritage objects based on analytical pyrolysis coupled with mass spectrometry. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

2017-12-01

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

Modelling of biomass pyrolysis

International Nuclear Information System (INIS)

Kazakova, Nadezhda; Petkov, Venko; Mihailov, Emil

2015-01-01

Pyrolysis is an essential preliminary step in a gasifier. The first step in modelling the pyrolysis process of biomass is creating a model for the chemical processes taking place. This model should describe the used fuel, the reactions taking place and the products created in the process. The numerous different polymers present in the organic fraction of the fuel are generally divided in three main groups. So, the multistep kinetic model of biomass pyrolysis is based on conventional multistep devolatilization models of the three main biomass components - cellulose, hemicelluloses, and lignin. Numerical simulations have been conducted in order to estimate the influence of the heating rate and the temperature of pyrolysis on the content of the virgin biomass, active biomass, liquid, solid and gaseous phases at any moment. Keywords: kinetic models, pyrolysis, biomass pyrolysis.

Flash pyrolysis kinetics of pine wood

NARCIS (Netherlands)

Wagenaar, B.M.; Prins, W.; van Swaaij, Willibrordus Petrus Maria

1993-01-01

The kinetics of sawdust pyrolysis in the temperature range from 300 to 600 °C has been measured. A thermogravimetric analyser was applied for the temperature range from 300 to 450 °C while for measurements in the temperature range from 450 to 600 °C, an entrained flow reactor has been used. The

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Olive bagasse (Olea europa L.) pyrolysis

Energy Technology Data Exchange (ETDEWEB)

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

2006-02-15

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

Petrographic and Geochemical Analyses of Kirana Hills Shield Rocks around Sargodha and Economic Potential

Directory of Open Access Journals (Sweden)

Muhammad Waseem Khan

2017-04-01

Full Text Available The present study deals with geochemical and petrographic analysis of the Kirana Hill shield rocks of Punjab plains from Buland, Hachi, Shaheen Abad, Shaikh and Machh hills. On basis of the current studies certain modifications have been made in the classification and nomenclature of rocks exposed in the study areas. Chemical analyses have also been carried out in order to calculate Cross Iddings, Pirsson, and Washington (CIPW norms”, to strengthen nomenclature scheme and finally rocks are classified by using “MAGMA SOFTWARE”. Rhyolites predominate over the basalts/dolerites, andesites, and phyllite/ slate. Rhyolitic rocks are light grey, greenish grey and light brown in color, aphanitic in nature. The observed microscopic textures are aphyric, phyric or porphyritic and micropoikilitc. Moreover, some rhyolitic rocks also show flow texture. They are either cryptocrystalline to microcrystalline or microcrystalline to cryptocrystalline. No glassy material has been observed in any thin section. Mafic rocks are characterized by the presence of ferromagnesian minerals with plagioclase. Andesites exhibit mainly porphyritic texture, but aphyric texture has also been observed in few samples. Hydrothermal alterations are also very common in these rocks. Other rock assemblages identified during laboratory studies from Kirana area include: tuffs i.e. (Lithic Crystal Tuff and Lithic Tuff, basaltic andesite, rhyodacite/ dacite, slate/ phyllite, ankeritic rocks/ veins and quartzofeldspathic veins. Our studies also reveal that no evidence of quartzite has been found in the samples collected from above mentioned areas of Kirana, although it has been reported in previous literature. Iron (Fe has been observed in rhyolite as well as other volcanic rocks of Kirana hills, its presence suggests magma from deep mantle instead of crustal melting / anatexis. In the present analysis some primary and secondary copper minerals including chalcopyrite, atacamite and

Modeling of biomass pyrolysis

International Nuclear Information System (INIS)

Samo, S.R.; Memon, A.S.; Akhund, M.A.

1995-01-01

The fuels used in industry and power sector for the last two decades have become expensive. As a result renewable energy source have been emerging increasingly important, of these, biomass appears to be the most applicable in the near future. The pyrolysis of biomass plays a key role amongst the three major and important process generally encountered in a gas producer, namely, pyrolysis, combustion and reduction of combustion products. Each biomass has its own pyrolysis characteristics and this important parameters must be known for the proper design and efficient operation of a gasification system. Thermogravimetric analysis has been widely used to study the devolatilization of solid fuels, such as biomass. It provides the weight loss history of a sample heated at a predetermined rate as a function of time and temperature. This paper presents the experimental results of modelling the weight loss curves of the main biomass components i.e. cellulose, hemicellulose and lignin. Thermogravimetric analysis of main components of biomass showed that pyrolysis is first order reaction. Furthermore pyrolysis of cellulose and hemicelluloe can be regarded as taking place in two stages, for while lignin pyrolysis is a single stage process. This paper also describes the Thermogravimetric Analysis (TGA) technique to predict the weight retained during pyrolysis at any temperature, for number of biomass species, such as cotton stalk, bagasse ad graoundnut shell. (author)

Pyrolysis characteristics of typical biomass thermoplastic composites

Directory of Open Access Journals (Sweden)

Hongzhen Cai

Full Text Available 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. Keywords: Biomass thermoplastic composite, Calcium carbonate, Pyrolysis characteristic

Thermal-maturity limit for primary thermogenic-gas generation from humic coals as determined by hydrous pyrolysis

Science.gov (United States)

Lewan, Michael; Kotarba, M.J.

2014-01-01

Hydrous-pyrolysis experiments at 360°C (680°F) for 72 h were conducted on 53 humic coals representing ranks from lignite through anthracite to determine the upper maturity limit for hydrocarbon-gas generation from their kerogen and associated bitumen (i.e., primary gas generation). These experimental conditions are below those needed for oil cracking to ensure that generated gas was not derived from the decomposition of expelled oil generated from some of the coals (i.e., secondary gas generation). Experimental results showed that generation of hydrocarbon gas ends before a vitrinite reflectance of 2.0%. This reflectance is equivalent to Rock-Eval maximum-yield temperature and hydrogen indices (HIs) of 555°C (1031°F) and 35 mg/g total organic carbon (TOC), respectively. At these maturity levels, essentially no soluble bitumen is present in the coals before or after hydrous pyrolysis. The equivalent kerogen atomic H/C ratio is 0.50 at the primary gas-generation limit and indicates that no alkyl moieties are remaining to source hydrocarbon gases. The convergence of atomic H/C ratios of type-II and -I kerogen to this same value at a reflectance of indicates that the primary gas-generation limits for humic coal and type-III kerogen also apply to oil-prone kerogen. Although gas generation from source rocks does not exceed vitrinite reflectance values greater than , trapped hydrocarbon gases can remain stable at higher reflectance values. Distinguishing trapped gas from generated gas in hydrous-pyrolysis experiments is readily determined by of the hydrocarbon gases when a -depleted water is used in the experiments. Water serves as a source of hydrogen in hydrous pyrolysis and, as a result, the use of -depleted water is reflected in the generated gases but not pre-existing trapped gases.

Laser induced pyrolysis techniques

International Nuclear Information System (INIS)

Vanderborgh, N.E.

1976-01-01

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

Modelling solid-convective flash pyrolysis of straw and wood in the Pyrolysis Centrifuge Reactor

DEFF Research Database (Denmark)

Bech, Niels; Larsen, Morten Boberg; Jensen, Peter Arendt

2009-01-01

in the Pyrolysis Centrifuge Reactor, a novel solid-convective flash pyrolysis reactor. The model relies on the original concept for ablative pyrolysis of particles being pyrolysed through the formation of an intermediate liquid compound which is further degraded to form liquid organics, char, and gas. To describe...

Recycling slaughterhouse waste into fertilizer: how do pyrolysis temperature and biomass additions affect phosphorus availability and chemistry?

Science.gov (United States)

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.

Pyrolysis characteristics of typical biomass thermoplastic composites

Science.gov (United States)

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.

Pyrolysis Model Development for a Multilayer Floor Covering

Directory of Open Access Journals (Sweden)

Mark B. McKinnon

2015-09-01

Full Text Available Comprehensive pyrolysis models that are integral to computational fire codes have improved significantly over the past decade as the demand for improved predictive capabilities has increased. High fidelity pyrolysis models may improve the design of engineered materials for better fire response, the design of the built environment, and may be used in forensic investigations of fire events. A major limitation to widespread use of comprehensive pyrolysis models is the large number of parameters required to fully define a material and the lack of effective methodologies for measurement of these parameters, especially for complex materials. The work presented here details a methodology used to characterize the pyrolysis of a low-pile carpet tile, an engineered composite material that is common in commercial and institutional occupancies. The studied material includes three distinct layers of varying composition and physical structure. The methodology utilized a comprehensive pyrolysis model (ThermaKin to conduct inverse analyses on data collected through several experimental techniques. Each layer of the composite was individually parameterized to identify its contribution to the overall response of the composite. The set of properties measured to define the carpet composite were validated against mass loss rate curves collected at conditions outside the range of calibration conditions to demonstrate the predictive capabilities of the model. The mean error between the predicted curve and the mean experimental mass loss rate curve was calculated as approximately 20% on average for heat fluxes ranging from 30 to 70 kW·m−2, which is within the mean experimental uncertainty.

Pyrolysis Characteristics and Kinetics of Phoenix Tree Residues as a Potential Energy

Directory of Open Access Journals (Sweden)

H. Li

2015-09-01

Full Text Available By using a thermogravimetric analyser under argon atmosphere, the pyrolysis process and the kinetic model of phoenix tree residues (the little stem, middle stem, and leaf at a 30 °C min−1 heating rate and the phoenix tree mix at three different heating rates (10 °C min−1, 30 °C min−1, and 50 °C min−1 were examined. The catalyst and the co-pyrolysis samples were at a 30 °C min−1 heating rate. The catalysts were Na2CO3, ZnCl2 and CaO in a mass fraction of 5 %. The experimental results revealed that the phoenix tree residues pyrolysis process consisted of three stages: dehydration stage, main pyrolysis stage, and the slow decomposition of residues. As the heating rate increased, the pyrolysis characteristic temperature of the phoenix tree grew, there was a backward-shift of the pyrolysis rate curve, and the mass loss rate gradually increased. The phoenix tree residues’ activation energy changed throughout the whole pyrolysis process, and the pyrolysis temperature ranges of the three main components (cellulose, hemicellulose, and lignin existed in overlapping phenomenon. As compared to the little stem, middle stem, and leaf, the phoenix tree mix was more likely to be pyrolysed under the same heating rate. Different catalysts had a different impact on the pyrolysis: ZnCl2 moved the start point of the reaction to the lower temperatures, but did not speed up the reaction; Na2CO3 speeded up the reaction without changing the start point of the reaction; CaO speeded up the reaction, moved the start point of the reaction to higher temperatures.

Understanding the fast pyrolysis of lignin.

Science.gov (United States)

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

2011-11-18

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

Refining fast pyrolysis of biomass

NARCIS (Netherlands)

Westerhof, Roel Johannes Maria

2011-01-01

Pyrolysis oil produced from biomass is a promising renewable alternative to crude oil. Such pyrolysis oil has transportation, storage, and processing benefits, none of which are offered by the bulky, inhomogeneous solid biomass from which it originates. However, pyrolysis oil has both a different

Pyrolysis oil as diesel fuel

Energy Technology Data Exchange (ETDEWEB)

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

1997-12-31

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

Pyrolysis oil as diesel fuel

Energy Technology Data Exchange (ETDEWEB)

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

1996-12-31

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

Fast Pyrolysis of Lignin Using a Pyrolysis Centrifuge Reactor

DEFF Research Database (Denmark)

Trinh, Ngoc Trung; Jensen, Peter Arendt; Sárossy, Zsuzsa

2013-01-01

Fast pyrolysis of lignin from an ethanol plant was investigated on a lab scale pyrolysis centrifuge reactor (PCR) with respect to pyrolysis temperature, reactor gas residence time, and feed rate. A maximal organic oil yield of 34 wt % dry basis (db) (bio-oil yield of 43 wt % db) is obtained...... at temperatures of 500−550 °C, reactor gas residence time of 0.8 s, and feed rate of 5.6 g/min. Gas chromatography mass spectrometry and size-exclusion chromatography were used to characterize the Chemical properties of the lignin oils. Acetic acid, levoglucosan, guaiacol, syringols, and p-vinylguaiacol are found...... components and molecular mass distribution of the lignin oils. The obtained lignin oil has a very different components composition when compared to a beech wood oil....

Pyrolysis of Coconut Shell: An Experimental Investigation

Directory of Open Access Journals (Sweden)

E. Ganapathy Sundaram

2009-12-01

Full Text Available Fixed-bed slow pyrolysis experiments of coconut shell have been conducted to determine the effect of pyrolysis temperature, heating rate and particle size on the pyrolysis product yields. The effect of vapour residence time on the pyrolysis yield was also investigated by varying the reactor length. Pyrolysis experiments were performed at pyrolysis temperature between 400 and 600°C with a constant heating rate of 60°C/min and particle sizes of 1.18-1.80 mm. The optimum process conditions for maximizing the liquid yield from the coconut shell pyrolysis in a fixed bed reactor were also identified. The highest liquid yield was obtained at a pyrolysis temperature of 550 °C, particle size of 1.18-1.80 mm, with a heating rate of 60 °C/min in a 200 mm length reactor. The yield of obtained char, liquid and gas was 22-31 wt%, 38-44 wt% and 30-33 wt% respectively at different pyrolysis conditions. The results indicate that the effects of pyrolysis temperature and particle size on the pyrolysis yield are more significant than that of heating rate and residence time. The various characteristics of pyrolysis oil obtained under the optimum conditions for maximum liquid yield were identified on the basis of standard test methods.

The use of tyre pyrolysis oil in diesel engines.

Science.gov (United States)

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

2008-12-01

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

Analytical solutions for recession analyses of sloping aquifers - applicability on relict rock glaciers in alpine catchments

Science.gov (United States)

Pauritsch, Marcus; Birk, Steffen; Hergarten, Stefan; Kellerer-Pirklbauer, Andreas; Winkler, Gerfried

2014-05-01

Rock glaciers as aquifer systems in alpine catchments may strongly influence the hydrological characteristics of these catchments. Thus, they have a high impact on the ecosystem and potential natural hazards such as for example debris flow. Therefore, knowledge of the hydrodynamic processes, internal structure and properties of these aquifers is important for resource management and risk assessment. The investigation of such aquifers often turns out to be expensive and technically complicated because of their strongly limited accessibility. Analytical solutions of discharge recession provide a quick and easy way to estimate aquifer parameters. However, due to simplifying assumptions the validity of the interpretation is often questionable. In this study we compared results of an analytical solution of discharge recessions with results based on a numerical model. This was done in order to analyse the range of uncertainties and the applicability of the analytical method in alpine catchment areas. The research area is a 0.76 km² large catchment in the Seckauer Tauern Range, Austria. The dominant aquifer in this catchment is a rock glacier, namely the Schöneben Rock Glacier. This relict rock glacier (i.e. containing no permafrost at present) covers an area of 0.11 km² and is drained by one spring at the rock glacier front. The rock glacier consists predominantly of gneissic sediments (mainly coarse-grained, blocky at the surface) and extends from 1720 to 1905 m a.s.l.. Discharge of the rock glacier spring is automatically measured since 2002. Electric conductivity and water temperature is monitored since 2008. An automatic weather station was installed in 2011 in the central part of the catchment. Additionally data of geophysical surveys (refraction seismic and ground penetrating radar) have been used to analyse the base slope and inner structure of the rock glacier. The measured data are incorporated into a numerical model implemented in MODFLOW. The numerical

Hybrid-renewable processes for biofuels production: concentrated solar pyrolysis of biomass residues

Energy Technology Data Exchange (ETDEWEB)

George, Anthe [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Geier, Manfred [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Dedrick, Daniel E. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2014-10-01

The viability of thermochemically-derived biofuels can be greatly enhanced by reducing the process parasitic energy loads. Integrating renewable power into biofuels production is one method by which these efficiency drains can be eliminated. There are a variety of such potentially viable "hybrid-renewable" approaches; one is to integrate concentrated solar power (CSP) to power biomass-to-liquid fuels (BTL) processes. Barriers to CSP integration into BTL processes are predominantly the lack of fundamental kinetic and mass transport data to enable appropriate systems analysis and reactor design. A novel design for the reactor has been created that can allow biomass particles to be suspended in a flow gas, and be irradiated with a simulated solar flux. Pyrolysis conditions were investigated and a comparison between solar and non-solar biomass pyrolysis was conducted in terms of product distributions and pyrolysis oil quality. A novel method was developed to analyse pyrolysis products, and investigate their stability.

Experimental and Chemical Kinetic Modeling Study of Dimethylcyclohexane Oxidation and Pyrolysis

KAUST Repository

Eldeeb, Mazen A.

2016-08-30

A combined experimental and chemical kinetic modeling study of the high-temperature ignition and pyrolysis of 1,3-dimethylcyclohexane (13DMCH) is presented. Ignition delay times are measured behind reflected shock waves over a temperature range of 1049–1544 K and pressures of 3.0–12 atm. Pyrolysis is investigated at average pressures of 4.0 atm at temperatures of 1238, 1302, and 1406 K. By means of mid-infrared direct laser absorption at 3.39 μm, fuel concentration time histories are measured under ignition and pyrolytic conditions. A detailed chemical kinetic model for 13DMCH combustion is developed. Ignition measurements show that the ignition delay times of 13DMCH are longer than those of its isomer, ethylcyclohexane. The proposed chemical kinetic model predicts reasonably well the effects of equivalence ratio and pressure, with overall good agreement between predicted and measured ignition delay times, except at low dilution levels and high pressures. Simulated fuel concentration profiles agree reasonably well with the measured profiles, and both highlight the influence of pyrolysis on the overall ignition kinetics at high temperatures. Sensitivity and reaction pathway analyses provide further insight into the kinetic processes controlling ignition and pyrolysis. The work contributes toward improved understanding and modeling of the oxidation and pyrolysis kinetics of cycloalkanes.

ANALYSES OF ROCK SURFACE COLOUR CHANGES DUE TO WEATHERING

OpenAIRE

GOKAY, Mehmet Kemal

2018-01-01

Description parameters of rock masses and minerals include their colours as well. Colours appear in daylight for surfaced rock masses are changing slightly due to weathering layers which have been covering its surface gradually. Healthy human eyes can manage to differentiate visible light spectrum to identify colours of substances including rock masses. Then visible blackish colours of magnetite minerals, reddish colours of Terra- Rosa soils, greenish colours of weathered copper ore, pure whi...

ANALYSES OF ROCK SURFACE COLOUR CHANGES DUE TO WEATHERING

OpenAIRE

GÖKAY, Mehmet Kemal

2018-01-01

Description parameters of rock masses and minerals include their colours as well. Colours appear in daylight for surfaced rock masses are changing slightly due to weathering layers which have been covering its surface gradually. Healthy human eyes can manage to differentiate visible spectrum to identify the colours of substance including rock masses. Then visible blackish colours of magnetite minerals, reddish colours of Terra- Rosa soils, greenish colours of weathered copper ore, pure white ...

Pyrolysis of Municipal Green Waste: A Modelling, Simulation and Experimental Analysis

Directory of Open Access Journals (Sweden)

Mohammed J. Kabir

2015-07-01

Full Text Available Pyrolysis is the thermo-chemical conversion of carbonaceous feedstock in the absence of oxygen to produce bio-fuel (bio-oil, bio-char and syn-gas. Bio-fuel production from municipal green waste (MGW through the pyrolysis process has attracted considerable attention recently in the renewable energy sector because it can reduce greenhouse gas emissions and contribute to energy security. This study analyses properties of MGW feedstock available in Rockhampton city of Central Queensland, Australia, and presents an experimental investigation of producing bio-fuel from that MGW through the pyrolysis process using a short sealed rotary furnace. It was found from the experiment that about 19.97% bio-oil, 40.83% bio-char and 29.77% syn-gas can be produced from the MGW. Then, a four-stage steady state simulation model is developed for pyrolysis process performance simulation using Aspen Plus software. In the first stage, the moisture content of the MGW feed is reduced. In the second stage, the MGW is decomposed according to its elemental constituents. In the third stage, condensate material is separated and, finally, the pyrolysis reactions are modelled using the Gibbs free energy minimisation approach. The MGW’s ultimate and proximate analysis data were used in the Aspen Plus simulation as input parameters. The model is validated with experimentally measured data. A good agreement between simulation and experimental results was found. More specifically, the variation of modelling and experimental elemental compositions of the MGW was found to be 7.3% for carbon, 15.82% for hydrogen, 7.04% for nitrogen and 5.56% for sulphur. The validated model is used to optimise the biofuel production from the MGW as a function of operating variables such as temperature, moisture content, particle size and process heat air–fuel ratio. The modelling and optimisation results are presented, analysed and discussed.

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Catalytic biomass pyrolysis process

Science.gov (United States)

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

2018-04-17

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

Organic geochemical characterization of potential hydrocarbon source rocks in the upper Benue Trough

International Nuclear Information System (INIS)

Obaje, N. G.; Pearson, M. J.; Suh, C. E.; Dada, S. S.

1999-01-01

The Upper Benue Trough of Nigeria is the northeastern most portion of the Benue rift structure that extends from the northern limit of the Niger Delta in the south to the southern limit of the Chad basin int he northeast. this portion of the trough is made up of two arms: the Gongola Arm and the Yola Arm. Stratigraphic sequence in the Gongola Arm comprises the continental Albian Bima Sandstone, the transitional Cenomanian Yolde Formation and the marine Turonian - Santonian Gongila, Pindiga, and Fika Formations. Overlying these are the continental Campane - Maastrichtian Gombe Sandstone and the Tertiary Kerri - Kerri Formation. In the Yola Arm, the Turonian - Santonian sequence is replaced by the equally marine Dukul, Jessu, Sekuliye Formations, Numanha Shale, and the Lamja Sandstone. Organic geochemical studies have been carried on outcrop sample form the Gongila, Pindiga, Dukul Formations, the Fika shale and the shaly units of the Gombe Sandstone, with the aim of assessing their source rock potential. Gas Chromatography (GC), Gas Chromatography - Mass Spectrometry (C - MS), and Rock Eval Pyrolysis were the major organic geochemical tools employed. Biomaker hydrocarbon signatures obtained from the GC - MS and the Rock Eval Pyrolysis results indicate that all he formations studied, except the Dukul formation, are immature and are all lean in organic matter

Pyrolysis of spent ion-exchanger resins

International Nuclear Information System (INIS)

Slametschka, Rainer; Braehler, Georg

2012-01-01

Initial tests have shown that ion exchangers (IEX) can be decomposed by pyrolysis with very good results, yielding an inert and chemically resistant product. No additives are necessary. The main constituent of the product, the pyrolysis residues or ash, is carbon. It has been discovered that the entire radioactive inventory remains in the pyrolysis residues during pyrolysis of the IEX. This is achieved by relatively low process temperatures that prevent highly volatile nuclides such as the caesium nuclides from passing into the gaseous phase. Sintered metal filters in pyrolysis plant ensure that even the radioactivity bonded to the dust remains in the pyrolysis residues. In addition to the radionuclides, the main constituents of the residue are carbon from the original polystyrene matrix and sulphur from the functional groups. The pyrolysis residues form a flowable solid material and not a melt. It is thus easy to handle and can be compacted or cemented, depending on the requirements for interim and permanent storage. Any further constituents such as inorganic filter materials or even other organic materials do not interfere with the process, they are dried, calcined or also pyrolysed. (orig.)

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

Science.gov (United States)

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

2016-01-01

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

Fractional condensation of biomass pyrolysis vapors

NARCIS (Netherlands)

Westerhof, Roel Johannes Maria; Brilman, Derk Willem Frederik; Garcia Perez, M.; Wang, Zhouhong; Oudenhoven, Stijn; van Swaaij, Willibrordus Petrus Maria; Kersten, Sascha R.A.

2011-01-01

In this paper, we have investigated the possibilities to steer the composition and, thus, the quality of pyrolysis liquids by the reactor temperature and the pyrolysis vapor condenser temperature. Pine wood was pyrolyzed in a 1 kg/h fluidized-bed pyrolysis reactor operated at 330 or 480 °C. The

Pyrolysis technologies for municipal solid waste: A review

Energy Technology Data Exchange (ETDEWEB)

Chen, Dezhen, E-mail: chendezhen@tongji.edu.cn [Thermal and Environmental Engineering Institute, Tongji University, Shanghai 200092 (China); Yin, Lijie; Wang, Huan [Thermal and Environmental Engineering Institute, Tongji University, Shanghai 200092 (China); He, Pinjing [State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China)

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 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, 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.

Analysing the breakthrough of rock 'n' roll (1930-1970) Multi-regime interaction and reconfiguration in the multi-level perspective

OpenAIRE

Geels, Frank W.

2007-01-01

The breakthrough of rock 'n' roll was part of broader transformations in the American music industry, involving changes in music instruments, music recording technology, audiences, radio programming and music styles. These transformations will be analysed as sociotechnical transition, using the multi-level perspective. One characteristic of the case is interactions between multiple regimes: radio and recording. Another characteristic is the presence of strong cultural components, with rock 'n...

Pyrolysis characteristics and pyrolysis products separation for recycling organic materials from waste liquid crystal display panels

Energy Technology Data Exchange (ETDEWEB)

Wang, Ruixue; Xu, Zhenming, E-mail: zmxu@sjtu.edu.cn

2016-01-25

Highlights: • Pyrolysis characteristics are conducted for a better understanding of LCDs pyrolysis. • Optimum design is developed which is significant to guide the further industrial process. • Acetic acid and TPP are recycled and separated. - Abstract: Waste liquid crystal display (LCD) panels mainly contain inorganic materials (glass substrate with indium-tin oxide film), and organic materials (polarizing film and liquid crystal). The organic materials should be removed beforehand since the organic matters would hinder the indium recycling process. In the present study, pyrolysis process is used to remove the organic materials and recycle acetic as well as and triphenyl phosphate (TPP) from waste LCD panels in an environmental friendly way. Several highlights of this study are summarized as follows: (i) Pyrolysis characteristics and pyrolysis kinetics analysis are conducted which is significant to get a better understanding of the pyrolysis process. (ii) Optimum design is developed by applying Box–Behnken Design (BBD) under response surface methodology (RSM) for engineering application which is significant to guide the further industrial recycling process. The oil yield could reach 70.53 wt% and the residue rate could reach 14.05 wt% when the pyrolysis temperature is 570 °C, nitrogen flow rate is 6 L min{sup −1} and the particle size is 0.5 mm. (iii) Furthermore, acetic acid and TPP are recycled, and then separated by rotary evaporation, which could reduce the consumption of fossil energy for producing acetic acid, and be reused in electronics manufacturing industry.

Pyrolysis characteristics and pyrolysis products separation for recycling organic materials from waste liquid crystal display panels

International Nuclear Information System (INIS)

Wang, Ruixue; Xu, Zhenming

2016-01-01

Highlights: • Pyrolysis characteristics are conducted for a better understanding of LCDs pyrolysis. • Optimum design is developed which is significant to guide the further industrial process. • Acetic acid and TPP are recycled and separated. - Abstract: Waste liquid crystal display (LCD) panels mainly contain inorganic materials (glass substrate with indium-tin oxide film), and organic materials (polarizing film and liquid crystal). The organic materials should be removed beforehand since the organic matters would hinder the indium recycling process. In the present study, pyrolysis process is used to remove the organic materials and recycle acetic as well as and triphenyl phosphate (TPP) from waste LCD panels in an environmental friendly way. Several highlights of this study are summarized as follows: (i) Pyrolysis characteristics and pyrolysis kinetics analysis are conducted which is significant to get a better understanding of the pyrolysis process. (ii) Optimum design is developed by applying Box–Behnken Design (BBD) under response surface methodology (RSM) for engineering application which is significant to guide the further industrial recycling process. The oil yield could reach 70.53 wt% and the residue rate could reach 14.05 wt% when the pyrolysis temperature is 570 °C, nitrogen flow rate is 6 L min"−"1 and the particle size is 0.5 mm. (iii) Furthermore, acetic acid and TPP are recycled, and then separated by rotary evaporation, which could reduce the consumption of fossil energy for producing acetic acid, and be reused in electronics manufacturing industry.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-04-06

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

Multisteps Global Kinetic Analysis of MSW Slow Pyrolysis

Directory of Open Access Journals (Sweden)

Dwi Aries Himawanto

2013-12-01

Full Text Available The goal of this research is to find relationships between single components slow pyrolysis characteristics and mixed component slow pyrolysis characteristics of segregated municipal solid wastes (MSW. The material of this research consists of organic wastes (bamboo wastes and banana leaves wastes and inorganic wastes (styrofoam wastes and snack wrapping wastes. The materials which used to study were the unprosessing waste. The samples were collected, dried and crushed until passing 20 mesh shieves then characterized in self manufactured macro balance. The thermogravimetry analyses were done to find the MSW slow pyrolysis characteristics. The 20 gram sample was placed in the furnace whose temperature is increased with 10 0C/min heating rate until reached 400 0 final temperature and held for 30 minutes before the sample is cooled into room temperature. One hundred ml/min nitrogen introduced from the bottom of furnace as a swept gas. The results of the research show that the global kinetic method could be used to predict the MSW single component activation energy but it should be modified to calculate the mixed sample activation energy . The predictive activation energy values which calculated based on weighed sum of single component have 18.5 % deviations if compared with experimental result.

Integrated biomass pyrolysis with organic Rankine cycle for power generation

Science.gov (United States)

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

2018-02-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Antonakou, E.V. [Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Kalogiannis, K.G.; Stephanidis, S.D. [Chemical Process Engineering Research Institute, 57001 Thermi, Thessaloniki (Greece); Triantafyllidis, K.S. [Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece); Chemical Process Engineering Research Institute, 57001 Thermi, Thessaloniki (Greece); Lappas, A.A. [Chemical Process Engineering Research Institute, 57001 Thermi, Thessaloniki (Greece); Achilias, D.S., E-mail: axilias@chem.auth.gr [Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece)

2014-12-15

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1996-12-31

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1995-12-31

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

Comprehensive Interpretation of the Laboratory Experiments Results to Construct Model of the Polish Shale Gas Rocks

Science.gov (United States)

Jarzyna, Jadwiga A.; Krakowska, Paulina I.; Puskarczyk, Edyta; Wawrzyniak-Guz, Kamila; Zych, Marcin

2018-03-01

More than 70 rock samples from so-called sweet spots, i.e. the Ordovician Sa Formation and Silurian Ja Member of Pa Formation from the Baltic Basin (North Poland) were examined in the laboratory to determine bulk and grain density, total and effective/dynamic porosity, absolute permeability, pore diameters size, total surface area, and natural radioactivity. Results of the pyrolysis, i.e., TOC (Total Organic Carbon) together with S1 and S2 - parameters used to determine the hydrocarbon generation potential of rocks, were also considered. Elemental composition from chemical analyses and mineral composition from XRD measurements were also included. SCAL analysis, NMR experiments, Pressure Decay Permeability measurements together with water immersion porosimetry and adsorption/ desorption of nitrogen vapors method were carried out along with the comprehensive interpretation of the outcomes. Simple and multiple linear statistical regressions were used to recognize mutual relationships between parameters. Observed correlations and in some cases big dispersion of data and discrepancies in the property values obtained from different methods were the basis for building shale gas rock model for well logging interpretation. The model was verified by the result of the Monte Carlo modelling of spectral neutron-gamma log response in comparison with GEM log results.

Time resolved pyrolysis of char

DEFF Research Database (Denmark)

Egsgaard, H.; Ahrenfeldt, J.; Henriksen, U.B.

pyrolysis, and slow heating in direct combination with mass spectrometry, gas chromatography/mass spectrometry and flame ionization detection, respectively. Characteristic ions derived from the flash pyrolysis-gas chromatography/mass spectrometry data enable the release of volatiles to be time and, hence...

Pyrolysis model for an alpha waste incinerator prototype

International Nuclear Information System (INIS)

Orloff, D.I.

1978-01-01

The development of a theoretical model of the pyrolysis stage of an SRL prototype alpha waste incinerator is discussed. Pyrolysis rates for single component porous beds of Teflon (Registered trademark of Du Pont) and natural rubber have been measured on a bench-scale furnace. Experimental pyrolysis rates compare favorably to the predictions of a quasi-steady regression model. In addition, the pyrolysis rate is shown to be a weak function of the thermal diffusivity of the porous polymer bed. As a consequence, pyrolysis is controlled by thermal degradation kinetics rather than by diffusion or conduction

Mineralogical, chemical and K-Ar isotopic changes in Kreyenhagen Shale whole rocks and <2 µm clay fractions during natural burial and hydrous-pyrolysis experimental maturation

Science.gov (United States)

Clauer, Norbert; Lewan, Michael D.; Dolan, Michael P.; Chaudhuri, Sambhudas; Curtis, John B.

2014-01-01

Progressive maturation of the Eocene Kreyenhagen Shale from the San Joaquin Basin of California was studied by combining mineralogical and chemical analyses with K–Ar dating of whole rocks and sequence, indicating that there is no detectable variation in the crystallo-chemical organization of the K-bearing alumino-silicates with depth. No supply of K from outside of the rock volumes occurred, which indicates a closed-system behavior for it. Conversely, the content of the total organic carbon (TOC) content decreases significantly with burial, based on the progressive increasing Al/TOC ratio of the whole rocks. The initial varied mineralogy and chemistry of the rocks and their <2 μm fractions resulting from differences in detrital sources and depositional settings give scattered results that homogenize progressively during burial due to increased authigenesis, and concomitant increased alteration of the detrital material.

Exploratory studies on fast pyrolysis oil upgrading

NARCIS (Netherlands)

Mahfud, Farchad Husein

2007-01-01

Pyrolysis oil is a dark brown liquid which can be produced in high yield from different kind of biomass sources by means of fast pyrolysis. Pyrolysis oil is considered as a promising second generation energy carrier and may play an important role in the future of "biobased economies". The energy

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

NARCIS (Netherlands)

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

2008-01-01

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

Composition of coal tar from pyrolysis and hydropyrolysis of Shenmu coal macerals

Energy Technology Data Exchange (ETDEWEB)

Sun, Q.; Li, W.; Chen, H.; Li, B. [Shandong Academy of Sciences, Jinan (China)

2005-08-15

To understand the relationship of the tar compositions and the coal macerals, the tars obtained from the pyrolysis and hydropyrolysis of Shenmu coal macerals in a fixed-bed reactor were analysed using GC-MS. And the effects of petrographic component, atmosphere and pressure on the yield of aromatic hydrocarbon, phenols, hydrocarbons, oxygen-containing heterocycle and PAHs were systematically investigated. The results show that there is great difference in the composition and the relative content of long chain hydrocarbons, aromatic hydrocarbons, phenols, oxygen-containing heterocycle and PAHs in tars from vitrinite and inertinite pyrolysis. Vitrinite tar contains high content of hydrocarbon with long chain, and inertinite tar contains high content of aromatic hydrocarbons, phenols, oxygen-containing heterocycle and PAHs. It suggests that vitrinite has lower aromaticity and longer chain in its structure than inertinite, which is in well agreement with the result from {sup 13}C NMR and FT-IR test. The tar yield of hydropyrolysis is higher than that of pyrolysis. With increasing the hydrogen pressure, the yield of tar increases greatly. The content of phenols and naphthalene in vitrinite tar form hydropyrolysis under 0.1 MPa is much lower than that form pyrolysis, while that of inertinite tar changes a little. The difference of tar compositions and relative content during pyrolysis and hydropyrolysis reflects the effect of hydrogenation and hydrocracking reactions and the structure characteristics of the macerals. 12 refs., 3 figs.

Waste truck-tyre processing by flash pyrolysis in a conical spouted bed reactor

International Nuclear Information System (INIS)

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

2017-01-01

Highlights: • Flash pyrolysis improves TPO and limonene yields vs. slow pyrolysis. • The most suitable temperature for TPO and limonene maximization was 475 °C. • Operating at 575 °C gas yields and char quality was enhanced. • Temperature showed a limited effect on sulphur distribution among products. - Abstract: The flash pyrolysis of waste truck-tyres was studied in a conical spouted bed reactor (CSBR) operating in continuous regime. The influence of temperature on product distribution was analysed in the 425–575 °C range. A detailed characterization of the pyrolysis products was carried out in order to assess their most feasible application. Moreover, special attention was paid to the sulphur distribution among the products. The analysis of gaseous products was carried out using a micro-GC and the tyre pyrolysis oil (TPO) by means of GC-FID using peak areas for quantification, with GC/MS for identification and elemental analysis. Finally, the char was subjected to elemental analysis and surface characterization. According to the results, 475 °C is an appropriate temperature for the pyrolysis of waste tyres, given that it ensures total devolatilisation of tyre rubber and a high TPO yield, 58.2 wt.%. Moreover, the quality of the oil is optimum at this temperature, especially in terms of high concentrations of valuable chemicals, such as limonene. An increase in temperature to 575 °C reduced the TPO yield to 53.9 wt.% and substantially changed its chemical composition by increasing the aromatic content. However, the quality of the recovered char was improved at high temperatures.

Biomass pyrolysis for chemicals

Energy Technology Data Exchange (ETDEWEB)

De Wild, P.

2011-07-15

The problems associated with the use of fossil fuels demand a transition to renewable sources (sun, wind, water, geothermal, biomass) for materials and energy where biomass provides the only renewable source for chemicals. In a biorefinery, biomass is converted via different technologies into heat, power and various products. Here, pyrolysis (thermal degradation without added oxygen) of lignocellulosic biomass can play an important role, because it leads to an array of useful chemicals. Examples are furfural and acetic acid from hemicellulose, levoglucosan from cellulose and phenols and biochar from lignin. Since the three major biomass polymers hemicellulose, cellulose and lignin possess dissimilar thermal stabilities and reactivities, type and amount of degradation products are tunable by proper selection of the pyrolysis conditions. To determine if step-wise pyrolysis would be suitable for the production of chemicals, staged degasification of lignocellulosic biomass was studied. Due to limited yields, a hot pressurized water pre-treatment (aquathermolysis) followed by pyrolysis was subsequently developed as an improved version of a staged approach to produce furfural and levoglucosan from the carbohydrate fraction of the biomass. Lignin is the only renewable source for aromatic chemicals. Lignocellulosic biorefineries for bio-ethanol produce lignin as major by-product. The pyrolysis of side-streams into valuable chemicals is of prime importance for a profitable biorefinery. To determine the added-value of lignin side-streams other than their use as fuel for power, application research including techno-economic analysis is required. In this thesis, the pyrolytic valorisation of lignin into phenols and biochar was investigated and proven possible.

Thermal and catalytic pyrolysis of plastic waste

Directory of Open Access Journals (Sweden)

Débora Almeida

2016-02-01

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

Fuels Combustion Research: Supercritical Fuel Pyrolysis

National Research Council Canada - National Science Library

Glassman, Irvin

2001-01-01

.... The focus during the subject period was directed to understanding the pyrolysis and combustion of endothermic fuels under subcritical conditions and the pyrolysis of these fuels under supercritical conditions...

Fuels Combustion Research: Supercritical Fuel Pyrolysis

National Research Council Canada - National Science Library

Glassman, Irvin

2000-01-01

.... The focus during the subject period was directed to understanding the pyrolysis and combustion of endothermic fuels under subcritical conditions and the pyrolysis of these fuels under supercritical conditions...

The catalytic cracking mechanism of lignite pyrolysis char on tar

International Nuclear Information System (INIS)

Lei, Z.; Huibin, H.; Xiangling, S.; Zhenhua, M.; Lei, Z.

2017-01-01

The influence of different pyrolysis conditions for tar catalytic cracking will be analyzed according to the lignite pyrolysis char as catalyst on pyrolytic tar in this paper. The pyrolysis char what is the by-product of the cracking of coal has an abundant of pore structure and it has good catalytic activity. On this basis, making the modified catalyst when the pyrolysis char is activation and loads Fe by impregnation method. The cracking mechanism of lignite pyrolytic tar is explored by applying gas chromatograph to analyze splitting products of tar. The experimental results showed that: (1) The effect of tar cracking as the pyrolysis temperature, the heating rate, the volatilization of pyrolysis char and particle size increasing is better and better. The effect of the catalytic and cracking of lignite pyrolysis char in tar is best when the heating rate, the pyrolysis temperature, the volatiles of pyrolysis char, particle size is in specific conditions.(2) The activation of pyrolysis char can improve the catalytic effect of pyrolysis char on the tar cracking. But it reduces the effect of the tar cracking when the pyrolysis char is activation loading Fe. (author)

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

Directory of Open Access Journals (Sweden)

Renato O. Arazo

2017-01-01

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

Coal pyrolysis under hydrogen-rich gases

Energy Technology Data Exchange (ETDEWEB)

Liao, H.; Sun, C.; Li, B.; Liu, Z. [Chinese Academy of Sciences, Taiyuan (China). State Key Laboratory of Coal Conversion, Institute of Coal Chemistry

1998-04-01

To improve the economy of the pyrolysis process by reducing the hydrogen cost, it is suggested to use cheaper hydrogen-rich gases such as coke-oven gas (COG) or synthesis gas (SG) instead of pure hydrogen. The pyrolysis of Chinese Xianfeng lignite which was carried out with real COG and SG at 3-5 MPa, a final temperature of 650{degree}C and a heating rate of 5{degree}C/min in a 10g fixed-bed reactor is compared with coal pyrolysis with pure hydrogen and nitrogen under the same conditions. The results indicate that compared with hydropyrolysis at the same total pressure, the total conversion and tar yields from coal pyrolysis with COG and SG decreases while the unwanted water increases. However, at the same H{sub 2} partial pressure, the tar yields and yields of BBTX, PCX and naphthalene from the pyrolysis of coal with COG and SG are all significantly higher than those of hydropyrolysis. Therefore, it is possible to use COG and SG instead of pure hydrogen. 8 refs., 3 figs., 6 tabs.

CHARACTERIZATION OF BIO-OIL FROM PALM KERNEL SHELL PYROLYSIS

Directory of Open Access Journals (Sweden)

R. Ahmad

2014-12-01

Full Text Available Pyrolysis of palm kernel shell in a fixed-bed reactor was studied in this paper. The objectives were to investigate the effect of pyrolysis temperature and particle size on the products yield and to characterize the bio-oil product. In order to get the optimum pyrolysis parameters on bio-oil yield, temperatures of 350, 400, 450, 500 and 550 °C and particle sizes of 212–300 µm, 300–600 µm, 600µm–1.18 mm and 1.18–2.36 mm under a heating rate of 50 °C min-1 were investigated. The maximum bio-oil yield was 38.40% at 450 °C with a heating rate of 50 °C min-1 and a nitrogen sweep gas flow rate of 50 ml min-1. The bio-oil products were analysed by Fourier transform infra-red spectroscopy (FTIR and gas chromatography–mass spectroscopy (GCMS. The FTIR analysis showed that the bio-oil was dominated by oxygenated species. The phenol, phenol, 2-methoxy- and furfural that were identified by GCMS analysis are highly suitable for extraction from the bio-oil as value-added chemicals. The highly oxygenated oils need to be upgraded in order to be used in other applications such as transportation fuels.

Mass spectrometric studies of fast pyrolysis of cellulose

Energy Technology Data Exchange (ETDEWEB)

Degenstein, John; Hurt, Matt; Murria, Priya; Easton, McKay; Choudhari, Harshavardhan; Yang, Linan; Riedeman, James; Carlsen, Mark; Nash, John; Agrawal, Rakesh; Delgass, W.; Ribeiro, Fabio; Kenttämaa, Hilkka

2015-01-01

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

A comprehensive study of methyl decanoate pyrolysis

International Nuclear Information System (INIS)

Pyl, Steven P.; Van Geem, Kevin M.; Puimège, Philip; Sabbe, Maarten K.; Reyniers, Marie-Françoise; Marin, Guy B.

2012-01-01

The thermal decomposition of methyl decanoate (MD) was studied in a bench-scale pyrolysis set-up equipped with a dedicated on-line analysis section including a GC × GC-FID/(TOF-MS). This analysis section enables quantitative and qualitative on-line analyses of the entire reactor effluent with high level of detail including measurement of formaldehyde and water. The reactor temperature was varied from 873 K to 1123 K at a fixed pressure of 1.7 bar and a fixed residence time of 0.5 s, for both high (10mol N 2 /mol MD ) and low (0.6mol N 2 /mol MD ) nitrogen dilution. Thus covering a wide conversion range in both dilution regimes. In these experiments, significant amounts of large linear olefins and unsaturated esters were observed at lower temperatures, the amounts of which decreased at higher temperatures in favor of permanent gasses (CO, CO 2 , CH 4 ) and light olefins. At the highest temperatures more than 5 wt% of mono-aromatic and poly-aromatic components were observed. The acquired dataset was used to validate 3 recently published microkinetic models which were developed to model oxidation and/or pyrolysis of methyl decanoate. The results showed that these models accurately predict the product distribution, although important discrepancies were observed for some major products such as certain unsaturated esters, CO 2 and H 2 O. Reaction path analyses and CBS-QB3 quantum-chemical calculations are presented and discussed in order to explain the observed differences. -- Highlights: ► New extensive experimental dataset for the pyrolysis of methyl decanoate in a tubular reactor. ► A dedicated separation section including on-line GC × GC allows to obtain quantitative data for over 150 components. ► High level ab-initio calculations for important reactions of the methyl decanoate decomposition. ► Identification of missing reactions/reaction families/inaccurate kinetics in the presently available kinetic models.

Research and development plan for the Slagging Pyrolysis Incinerator

International Nuclear Information System (INIS)

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

1979-01-01

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

Rock pushing and sampling under rocks on Mars

Science.gov (United States)

Moore, H.J.; Liebes, S.; Crouch, D.S.; Clark, L.V.

1978-01-01

Viking Lander 2 acquired samples on Mars from beneath two rocks, where living organisms and organic molecules would be protected from ultraviolet radiation. Selection of rocks to be moved was based on scientific and engineering considerations, including rock size, rock shape, burial depth, and location in a sample field. Rock locations and topography were established using the computerized interactive video-stereophotogrammetric system and plotted on vertical profiles and in plan view. Sampler commands were developed and tested on Earth using a full-size lander and surface mock-up. The use of power by the sampler motor correlates with rock movements, which were by plowing, skidding, and rolling. Provenance of the samples was determined by measurements and interpretation of pictures and positions of the sampler arm. Analytical results demonstrate that the samples were, in fact, from beneath the rocks. Results from the Gas Chromatograph-Mass Spectrometer of the Molecular Analysis experiment and the Gas Exchange instrument of the Biology experiment indicate that more adsorbed(?) water occurs in samples under rocks than in samples exposed to the sun. This is consistent with terrestrial arid environments, where more moisture occurs in near-surface soil un- der rocks than in surrounding soil because the net heat flow is toward the soil beneath the rock and the rock cap inhibits evaporation. Inorganic analyses show that samples of soil from under the rocks have significantly less iron than soil exposed to the sun. The scientific significance of analyses of samples under the rocks is only partly evaluated, but some facts are clear. Detectable quantities of martian organic molecules were not found in the sample from under a rock by the Molecular Analysis experiment. The Biology experiments did not find definitive evidence for Earth-like living organisms in their sample. Significant amounts of adsorbed water may be present in the martian regolith. The response of the soil

Vacuum pyrolysis of waste tires with basic additives

International Nuclear Information System (INIS)

Zhang Xinghua; Wang Tiejun; Ma Longlong; Chang Jie

2008-01-01

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

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Investigation on pyrolysis of some organic raw materials

Directory of Open Access Journals (Sweden)

Purevsuren B

2017-02-01

Full Text Available We have been working on pyrolysis of some organic raw materials including different rank coals, oil shale, wood waste, animal bone, cedar shell, polypropylene waste, milk casein and characterization of obtained hard residue, tar and pyrolytic water and gas after pyrolysis. The technical characteristics of these organic raw materials have been determined and the thermal stability characteristics such as thermal stability indices (T5% and T25% determined by using thermogravimetric analysis. The pyrolysis experiments were performed at different heating temperatures and the yields of hard residue, tar, pyrolysis water and gaseous products were determined and discussed. The main technical characteristics of hard residue of organic raw materials after pyrolysis have been determined and the adsorption ability of pyrolysis hard residue and its activated carbon of organic raw materials also determined. The pyrolysis tars of organic raw materials were distilled in air condition and determined the yields of obtained light, middle and heavy fractions and bitumen like residue with different boiling temperature. This is the first time to investigate the curing ability of pyrolysis tars of organic raw materials for epoxy resin and the results of these experiments showed that only tar of milk casein has the highest (95.0%, tar of animal bone has certain (18.70% and tars of all other organic raw materials have no curing ability for epoxy resin.

THE EFFECT OF AMOUNT OF NATURAL ZEOLIT CATALYST IN PRODUCT OF POLYPROPILENE (PP PLASTIC WASTE PYROLYSIS

Directory of Open Access Journals (Sweden)

khalimatus sa'diyah

2015-12-01

Full Text Available To overcome the waste problem, especially plastic waste , environmental concerned scientists from various disciplines have conducted various research and actions. Catalytic pyrolysis processes was chosen as an alternative method to recycle plastic waste. The purpose of this experiment was to determine the effect of natural zeolit catalyst on the pyrolysis process with oxygen-free conditions to obtain maximum hydrocarbon compounds (gasoline fraction in C5-C9. The process of pyrolysis was conducted in 3.5 dm3 unstirred stainless steel semi-batch reactor. This process operated at atmospheric pressure with nitrogen injection. Plastic waste that used in this particular paper was 50 grams of polypropylene (PP. In pyrolysis process, natural zeolite catalysts was added 2,5 gram (5% weight of natural zeolite per weight of plastic waste samples, 5 gram (10% , and 10 gram (20%. Temperature of pyrolysis was 450°C and were maintained until 30 minutes. Steam that produced from pyrolisis was condensed and analysed by gas chromatography–mass spectrometry (GC-MS to determine yield of hydrocarbons produced. From the analysis of GC-MS, liquid products of pyrolysis contained lots of aromatic hydrocarbons. The optimal amount of catalyst that produce liquid with hydrocarbon compound that has the quality of gasoline was 10 gram (20% with ≤C9 composition as 29,16% n-paraffin, 9,22% cycloparaffin, and 61,64% aromatics.

Pyrolysis model for an alpha waste incinerator prototype

International Nuclear Information System (INIS)

Orloff, D.I.

1979-01-01

The development of a theoretical model of the pyrolysis stage of a Savnnah River Laboratory prototype alpha waste incinerator is discussed. pyrolysis rates for single-component porous bed of Teflon (registered trademark of Du Pont de Nemours and Co.) have been measured on a bench-scale furnace. Experimental pyrolysis rates compare favorably to the predictions of a quasisteady regression model. In addition, the pyrolysis rate is shown to be a weak function of the thermal diffusivity of the porous polymer bed. 13 refs

Platinum, palladium, and rhodium analyses of ultramafic and mafic rocks from the Stillwater Complex, Montana

Science.gov (United States)

Page, Norman J; Riley, Leonard Benjamin; Haffty, Joseph

1969-01-01

Analyses by a combination fire- assay-solution-optical-emission spectrographic method of 137 rocks from the Stillwater Complex, Mont., indicate that platinum, palladium, and rhodium are preferentially concentrated in chromitite zones. The A chromitite zone (21 samples) has an average of 988.9 ppb (pans per billion, 10-9) Pt, 2290.2 ppb Pd, and 245.9 ppb Rh and reaches a maximum (to date) of 8,000 ppb Pt, 11,000 ppb Pd, and 1,700 ppb Rh.

Analysing the breakthrough of rock 'n' roll (1930-1970) : multi-regime interaction and reconfiguration in the multi-level perspective

NARCIS (Netherlands)

Geels, F.W.

2007-01-01

The breakthrough of rock ‘n’ roll was part of broader transformations in the American music industry, involving changes in music instruments, music recording technology, audiences, radio programming and music styles. These transformations will be analysed as sociotechnical transition, using the

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

Energy Technology Data Exchange (ETDEWEB)

Chen, Dezhen, E-mail: chendezhen@tongji.edu.cn [Thermal & Environmental Engineering Institute, Tongji University, Shanghai 200092 (China); Yin, Lijie; Wang, Huan [Thermal & Environmental Engineering Institute, Tongji University, Shanghai 200092 (China); He, Pinjing [State Key Laboratory of Pollution Control and Resource Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China)

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 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, 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.

Catalytic pyrolysis of hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Vail' eva, N A; Buyanov, R A

1979-01-01

Catalytic pyrolysis of petroleum fractions (undecane) was performed with the object of clarifying such questions as the mechanism of action of the catalyst, the concepts of activity and selectivity of the catalyst, the role of transport processes, the temperature ranges and limitations of the catalytic process, the effect of the catalyst on secondary processes, and others. Catalysts such as quartz, MgO, Al/sub 2/O/sub 3/, were used. Analysis of the experimental findings and the fact that the distribution of products is independent of the nature of the surface, demonstrate that the pyrolysis of hydrocarbons in the presence of catalysts is based on the heterogeneous-homogeneous radical-chain mechanism of action, and that the role of the catalysts reduces to increasing the concentration of free radicals. The concept of selectivity cannot be applied to catalysts here, since they do not affect the mechanism of the unfolding of the process of pyrolysis and their role consists solely in initiating the process. In catalytic pyrolysis the concepts of kinetic and diffusive domains of unfolding of the catalytic reaction do not apply, and only the outer surface of the catalyst is engaged, whereas the inner surface merely promotes deletorious secondary processes reducing the selectivity of the process and the activity of the catalyst. 6 references, 2 figures.

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

Science.gov (United States)

Sensöz, Sevgi; Angin, Dilek

2008-09-01

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

Pyrolysis gas chromatographic atomic emission detection for sediments, coals and other petrochemical precursors

Energy Technology Data Exchange (ETDEWEB)

Seeley, J.A.; Zeng, Y.D.; Uden, P.C.; Eglinton, T.I.; Ericson, I. (Massachusetts University, Amherst, MA (USA). Dept. of Chemistry)

1992-09-01

On-line flash pyrolysis coupled to a capillary gas chromatograph for the characterization of marine sediments, coals and other heterogeneous solid samples is described. A helium microwave-induced plasma is used for chromatographic detection by atomic emission spectrometry. Simultaneous multi-element detection is achieved with a photodiode array detector. The optical path of the gas chromatographic atomic emission detector is purged with helium, allowing simultaneous, sensitive detection of atomic emission from sulfur 181 nm, phosphorous 186 nm, arsenic 189 nm, selenium 196 nm and carbon 193 nm. Several sediment and coal samples have been analysed for their carbon, nitrogen, sulfur, oxygen, phosphorous, arsenic and selenium content. Qualitative information indicating the occurrence and distribution of these elements in the samples can be used to gauge the relative stage of diagenetic evolution of the samples and provide information on their depositional environment. In some instances the chromatographic behaviour of the compounds produced upon pyrolysis is improved through on-line alkylation. This on-line derivatization is achieved by adding liquid reagents to the pyrolysis probe or by adding liquid reagents to the pyrolysis probe or by adding solid reagents either to the solid sample or by packing the reagent in the injection port of the chromatograph.

Desulfurized gas production from vertical kiln pyrolysis

Science.gov (United States)

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

1978-05-30

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

Morphological characteristics of waste polyethylene/polypropylene plastics during pyrolysis and representative morphological signal characterizing pyrolysis stages.

Science.gov (United States)

Wang, H; Chen, D; Yuan, G; Ma, X; Dai, X

2013-02-01

In this work, the morphological characteristics of waste polyethylene (PE)/polypropylene (PP) plastics during their pyrolysis process were investigated, and based on their basic image changing patterns representative morphological signals describing the pyrolysis stages were obtained. PE and PP granules and films were used as typical plastics for testing, and influence of impurities was also investigated. During pyrolysis experiments, photographs of the testing samples were taken sequentially with a high-speed infrared camera, and the quantitative parameters that describe the morphological characteristics of these photographs were explored using the "Image Pro Plus (v6.3)" digital image processing software. The experimental results showed that plastics pyrolysis involved four stages: melting, two stages of decomposition which are characterized with bubble formation caused by volatile evaporating, and ash deposition; and each stage was characterized with its own phase changing behaviors and morphological features. Two stages of decomposition are the key step of pyrolysis since they took up half or more of the reaction time; melting step consumed another half of reaction time in experiments when raw materials were heated up from ambient temperatures; and coke-like deposition appeared as a result of decomposition completion. Two morphological signals defined from digital image processing, namely, pixel area of the interested reaction region and bubble ratio (BR) caused by volatile evaporating were found to change regularly with pyrolysis stages. In particular, for all experimental scenarios with plastics films and granules, the BR curves always exhibited a slowly drop as melting started and then a sharp increase followed by a deep decrease corresponding to the first stage of intense decomposition, afterwards a second increase - drop section corresponding to the second stage of decomposition appeared. As ash deposition happened, the BR dropped to zero or very low

Pyrolysis of biofuels of the future: Sewage sludge and microalgae – Thermogravimetric analysis and modelling of the pyrolysis under different temperature conditions

International Nuclear Information System (INIS)

Soria-Verdugo, Antonio; Goos, Elke; Morato-Godino, Andrés; García-Hernando, Nestor; Riedel, Uwe

2017-01-01

Highlights: • Pyrolysis of microalgae and sewage sludge is studied by thermogravimetric analysis. • Accurate values of the kinetic parameters of the pyrolysis reaction are reported. • Pyrolysis is modeled for parabolic and exponential temperature increases. • Estimations of the model are compared with experimental measurements in TGA. • Excellent agreement is reached between the model estimations and the experiments. - Abstract: The pyrolysis process of both microalgae and sewage sludge was investigated separately, by means of non-isothermal thermogravimetric analysis. The Distributed Activation Energy Model (DAEM) was employed to obtain the pyrolysis kinetic parameters of the samples, i.e. the activation energy E_a and the pre-exponential factor k_0. Nine different pyrolysis tests at different constant heating rates were conducted for each sample in a thermogravimetric analyzer (TGA) to obtain accurate values of the pyrolysis kinetic parameters when applying DAEM. The accurate values of the activation energy and the pre-exponential factor that characterize the pyrolysis reaction of Chlorella vulgaris and sewage sludge were reported, together with their associated uncertainties. The activation energy and pre-exponential factor for the C. vulgaris vary between 150–250 kJ/mol and 10"1"0–10"1"5 s"−"1 respectively, whereas values ranging from 200 to 400 kJ/mol were obtained for the sewage sludge activation energy, and from 10"1"5 to 10"2"5 s"−"1 for its pre-exponential factor. These values of E_a and k_0 were employed to estimate the evolution of the reacted fraction with temperature during the pyrolysis of the samples under exponential and parabolic temperature increases, more typical for the pyrolysis reaction of fuel particles in industrial reactors. The estimations of the relation between the reacted fraction and the temperature for exponential and parabolic temperature increases were found to be in good agreement with the experimental values

Numerical Analyses of the Influence of Blast-Induced Damaged Rock Around Shallow Tunnels in Brittle Rock

Science.gov (United States)

Saiang, David; Nordlund, Erling

2009-06-01

Most of the railway tunnels in Sweden are shallow-seated (rock cover) and are located in hard brittle rock masses. The majority of these tunnels are excavated by drilling and blasting, which, consequently, result in the development of a blast-induced damaged zone around the tunnel boundary. Theoretically, the presence of this zone, with its reduced strength and stiffness, will affect the overall performance of the tunnel, as well as its construction and maintenance. The Swedish Railroad Administration, therefore, uses a set of guidelines based on peak particle velocity models and perimeter blasting to regulate the extent of damage due to blasting. However, the real effects of the damage caused by blasting around a shallow tunnel and their criticality to the overall performance of the tunnel are yet to be quantified and, therefore, remain the subject of research and investigation. This paper presents a numerical parametric study of blast-induced damage in rock. By varying the strength and stiffness of the blast-induced damaged zone and other relevant parameters, the near-field rock mass response was evaluated in terms of the effects on induced boundary stresses and ground deformation. The continuum method of numerical analysis was used. The input parameters, particularly those relating to strength and stiffness, were estimated using a systematic approach related to the fact that, at shallow depths, the stress and geologic conditions may be highly anisotropic. Due to the lack of data on the post-failure characteristics of the rock mass, the traditional Mohr-Coulomb yield criterion was assumed and used. The results clearly indicate that, as expected, the presence of the blast-induced damage zone does affect the behaviour of the boundary stresses and ground deformation. Potential failure types occurring around the tunnel boundary and their mechanisms have also been identified.

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

Science.gov (United States)

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

2015-02-01

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

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

Science.gov (United States)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2010-01-01

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V

Auto shredder residue recycling: Mechanical separation and pyrolysis

International Nuclear Information System (INIS)

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

2012-01-01

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

Wood pyrolysis oil for diesel engines

Energy Technology Data Exchange (ETDEWEB)

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

1996-12-01

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

Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

Science.gov (United States)

Nicholas, Christpher P; Boldingh, Edwin P

2013-12-17

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

Conditioning of traced rock section for diffusion profile analyses

International Nuclear Information System (INIS)

Dewonck, S.; Auriere, C.

2010-01-01

Document available in extended abstract form only. The French National Agency for radioactive waste management investigates for a high-level radioactive waste repository in deep geological formation. The Andra's disposal concept is based notably on the impermeable properties of the host rock barrier (the Callovo-Oxfordian mud-stone of the Eastern Paris Basin). Diffusion is assumed to be the main transport mechanism governing radionuclide migration through argillite. Diffusion properties were measured in situ, in the constrained rock, by experiments taken place at the Andra's Underground Research Laboratory. The diffusion experiments consist in injecting a traced solution as pulse, in a packed-off borehole interval, at a pressure similar of the hydraulic pressure of the rock. After several months of circulation, the traced solution is purged and the downhole equipment is dismantled. With a drilling machine, the overcoring of the rock section around the injection interval is performed to analyze the repartition of the radionuclides in the clay section. Totally new technical developments were necessary to make these tasks possible. This contribution reports on: - the method developed to going up the over-core from the gallery to the surface without damaging the traced clay section and avoiding any contamination of the underground installation by dust particles, - the specific room created to sampling the rock section in diffusion profiles with respect of radioprotection laws. In gallery, the over-core is extracted from the core barrel directly to a metallic box especially built to transport the clay section to the surface. This box is a good confining device avoiding all radioactive contamination of the galleries and the shaft. Moreover, this box made in iron decrease the dose equivalent rate and consecutively it's not necessary to have safety classification to transport the core. When the over-core is in the radioactive cutting room, technicians have

Pyrolysis of rubber gloves in integral pyrolysis test plant

International Nuclear Information System (INIS)

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

2010-01-01

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

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Evaluation of Integrated Time-Temperature Effect in Pyrolysis Process of Historically Contaminated Soils with Cadmium (Cd and Lead (Pb

Directory of Open Access Journals (Sweden)

Bulmău C

2013-04-01

Full Text Available It is already known that heavy metals pollution causes important concern to human and ecosystem health. Heavy metals in soils at the European level represents 37.3% between main contaminates affecting soils (EEA, 2007. This paper illustrates results obtained in the framework of laboratory experiments concerning the evaluation of integrated time-temperature effect in pyrolysis process applied to contaminated soil by two different ways: it is about heavy metals historically contaminated soil from one of the most polluted areas within Romania, and artificially contaminated with PCB-containing transformer oil. In particular, the authors focused on a recent evaluation of pyrolysis efficiency on removing lead (Pb and cadmium (Cd from the contaminated soil. The experimental study evaluated two important parameters related to the studied remediation methodology: thermal process temperature and the retention time in reactor of the contaminated soils. The remediation treatments were performed in a rotary kiln reactor, taking into account three process temperatures (400°C, 600°C and 800°C and two retention times: 30 min. and 60 min. Completed analyses have focused on pyrolysis solids and gas products. Consequently, both ash and gas obtained after pyrolysis process were subjected to chemical analyses.

Alternative fuel produced from thermal pyrolysis of waste tires and its use in a DI diesel engine

International Nuclear Information System (INIS)

Wang, Wei-Cheng; Bai, Chi-Jeng; Lin, Chi-Tung; Prakash, Samay

2016-01-01

Highlights: • The liquid, solid and gas yields from pyrolysis of waste tires were investigated. • For energy and economic consideration, pre-treatments of TPO were avoided. • Various proportions of TPO-diesel mixture were tested in a DI diesel engine. • TPOs derived from various pyrolysis temperatures were also tested in engine. • Fuel consumption, cylinder pressure, engine power, and SO2 emission were discussed. - Abstract: Alternative fuels from waste material have been receiving attentions due to the increasing demand of fossil fuels. Pyrolysis has been a considerable solution for processing waste tires because it gives clean emissions and produces valuable liquid or solid products. Pyrolysis oil from waste tires has become a potential replacement for petroleum diesel due to the similar physical and chemical properties to diesel fuel. In this study, waste tires were pyrolyzed in a lab-scale fixed bed reactor with various reaction temperatures. The liquid, solid and gas product yields from different pyrolysis temperatures were compared, as well as the analyses of property and element for the oil product. Due to the energy and economic consideration, the pre-treatments of TPO before adding into regular diesel were avoided. The TPO derived from various pyrolysis temperatures were mixed with regular diesel at different proportions and subsequently tested in a DI diesel engine. The engine performance, such as fuel consumption, cylinder pressure, engine power, and SO_2 emission, were examined and discussed. The results indicated that increasing the TPO fraction in diesel lead to worse engine performance, but it can be recovered using TPOs produced from higher pyrolysis temperatures.

Pyrolysis Recovery of Waste Shipping Oil Using Microwave Heating

Directory of Open Access Journals (Sweden)

Wan Adibah Wan Mahari

2016-09-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2003-01-01

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

Characterisation of model compounds and a synthetic coal by TG/MS/FTIR to represent the pyrolysis behaviour of coal

Energy Technology Data Exchange (ETDEWEB)

Arenillas, A.; Pevida, C.; Rubiera, F.; Garcia, R.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain)

2004-06-01

Coal pyrolysis is the initial, accompanying reaction of a number of coal conversion processes such as hydrogenation, combustion and gasification. However, because of the inherent complexity of coal composition, it is difficult to describe coal pyrolysis clearly. Single model compounds have been used before in order to provide additional insight into the complex processes that occur in the pyrolysis of coal. Yet the picture obtained is a simplified one and certain important aspects such as coal structure, interactions between different surface groups and cross-links are omitted. The approach used in this work involves the preparation of a synthetic coal, SC, with a known structure by curing a mixture of single, well-defined model compounds. By means of chemical characterisation, the SC was shown to contain the macroscopic features of a high volatile coal (proximate and ultimate analyses). FTIR characterisation revealed the presence of functional groups similar to those of coal in the structure of the SC. Temperature-programmed pyrolysis tests were performed in a thermobalance linked to a mass spectrometer and a Fourier transform infrared analyser (TG/MS/FTIR). The thermal behaviour of the synthetic coal (i.e., rate of mass loss and the evolution profiles of gaseous compounds during pyrolysis tests) is very similar to that of the high volatile bituminous coal which was used as a reference material. The great advantage of using SC lies in the fact that its composition and structure can be accurately determined and employed in subsequent applications in basic and mechanistic studies.

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

International Nuclear Information System (INIS)

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

2014-01-01

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

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

Energy Technology Data Exchange (ETDEWEB)

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

2014-12-15

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

Fates of Chemical Elements in Biomass during Its Pyrolysis.

Science.gov (United States)

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

2017-05-10

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

Fast pyrolysis of linseed. Product yields and compositions

Energy Technology Data Exchange (ETDEWEB)

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

2004-06-01

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

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

Science.gov (United States)

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

2016-11-01

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

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

Science.gov (United States)

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

2014-12-01

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

Reaction mechanisms in cellulose pyrolysis: a literature review

Energy Technology Data Exchange (ETDEWEB)

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

1977-08-01

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

An experimental and kinetic modeling study of glycerol pyrolysis

International Nuclear Information System (INIS)

Fantozzi, F.; Frassoldati, A.; Bartocci, P.; Cinti, G.; Quagliarini, F.; Bidini, G.; Ranzi, E.M.

2016-01-01

Highlights: • Glycerol pyrolysis can produce about 44–48%v hydrogen at 750–800 °C. • A simplified 452 reactions kinetic model of glycerol pyrolysis has been developed. • The model has good agreement with experimental data. • Non condensable gas yields can reach 70%. - Abstract: Pyrolysis of glycerol, a by-product of the biodiesel industry, is an important potential source of hydrogen. The obtained high calorific value gas can be used either as a fuel for combined heat and power (CHP) generation or as a transportation fuel (for example hydrogen to be used in fuel cells). Optimal process conditions can improve glycerol pyrolysis by increasing gas yield and hydrogen concentration. A detailed kinetic mechanism of glycerol pyrolysis, which involves 137 species and more than 4500 reactions, was drastically simplified and reduced to a new skeletal kinetic scheme of 44 species, involved in 452 reactions. An experimental campaign with a batch pyrolysis reactor was properly designed to further validate the original and the skeletal mechanisms. The comparisons between model predictions and experimental data strongly suggest the presence of a catalytic process promoting steam reforming of methane. High pyrolysis temperatures (750–800 °C) improve process performances and non-condensable gas yields of 70%w can be achieved. Hydrogen mole fraction in pyrolysis gas is about 44–48%v. The skeletal mechanism developed can be easily used in Computational Fluid Dynamic software, reducing the simulation time.

A kinetic reaction model for biomass pyrolysis processes in Aspen Plus

International Nuclear Information System (INIS)

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

2017-01-01

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

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

Science.gov (United States)

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

2012-03-01

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

Pyrolysis of waste tyres: a review.

Science.gov (United States)

Williams, Paul T

2013-08-01

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

Hot char-catalytic reforming of volatiles from MSW pyrolysis

International Nuclear Information System (INIS)

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

2017-01-01

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

Rotor for a pyrolysis centrifuge reactor

DEFF Research Database (Denmark)

2015-01-01

The present invention relates to a rotor for a pyrolysis centrifuge reactor, said rotor comprising a rotor body having a longitudinal centre axis, and at least one pivotally mounted blade being adapted to pivot around a pivot axis under rotation of the rotor body around the longitudinal centre axis....... Moreover, the present invention relates to a pyrolysis centrifuge reactor applying such a rotor....

Historical Developments of Pyrolysis Reactors : A Review

NARCIS (Netherlands)

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

2017-01-01

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

Novel technique for coal pyrolysis and hydrogenation product analysis

Energy Technology Data Exchange (ETDEWEB)

Pfefferle, L.D.; Boyle, J.

1993-03-15

A microjet reactor coupled to a VUV photoionization time-of-flight mass spectrometer has been used to obtain species measurements during high temperature pyrolysis and oxidation of a wide range of hydrocarbon compounds ranging from allene and acetylene to cyclohexane, benzene and toluene. Initial work focused on calibration of the technique, optimization of ion collection and detection and characterization of limitations. Using the optimized technique with 118 nm photoionization, intermediate species profiles were obtained for analysis of the hydrocarbon pyrolysis and oxidation mechanisms. The soft'' ionization, yielding predominantly molecular ions, allowed the study of reaction pathways in these high temperature systems where both sampling and detection challenges are severe. Work has focused on the pyrolysis and oxidative pyrolysis of aliphatic and aromatic hydrocarbon mixtures representative of coal pyrolysis and hydropyrolysis products. The detailed mass spectra obtained during pyrolysis and oxidation of hydrocarbon mixtures is especially important because of the complex nature of the product mixture even at short residence times and low primary reactant conversions. The combustion community has advanced detailed modeling of pyrolysis and oxidation to the C4 hydrocarbon level but in general above that size uncertainties in rate constant and thermodynamic data do not allow us to a priori predict products from mixed hydrocarbon pyrolyses using a detailed chemistry model. For pyrolysis of mixtures of coal-derived liquid fractions with a large range of compound structures and molecular weights in the hundreds of amu the modeling challenge is severe. Lumped models are possible from stable product data.

Photocatalytic Desulfurization of Waste Tire Pyrolysis Oil

Directory of Open Access Journals (Sweden)

Napida Hinchiranan

2011-11-01

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

Reactions of oxygen containing structures in coal pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Hodek, W.; Kirschstein, J.; Van Heek, K.-H. (DMT-Gesellschaft fuer Forschung und Pruefung mbH, Essen (Germany, F.R.))

1991-03-01

In coal pyrolysis O-containing structures such as ether bridges and phenolic groups play an important role. Their reactions were studied by non-isothermal pyrolysis of a high volatile bituminous coal and some model polymers with gas chromatographic detection of the gaseous pyrolysis products. The coal was separated into the maceral groups vitrinite, exinite and inertinite, which showed markedly different pyrolysis behaviour. The formation of CO, methane and benzene was measured versus temperature. By comparison with polyphenyleneoxide and phenol-formaldehyde resins, it was found that the main volatilization, during which most of the tar is evolved, is initiated by cleavage of alkyl-aryl-ethers. Rearrangements of the primarily formed radicals lead to the formation of CO and methane at higher temperatures. 5 refs., 8 figs., 1 tab.

Controlled air pyrolysis incinerator

International Nuclear Information System (INIS)

Dufrane, K.H.; Wilke, M.

1982-01-01

An advanced controlled air pyrolysis incinerator has been researched, developed and placed into commercial operation for both radioactive and other combustible wastes. Engineering efforts cocentrated on providing an incinerator which emitted a clean, easily treatable off-gas and which produced a minimum amount of secondary waste. Feed material is continuously fed by gravity into the system's pyrolysis chamber without sorting, shredding, or other such pretreatment. Metal objects, liquids such as oil and gasoline, or solid products such as resins, blocks of plastic, tire, animal carcasses, or compacted trash may be included along with normal processed waste. The temperature of the waste is very gradually increased in a reduced oxygen atmosphere. Volatile pyrolysis gases are produced, tar-like substances are cracked and the resulting product, a relatively uniform, easily burnable material, is introduced into the combustion chamber. Steady burning is thus accomplished under easily controlled excess air conditions with the off-gasthen passing through a simple dry clean-up system. Gas temperatures are then reduced by air dilution before passing through final HEPA filters. Both commercial and nuclear installations have been operated with the most recent application being the central incinerator to service West Germany's nuclear reactors

Possibilities of instrumental neutron activation and X-ray fluorescence analyses of sedimentary-magmatic metamorphosed rocks from deep borehole drill cores

International Nuclear Information System (INIS)

Gurevich, A.L.; Drynkin, V.I.; Lejpunskaya, D.I.

1977-01-01

The possibilities for instrumental neutron-activation and X-ray fluorescence analyses of rocks of metamorphized sedimentary magmatic complexes have been studied with the aid of deep-hole core. The principal characteristics of the conditions of irradiation and of sample measurement ensuring the determination of the content of 26 elements are presented. The use of X-ray fluorescence analysis enables one to determine additionally the content of stron-tium and niobium. Standard specimens of the composition of rocks and complex reference compounds based on phenol formaldehyde resins are used as metrolo.o.ical auxiliaries in the calibration system and in evaluating the correctness of the techniques of instrumental neutron activation and fluorescence analysis. The ranges of the contents to be determined, the sensitivity and relative standard deviation are given. The contribution from the nonuniformity of the specimens to the summary error of element determination is estimated. It is shown that the accuracy and error of analyses are within the allowable range

Device for removing pyrolysis residues from a pyrolysis plant. Vorrichtung zum Austragen von Verschwelungsrueckstaenden aus einer Pyrolyseanlage

Energy Technology Data Exchange (ETDEWEB)

Eisenmann, A

1985-03-28

The purpose of the invention is a device for removing the hot solid pyrolysis residues of heterogeneous composition from an hermetically sealed pyrolysis plant, especially one for pyrolysing refuse and other materials. In order to achieve continuous permanent operation with hermetic sealing of the system to the atmosphere, the device according to the invention has a lock on the funnel-shaped floor of a shaft, which has a worm conveyor after it. There is a spray device in an hermetically sealed chamber of the lock, through which the hot pyrolysis residues are sprayed, in order to bind the dust particles and simultaneously to reduce the temperature. A sludge pump is connected to the worm conveyor, which removes the material to silos.

Vacuum pyrolysis of swine manure : biochar production and characteristics

Energy Technology Data Exchange (ETDEWEB)

Verma, M. [Inst. de recherche et de developpement en agroenvironnement Inc., Quebec City, PQ (Canada); Centre de recherche industrielle du Quebec, Quebec City, PQ (Canada); Godbout, S.; Larouche, J.P.; Lemay, S.P.; Pelletier, F. [Inst. de recherche et de developpement en agroenvironnement Inc., Quebec City, PQ (Canada); Solomatnikova, O. [Centre de recherche industrielle du Quebec, Quebec City, PQ (Canada); Brar, S.K. [Inst. national de la recherche scientifique, eau, terre et environnement, Quebec City, PQ (Canada)

2010-07-01

Quebec accounts for nearly 25 per cent of swine production in Canada. The issue of swine manure is addressed through land spreading and conversion into fertilizer. However, current regulations restrict the use of swine manure as fertilizer on most farmlands due to the problem of surplus phosphorus and nitrogen. Although many technologies exist to separate phosphorus and nitrogen from the organic-rich dry matter in swine manure, about 40 per cent of the treated waste matter must still be disposed in an environmentally sound manner. This study investigated the technical feasibility of pretreating the swine manure solids into biofuels on a farm-scale basis using vacuum pyrolysis process. A custom built stainless steel pressure vessel was used to carry out pyrolysis reaction of swine manure biomass at a temperature range between 200 to 600 degrees C under vacuum. The pyrolytic vapour was condensed in 2 glass condensers in series. The biochar was collected directly from the pyrolysis vessel following completion of the pyrolysis batch. The non condensable vapour and gases were considered as losses. Biochar, bio-oil, an aqueous phase and a gas mixture were the 4 products of the pyrolysis process. A thermogravimetric analysis of the swine manure samples was conducted before the pyrolysis tests. The study showed that 238 degrees C is the optimal pyrolysis temperature for biochar production.

Thermal pyrolysis characteristics of macroalgae Cladophora glomerata.

Science.gov (United States)

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.

Hydrocarbon potential of Ordovician and Silurian rocks. Siljan Region (Sweden)

Energy Technology Data Exchange (ETDEWEB)

Berner, U. [Bundesanstalt fuer Geowissenschaften und Rohstoffe (BGR), Hannover (Germany); Lehnert, O. [Erlangen-Nuernberg Univ., Erlangen (Germany); Meinhold, G. [Goettingen Univ. (Germany)

2013-08-01

Hydrocarbon exploration in the vicinity of Europe's largest impact structure (Siljan, Central Sweden) focused for years on abiogenic concepts and largely neglected state of the art knowledge on hydrocarbon generation via thermal decomposition of organic matter. In our study we use sedimentary rocks obtained from three drill sites (Mora001, Stumsnaes 1 and Solberga 1) within the ring structure around the central uplift to investigate the hydrocarbon potential of Ordovician and Silurian strata of the region and also for comparison with the shale oil and gas potential of age equivalent rocks of the Baltic Sea. Elemental analyses provided information on concentrations of carbonate and organic carbon, total sulfur as well as on the composition of major and minor elements of the sediments. The data has been used to evaluate the depositional environment and possible diagenetic alterations of the organic matter. RockEval pyrolysis and solvent hydrocarbon extraction gave insight into the hydrocarbon generation potential and the type and thermal maturity of the sediments. From the geochemistry data of the studied wells it is obvious that changes of depositional environments (lacustrine - marine) have occurred during Ordovician and Silurian times. Although, the quality of the organic matter has been influenced in marine and brackish environments through sulfate reduction, we observe for a number of marine and lacustrine sediments a good to excellent preservation of the biological precursors which qualify the sediments as hydrocarbon source rocks (Type II kerogens). Lacustrine source rocks show a higher remaining hydrocarbon potential (up to {proportional_to}550 mg HC per g C{sub org}) than those of marine or brackish environments. Our investigations indicate that the thermal maturity of organic matter of the drill sites has reached the initial stage of oil generation. However, at Mora001 some of the sediments were stained with oil indicating that hydrocarbons have

Temperature Jump Pyrolysis Studies of RP 2 Fuel

Science.gov (United States)

2017-01-09

Briefing Charts 3. DATES COVERED (From - To) 15 December 2016 – 11 January 2017 4. TITLE AND SUBTITLE Temperature Jump Pyrolysis Studies of RP-2 Fuel...Rev. 8- 98) Prescribed by ANSI Std. 239.18 1 TEMPERATURE JUMP PYROLYSIS STUDIES OF RP-2 FUEL Owen Pryor1, Steven D. Chambreau2, Ghanshyam L...17026 7 Temperature Jump Pyrolysis at AFRL Edwards Rapid heating of a metal filament at a rate of 600 – 800 K/s, and the set temperature is held for

Experimental investigation of pyrolysis process of corn straw

OpenAIRE

Lei Wang; Shengqiang Shen; Shuhua Yang; Xinguang Shi

2010-01-01

The present paper was performed to analyze the pyrolysis process of corn straw. Based on the thermogravimetric analysis, the component of pyrolysis gas of corn straw was tested using the gas chromatograph analyzer. Experimental results showed that, as the reaction temperature increases, the component of H 2 and CH 4 increases, whereas the component of CO and CO 2 decreases. Finally, the mechanism of pyrolysis process of corn straw was revealed from the point of view of the molecular structure...

Rapid quantification of biomarkers during kerogen microscale pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Stott, A.W.; Abbott, G.D. [Fossil Fuels and Environmental Geochemistry NRG, The University, Newcastle-upon-Tyne (United Kingdom)

1995-02-01

A rapid, reproducible method incorporating closed system microscale pyrolysis and thermal desorption-gas chromatography/mass spectrometry has been developed and applied to the quantification of sterane biomarkers released during pyrolysis of the Messel oil shale kerogen under confined conditions. This method allows a substantial experimental concentration-time data set to be collected at accurately controlled temperatures, due to the low thermal inertia of the microscale borosilicate glass reaction vessels, which facilitates kinetic studies of biomarker reactions during kerogen microscale pyrolysis

Insights into pyrolysis and co-pyrolysis of biomass and polystyrene: Thermochemical behaviors, kinetics and evolved gas analysis

International Nuclear Information System (INIS)

Özsin, Gamzenur; Pütün, Ayşe Eren

2017-01-01

Highlights: • TGA/MS/FT-IR was used to explore effect of polystyrene on pyrolytic decomposition of biomass. • The model-free iso-conversional methods were used for kinetic analysis. • Interactions occurred depending on the characteristics of the biomass. • TGA/MS and TGA/FT-IR coupling were used for gas analysis of co-pyrolysis for the first time. - Abstract: The purpose of this study was to investigate the effect on polystyrene (PS) during co-pyrolysis with biomass through thermal decomposition. The model-free iso-conversional methods (Kissinger, Friedman, Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose, Starink and Vyazovkin) were adopted to calculate activation energy of the pyrolysis and co-pyrolysis process of two biomass samples (walnut shell: WS and peach stones: PST) with PS. It is found that biomass blending to PS decreased activation energy values and resulted in multi-step reaction mechanisms. Furthermore, changes in the evolution profiles of methyl, water, methoxy, carbon dioxide, benzene and styrene was monitored through evolved gas analysis via TGA/FT-IR and TGA/MS. Detection of temperature dependent release of volatiles indicated the differences occur as a result of compositional differences of biomass.

The use of plant-specific pyrolysis products as biomarkers in peat deposits

Science.gov (United States)

Schellekens, Judith; Bradley, Jonathan A.; Kuyper, Thomas W.; Fraga, Isabel; Pontevedra-Pombal, Xabier; Vidal-Torrado, Pablo; Abbott, Geoffrey D.; Buurman, Peter

2015-09-01

Peatlands are archives of environmental change that can be driven by climate and human activity. Proxies for peatland vegetation composition provide records of (local) environmental conditions that can be linked to both autogenic and allogenic factors. Analytical pyrolysis offers a molecular fingerprint of peat, and thereby a suite of environmental proxies. Here we investigate analytical pyrolysis as a method for biomarker analysis. Pyrolysates of 48 peatland plant species were compared, comprising seventeen lichens, three Sphagnum species, four non-Sphagnum mosses, eleven graminoids (Cyperaceae, Juncaceae, Poaceae), five Ericaceae and six species from other families. This resulted in twenty-one potential biomarkers, including new markers for lichens (3-methoxy-5-methylphenol) and graminoids (ferulic acid methyl ester). The potential of the identified biomarkers to reconstruct vegetation composition is discussed according to their depth records in cores from six peatlands from boreal, temperate and tropical biomes. The occurrence of markers for Sphagnum, graminoids and lichens in all six studied peat deposits indicates that they persist in peat of thousands of years old, in different vegetation types and under different conditions. In order to facilitate the quantification of biomarkers from pyrolysates, typically expressed as proportion (%) of the total quantified pyrolysis products, an internal standard (5-α-androstane) was introduced. Depth records of the Sphagnum marker 4-isopropenylphenol from the upper 3 m of a Sphagnum-dominated peat, from samples analysed with and without internal standard showed a strong positive correlation (r2 = 0.72, P use of analytical pyrolysis in biomarker research by avoiding quantification of a high number of products.

NMR spectroscopy of coal pyrolysis products

Energy Technology Data Exchange (ETDEWEB)

Polonov, V.M.; Kalabin, G.A.; Kushnarev, D.F.; Shevchenko, G.G.

1985-12-01

The authors consider the scope for using H 1 and C 13 NMR spectroscopy to describe the products from coal pyrolysis and hydrogenization. The accuracy of the structural information provided by the best NMR methods is also considered. The stuctural parameters derived from H 1 and C 13 NMR spectra are presented. Results demonstrate the high accuracy and sensitivity of the structural information provided by H 1 AND C 13 NMR spectra for coal products. There are substantial structural differences between the soluble products from medium-temperature coking of Cheremkhov coal and high-speed pyrolysis of Kan-Acha coal, and also differences in behavior during hydrogenation. These differences are related to the structure of the organic matter in the initial coal and to differences in the pyrolysis mechanisms.

Geologic field notes and geochemical analyses of outcrop and drill core from Mesoproterozoic rocks and iron-oxide deposits and prospects of southeast Missouri

Science.gov (United States)

Day, Warren C.; Granitto, Matthew

2014-01-01

The U.S. Geological Survey, in cooperation with the Missouri Department of Natural Resources/Missouri Geological Survey, undertook a study from 1988 to 1994 on the iron-oxide deposits and their host Mesoproterozoic igneous rocks in southeastern Missouri. The project resulted in an improvement of our understanding of the geologic setting, mode of formation, and the composition of many of the known deposits and prospects and the associated rocks of the St. Francois terrane in Missouri. The goal for this earlier work was to allow the comparison of Missouri iron-oxide deposits in context with other iron oxide-copper ± uranium (IOCG) types of mineral deposits observed globally. The raw geochemical analyses were released originally through the USGS National Geochemical Database (NGDB, http://mrdata.usgs.gov). The data presented herein offers all of the field notes, locations, rock descriptions, and geochemical analyses in a coherent package to facilitate new research efforts in IOCG deposit types. The data are provided in both Microsoft Excel (Version Office 2010) spreadsheet format (*.xlsx) and MS-DOS text formats (*.txt) for ease of use by numerous computer programs.

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

Science.gov (United States)

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

2013-08-27

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

Pyrolysis and Gasification

DEFF Research Database (Denmark)

Astrup, Thomas; Bilitewski, B.

2011-01-01

a waste management perspective, pyrolysis and gasification are of relatively little importance as an overall management option. Today, gasification is primarily used on specific waste fractions as opposed to mixed household wastes. The main commercial activity so far has been in Japan, with only limited....... Today gasification is used within a range of applications, the most important of which are conversion of coal into syngas for use as chemical feedstock or energy production; but also gasification of biomass and waste is gaining significant interest as emerging technologies for sustainable energy. From...... success in Europe and North America (Klein et al., 2004). However, pyrolysis and gasification of waste are generally expected to become more widely used in the future. A main reason for this is that public perceptions of waste incineration in some countries is a major obstacle for installing new...

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

Science.gov (United States)

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

2012-01-01

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

Oxidative desulfurization of tire pyrolysis oil

OpenAIRE

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

2016-01-01

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

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

Science.gov (United States)

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.

Sorption data bases for argillaceous rocks and bentonite for the provisional safety analyses for SGT-E2

International Nuclear Information System (INIS)

Baeyens, B.; Thoenen, T.; Bradbury, M. H.; Marques Fernandes, M.

2014-11-01

In Stage 1 of the Sectoral Plan for Deep Geological Repositories, four rock types have been identified as being suitable host rocks for a radioactive waste repository, namely, Opalinus Clay for a high-level (HLW) and a low- and intermediate-level (L/ILW) repository, and 'Brauner Dogger', Effingen Member and Helvetic Marls for a L/ILW repository. Sorption data bases (SDBs) for all of these host rocks are required for the provisional safety analyses, including all of the bounding porewater and mineralogical composition combinations. In addition, SDBs are needed for the rock formations lying below Opalinus Clay (lower confining units) and for the bentonite backfill in the HLW repository. In some previous work Bradbury et al. (2010) have described a methodology for developing sorption data bases for argillaceous rocks and compacted bentonite. The main factors influencing the sorption in such systems are the phyllosilicate mineral content, particular the 2:1 clay mineral content (illite/smectite/illite-smectite mixed layers) and the water chemistry which determines the radionuclide species in the aqueous phase. The source sorption data were taken predominantly from measurements on illite (or montmorillonite in the case of bentonite) and converted to the defined conditions in each system considered using a series of so called conversion factors to take into account differences in mineralogy, in pH and in radionuclide speciation. Finally, a Lab → Field conversion factor was applied to adapt sorption data measured in dispersed systems (batch experiments) to intact rock under in-situ conditions. This methodology to develop sorption data bases has been applied to the selected host rocks, lower confining units and compacted bentonite taking into account the mineralogical and porewater composition ranges defined. Confidence in the validity and correctness of this methodology has been built up through additional studies: (i) sorption values obtained in the manner

Sorption data bases for argillaceous rocks and bentonite for the provisional safety analyses for SGT-E2

Energy Technology Data Exchange (ETDEWEB)

Baeyens, B.; Thoenen, T.; Bradbury, M. H.; Marques Fernandes, M.

2014-11-15

In Stage 1 of the Sectoral Plan for Deep Geological Repositories, four rock types have been identified as being suitable host rocks for a radioactive waste repository, namely, Opalinus Clay for a high-level (HLW) and a low- and intermediate-level (L/ILW) repository, and 'Brauner Dogger', Effingen Member and Helvetic Marls for a L/ILW repository. Sorption data bases (SDBs) for all of these host rocks are required for the provisional safety analyses, including all of the bounding porewater and mineralogical composition combinations. In addition, SDBs are needed for the rock formations lying below Opalinus Clay (lower confining units) and for the bentonite backfill in the HLW repository. In some previous work Bradbury et al. (2010) have described a methodology for developing sorption data bases for argillaceous rocks and compacted bentonite. The main factors influencing the sorption in such systems are the phyllosilicate mineral content, particular the 2:1 clay mineral content (illite/smectite/illite-smectite mixed layers) and the water chemistry which determines the radionuclide species in the aqueous phase. The source sorption data were taken predominantly from measurements on illite (or montmorillonite in the case of bentonite) and converted to the defined conditions in each system considered using a series of so called conversion factors to take into account differences in mineralogy, in pH and in radionuclide speciation. Finally, a Lab → Field conversion factor was applied to adapt sorption data measured in dispersed systems (batch experiments) to intact rock under in-situ conditions. This methodology to develop sorption data bases has been applied to the selected host rocks, lower confining units and compacted bentonite taking into account the mineralogical and porewater composition ranges defined. Confidence in the validity and correctness of this methodology has been built up through additional studies: (i) sorption values obtained in the manner

Co-pyrolysis of lignite and sugar beet pulp

International Nuclear Information System (INIS)

Yilgin, M.; Deveci Duranay, N.; Pehlivan, D.

2010-01-01

Today, worldwide studies have been undertaken on the biomass usage and co-conversion of biomass and coal to seek out alternative fuels for supplying energy in an environmental friendly way. The objective of this work is to study co-pyrolysis of lignite and sugar beet pulp in 50/50 (wt./wt.) ratio of blend pellets, to elucidate their thermal behaviour under pyrolysis conditions and to assess major decomposition products in terms of their yields. A special chamber, which has enabled very fast heating rates, was used in the pyrolysis experiments carried at 600 deg. C. The results were interpreted in the light of liquid, solid and gaseous yields, resulting from thermal decomposition, and kinetics of thermogravimetric analysis. Proximate volatile matter and ash contents of the blends were different compared to those found by using individual values. Sugar beet pulp decomposed faster within a relatively narrow temperature range than lignite and underwent a significant shrinkage during pyrolysis. It was found that the chars left behind after the flash pyrolysis of these pellets at 600 deg. C have substantial amounts of volatile matter that would evolve upon further heating.

Pyrolysis process for the treatment of food waste.

Science.gov (United States)

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.

Production of liquid fuels and chemicals from pyrolysis of Bangladeshi bicycle/rickshaw tire wastes

Energy Technology Data Exchange (ETDEWEB)

Islam, M. Rofiqul; Tushar, M.S.H.K. [Department of Mechanical Engineering, Rajshahi University of Engineering and Technology, Rajshahi 6204 (Bangladesh); Haniu, H. [Department of Mechanical Engineering, Kitami Institute of Technology, Kitami City, Hokkaido 090-8507 (Japan)

2008-05-15

Tire wastes in the form of used bicycle/rickshaw tires available in Bangladesh were pyrolyzed in a fixed-bed fire-tube heating reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and feed size on the product yields and liquid product composition. Final temperature range studied was between 375 and 575 C and the highest liquid product yield was obtained at 475 C. Liquid products obtained under the most suitable conditions were characterized by elemental analyses, FT-IR, {sup 1}H NMR and GC-MS techniques. The results show that it is possible to obtain liquid products that are comparable to petroleum fuels and valuable chemical feedstock from bicycle/rickshaw tire wastes if the pyrolysis conditions are chosen accordingly. (author)

Studies on Pyrolysis Kinetic of Newspaper Wastes in a Packed Bed Reactor: Experiments, Modeling, and Product Characterization

Directory of Open Access Journals (Sweden)

Aparna Sarkar

2015-01-01

Full Text Available Newspaper waste was pyrolysed in a 50 mm diameter and 640 mm long reactor placed in a packed bed pyrolyser from 573 K to 1173 K in nitrogen atmosphere to obtain char and pyro-oil. The newspaper sample was also pyrolysed in a thermogravimetric analyser (TGA under the same experimental conditions. The pyrolysis rate of newspaper was observed to decelerate above 673 K. A deactivation model has been attempted to explain this behaviour. The parameters of kinetic model of the reactions have been determined in the temperature range under study. The kinetic rate constants of volatile and char have been determined in the temperature range under study. The activation energies 25.69 KJ/mol, 27.73 KJ/mol, 20.73 KJ/mol and preexponential factors 7.69 min−1, 8.09 min−1, 0.853 min−1 of all products (solid reactant, volatile, and char have been determined, respectively. A deactivation model for pyrolysis of newspaper has been developed under the present study. The char and pyro-oil obtained at different pyrolysis temperatures have been characterized. The FT-IR analyses of pyro-oil have been done. The higher heating values of both pyro-products have been determined.

Flash pyrolysis properties of algae and lignin residue

DEFF Research Database (Denmark)

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

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

Influence of Carbonization Temperature on Physicochemical Properties of Biochar derived from Slow Pyrolysis of Durian Wood (Durio zibethinus Sawdust

Directory of Open Access Journals (Sweden)

Zaira Zaman Chowdhury

2016-02-01

Full Text Available The objective of this study was to explore the influence of pyrolysis temperature on the physicochemical properties of biochar synthesized from durian wood (Durio zibethinus sawdust. Surface morphological features, including the porosity and BET surface area of biochars, provide appropriate dimensions for growing clusters of microorganisms with excellent water retention capacity in soil. Oxygen-containing surface functional groups play a vital role in improving soil fertility by increasing its cation and anion exchange capacities with reduced leaching of nutrients from the soil surface. Biochar was produced via slow pyrolysis of woody biomass (WS using a fixed bed reactor under an oxygen-free atmosphere at different pyrolysis temperatures (350, 450, and 550 °C. The biochars obtained were characterized using ultimate and proximate analyses, Brunauer-Emmett-Teller (BET surface area, field-emission scanning electron microscopy (FE-SEM, Fourier transform infrared spectroscopy (FTIR, and X-ray diffraction (XRD. The yield of biochar decreased from 66.46 to 24.56%, whereas the BET surface area increased sharply from 2.567 to 220.989 m2/g, when the pyrolysis temperature was increased from 350 to 550 °C. The results highlighted the effect of pyrolysis temperature on the structure of the biochar, which could be advantageous for agricultural industries.

Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

Science.gov (United States)

Nicholas, Christopher P; Boldingh, Edwin P

2013-12-17

A new family of aluminosilicate zeolites designated UZM-44 has been synthesized. These zeolites are represented by the empirical formula Na.sub.nM.sub.m.sup.k+T.sub.tAl.sub.1-xE.sub.xSi.sub.yO.sub.z where "n" is the mole ratio of Na to (Al+E), M represents a metal or metals from zinc, Group 1, Group 2, Group 3 and or the lanthanide series of the periodic table, "m" is the mole ratio of M to (Al+E), "k" is the average charge of the metal or metals M, T is the organic structure directing agent or agents, and E is a framework element such as gallium. The process involves contacting a carbonaceous biomass feedstock with UZM-44 at pyrolysis conditions to produce pyrolysis gases comprising hydrocarbons. The catalyst catalyzes a deoxygenation reaction converting oxygenated hydrocarbons into hydrocarbons and removing the oxygen as carbon oxides and water. A portion of the pyrolysis gases is condensed to produce low oxygen biomass-derived pyrolysis oil.

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

Science.gov (United States)

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

2014-11-01

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

Upgrading biomass pyrolysis bio-oil to renewable fuels.

Science.gov (United States)

2015-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-10-30

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

Combustion Properties of Biomass Flash Pyrolysis Oils: Final Project Report

Energy Technology Data Exchange (ETDEWEB)

C. R. Shaddix; D. R. Hardesty

1999-04-01

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

Effects of Non-Equilibrium Chemistry and Darcy-Forchheimer Flow of Pyrolysis Gas for a Charring Ablator

Science.gov (United States)

Chen, Yih-Kanq; Milos, Frank S.

2011-01-01

The Fully Implicit Ablation and Thermal Response code, FIAT, simulates pyrolysis and ablation of thermal protection materials and systems. The governing equations, which include energy conservation, a three-component decomposition model, and a surface energy balance, are solved with a moving grid. This work describes new modeling capabilities that are added to a special version of FIAT. These capabilities include a time-dependent pyrolysis gas flow momentum equation with Darcy-Forchheimer terms and pyrolysis gas species conservation equations with finite-rate homogeneous chemical reactions. The total energy conservation equation is also enhanced for consistency with these new additions. Parametric studies are performed using this enhanced version of FIAT. Two groups of analyses of Phenolic Impregnated Carbon Ablator (PICA) are presented. In the first group, an Orion flight environment for a proposed Lunar-return trajectory is considered. In the second group, various test conditions for arcjet models are examined. The central focus of these parametric studies is to understand the effect of pyrolysis gas momentum transfer on PICA material in-depth thermal responses with finite-rate, equilibrium, or frozen homogeneous gas chemistry. Results are presented, discussed, and compared with those predicted by the baseline PICA/FIAT ablation and thermal response model developed by the Orion Thermal Protection System Advanced Development Project.

Co-pyrolysis of low rank coals and biomass: Product distributions

Energy Technology Data Exchange (ETDEWEB)

Soncini, Ryan M.; Means, Nicholas C.; Weiland, Nathan T.

2013-10-01

Pyrolysis and gasification of combined low rank coal and biomass feeds are the subject of much study in an effort to mitigate the production of green house gases from integrated gasification combined cycle (IGCC) systems. While co-feeding has the potential to reduce the net carbon footprint of commercial gasification operations, the effects of co-feeding on kinetics and product distributions requires study to ensure the success of this strategy. Southern yellow pine was pyrolyzed in a semi-batch type drop tube reactor with either Powder River Basin sub-bituminous coal or Mississippi lignite at several temperatures and feed ratios. Product gas composition of expected primary constituents (CO, CO{sub 2}, CH{sub 4}, H{sub 2}, H{sub 2}O, and C{sub 2}H{sub 4}) was determined by in-situ mass spectrometry while minor gaseous constituents were determined using a GC-MS. Product distributions are fit to linear functions of temperature, and quadratic functions of biomass fraction, for use in computational co-pyrolysis simulations. The results are shown to yield significant nonlinearities, particularly at higher temperatures and for lower ranked coals. The co-pyrolysis product distributions evolve more tar, and less char, CH{sub 4}, and C{sub 2}H{sub 4}, than an additive pyrolysis process would suggest. For lignite co-pyrolysis, CO and H{sub 2} production are also reduced. The data suggests that evolution of hydrogen from rapid pyrolysis of biomass prevents the crosslinking of fragmented aromatic structures during coal pyrolysis to produce tar, rather than secondary char and light gases. Finally, it is shown that, for the two coal types tested, co-pyrolysis synergies are more significant as coal rank decreases, likely because the initial structure in these coals contains larger pores and smaller clusters of aromatic structures which are more readily retained as tar in rapid co-pyrolysis.

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

Energy Technology Data Exchange (ETDEWEB)

Ben Hassen-Trabelsi, A., E-mail: aidabenhassen@yahoo.fr [Centre de Recherche et de Technologies de l’Energie (CRTEn), Technopôle Borj-Cédria, B.P 95, 2050, Hammam Lif (Tunisia); Kraiem, T. [Centre de Recherche et de Technologies de l’Energie (CRTEn), Technopôle Borj-Cédria, B.P 95, 2050, Hammam Lif (Tunisia); Département de Géologie, Université de Tunis, 2092, Tunis (Tunisia); Naoui, S. [Centre de Recherche et de Technologies de l’Energie (CRTEn), Technopôle Borj-Cédria, B.P 95, 2050, Hammam Lif (Tunisia); Belayouni, H. [Département de Géologie, Université de Tunis, 2092, Tunis (Tunisia)

2014-01-15

Highlights: • Produced bio-fuels (bio-oil and bio-char) from some animal fatty wastes. • Investigated the effects of main parameters on pyrolysis products distribution. • Determined the suitable conditions for the production of the maximum of bio-oil. • Characterized bio-oils and bio-chars obtained from several animal fatty wastes. - Abstract: Several animal (lamb, poultry and swine) fatty wastes were pyrolyzed under nitrogen, in a laboratory scale fixed-bed reactor and the main products (liquid bio-oil, solid bio-char and syngas) were obtained. The purpose of this study is to produce and characterize bio-oil and bio-char obtained from pyrolysis of animal fatty wastes. The maximum production of bio-oil was achieved at a pyrolysis temperature of 500 °C and a heating rate of 5 °C/min. The chemical (GC–MS analyses) and spectroscopic analyses (FTIR analyses) of bio-oil showed that it is a complex mixture consisting of different classes of organic compounds, i.e., hydrocarbons (alkanes, alkenes, cyclic compounds…etc.), carboxylic acids, aldehydes, ketones, esters,…etc. According to fuel properties, produced bio-oils showed good properties, suitable for its use as an engine fuel or as a potential source for synthetic fuels and chemical feedstock. Obtained bio-chars had low carbon content and high ash content which make them unattractive for as renewable source energy.

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

International Nuclear Information System (INIS)

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

2014-01-01

Highlights: • Produced bio-fuels (bio-oil and bio-char) from some animal fatty wastes. • Investigated the effects of main parameters on pyrolysis products distribution. • Determined the suitable conditions for the production of the maximum of bio-oil. • Characterized bio-oils and bio-chars obtained from several animal fatty wastes. - Abstract: Several animal (lamb, poultry and swine) fatty wastes were pyrolyzed under nitrogen, in a laboratory scale fixed-bed reactor and the main products (liquid bio-oil, solid bio-char and syngas) were obtained. The purpose of this study is to produce and characterize bio-oil and bio-char obtained from pyrolysis of animal fatty wastes. The maximum production of bio-oil was achieved at a pyrolysis temperature of 500 °C and a heating rate of 5 °C/min. The chemical (GC–MS analyses) and spectroscopic analyses (FTIR analyses) of bio-oil showed that it is a complex mixture consisting of different classes of organic compounds, i.e., hydrocarbons (alkanes, alkenes, cyclic compounds…etc.), carboxylic acids, aldehydes, ketones, esters,…etc. According to fuel properties, produced bio-oils showed good properties, suitable for its use as an engine fuel or as a potential source for synthetic fuels and chemical feedstock. Obtained bio-chars had low carbon content and high ash content which make them unattractive for as renewable source energy

Effluent Gas Flux Characterization During Pyrolysis of Chicken Manure

Science.gov (United States)

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

2017-12-01

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

Toxicity of pyrolysis gases from polyether sulfone

Science.gov (United States)

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.

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

International Nuclear Information System (INIS)

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

2016-01-01

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

Pyrolysis mechanism of microalgae Nannochloropsis sp. based on model compounds and their interaction

International Nuclear Information System (INIS)

Wang, Xin; Tang, Xiaohan; Yang, Xiaoyi

2017-01-01

Highlights: • Pyrolysis experiments were conducted by model compounds of algal components. • Interaction affected little bio-crude yield of model compounds co-pyrolysis. • Some interaction pathways between microalgae components were recommended. • N-heterocyclic compounds were further pyrolysis products of Maillard reaction products. • Surfactant synthesis (lipid-amino acids and lipid-glucose) between algal components. - Abstract: Pyrolysis is one of important pathways to convert microalgae to liquid biofuels and key components of microalgae have different chemical composition and structure, which provides a barrier for large-scale microalgae-based liquid biofuel application. Microalgae component pyrolysis mechanism should be researched to optimal pyrolysis process parameters. In this study, single pyrolysis and co-pyrolysis of microalgal components (model compounds castor oil, soybean protein and glucose) were conducted to reveal interaction between them by thermogrametric analysis and bio-crude evaluation. Castor oil (model compound of lipid) has higher pyrolysis temperature than other model compounds and has the maximum contribution to bio-crude formation. Bio-crude from soybean protein has higher N-heterocyclic compounds as well as phenols, which could be important aromatic hydrocarbon source during biorefineries and alternative aviation biofuel production. Potential interaction pathways based on model compounds are recommended including further decomposition of Maillard reaction products (MRPs) and surfactant synthesis, which indicate that glucose played an important role on pyrolysis of microalgal protein and lipid components. The results should provide necessary information for microalgae pyrolysis process optimization and large-scale pyrolysis reactor design.

Method of pyrolysis for spent ion-exchange resins

International Nuclear Information System (INIS)

Aoyama, Yoshiyuki; Matsuda, Masami; Kawamura, Fumio; Yusa, Hideo.

1985-01-01

Purpose: To prevent the generation of noxious sulfur oxide and ammonia on the pyrolysis for spent ion-exchange resins discharged from nuclear power plants. Method: In the case where the pyrolysis is made for the cationic exchange resins having sulfonic acids as the ion-exchange group, alkali metals or alkaline earth metals capable of reacting with sulfonic acid groups to form solid sulfates are previously deposited by way of ion-exchange reactions prior to the pyrolysis. In another case of the anionic exchange resins having quarternary ammonium groups as the ion-exchange groups, halogenic elements capable of reacting with the ammonium groups to form solid ammonium salts are deposited to the ion-exchange resins through ion-exchange reactions prior to the pyrolysis. As a result, the amount of the binders used can be reduced, and this method can be used in a relatively simple processing facility. (Horiuchi, T.)

Pyrolysis of D-Glucose to Acrolein

Science.gov (United States)

Shen, Chong; Zhang, Igor Ying; Fu, Gang; Xu, Xin

2011-06-01

Despite of its great importance, the detailed molecular mechanism for carbohydrate pyrolysis remains poorly understood. We perform a density functional study with a newly developed XYG3 functional on the processes for D-glucose pyrolysis to acrolein. The most feasible reaction pathway starts from an isomerization from D-glucose to D-fructose, which then undergoes a cyclic Grob fragmentation, followed by a concerted electrocyclic dehydration to yield acrolein. This mechanism can account for the known experimental results.

Theoretical study of the pyrolysis of vanillin as a model of secondary lignin pyrolysis

Science.gov (United States)

Wang, Meng; Liu, Chao; Xu, Xiaoxiao; Li, Qibin

2016-06-01

The unimolecular and bimolecular decomposition reactions in processes of vanillin pyrolysis were theoretically investigated by employing density functional theory (DFT) method at M06-2X/6-31 G+(d,p) level. The result shows that the homolytic cleavage of O-CH3 bond could be the dominant initial step in the pyrolysis of vanillin. The hydrogen abstractions from functional groups of vanillin by the formed radicals play important roles in the formation of main products. Both formyl, hydroxyl and methoxyl group contribute to the formation of CO. Benzene is formed from the hydrogen addition reaction between hydrogen radical and phenol at high temperature.

Bio-oil from Flash Pyrolysis of Agricultural Residues

DEFF Research Database (Denmark)

Ibrahim, Norazana

This thesis describes the production of bio-oils from flash pyrolysis of agricultural residues, using a pyrolysis centrifugal reactor (PCR). By thermal degradation of agricultural residues in the PCR, a liquid oil, char and non-condensable gases are produced. The yield of each fraction...

Experiments and stochastic simulations of lignite coal during pyrolysis and gasification

International Nuclear Information System (INIS)

Ahmed, I.I.; Gupta, A.K.

2013-01-01

Highlights: ► Lignite pyrolysis and gasification has been conducted in a semi batch reactor. ► The objective is to understand mechanism of syngas evolution during pyrolysis. ► Stochastic simulations of lignite pyrolysis were conducted using Gillespie algorithm. ► First order, single step mechanism failed to fit cumulative yield of hydrogen. ► Evolution of hydrogen via pyrolysis of gaseous hydrocarbon following bridges scission. -- Abstract: Lignite pyrolysis and gasification has been conducted in a semi batch reactor at reactor temperatures of 800–950 °C in 50 °C intervals. CO 2 has been used as the gasifying agent for gasification experiments. The objective of this investigation is to understand the mechanism of syngas evolution during pyrolysis and to unravel the effect of CO 2 on pyrolysis mechanism. Stochastic simulations of lignite pyrolysis have been conducted using Gillespie algorithm. Two reaction mechanisms have been used in the simulations; first order, single step mechanism and the FLASHCHAIN mechanism. The first order single step mechanism was successful in fitting cumulative yield of CO 2 , CO, CH 4 and other hydrocarbons (C n H m ). The first order, single step failed to fit the cumulative yield of hydrogen, which suggests a more complex mechanism for hydrogen evolution. Evolution of CO 2 , CO, CH 4 , C n H m and H 2 flow rates has been monitored. The only effect of CO 2 on pyrolysis mechanism is promotion of reverse water gas shift reaction for the experiments described here. Methane evolution extended for slightly longer time than other hydrocarbons and hydrogen evolution extended for a slightly longer time than methane. This indicated the evolution of hydrogen via further pyrolysis of aliphatic hydrocarbon. It is also suggested that this step occurs in series after aliphatic hydrocarbons evolution by bridges scission.

Thermal behaviour during the pyrolysis of low rank perhydrous coals

Energy Technology Data Exchange (ETDEWEB)

Arenillas, A.; Rubiera, F.; Pis, J.J.; Cuesta, M.J.; Suarez-Ruiz, I. [Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain); Iglesias, M.J. [Area de Quimica Organica, Universidad de Almeria, Carretera de Sacramento, 04120 Almeria (Spain); Jimenez, A. [Area de Cristalografia y Mineralogia, Departamento de Geologia, Campus de Llamaquique, 33005 Oviedo (Spain)

2003-08-01

Perhydrous coals are characterised by high H/C atomic ratios and so their chemical structure is substantially modified with respect to that of conventional coals. As a result, perhydrous coals show different physico-chemical properties to common coals (i.e. higher volatile matter content, enhancement of oil/tar potential, relatively lower porosity and higher fluidity during carbonisation). However, there is little information about thermal behaviour during the pyrolysis of this type of coal. In this work, six perhydrous coals (H/C ratio between 0.83 and 1.07) were pyrolysed and analysed by simultaneous thermogravimetry/mass spectrometry. The results of this work have revealed the influence of high H/C values on the thermal behaviour of the coals studied. During pyrolysis the perhydrous coals exhibit very well defined, symmetrical peaks in the mass loss rate profiles, while normal coals usually show a broader peak. The shape of such curves suggests that in perhydrous coals fragmentation processes prevailed over condensation reactions. The high hydrogen content of perhydrous coals may stabilise the free radicals formed during heat treatment, increasing the production of light components.

Solar coal gasification reactor with pyrolysis gas recycle

Science.gov (United States)

Aiman, William R.; Gregg, David W.

1983-01-01

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

Effects of carbon dioxide on pyrolysis of peat

International Nuclear Information System (INIS)

Lee, Jechan; Yang, Xiao; Song, Hocheol; Ok, Yong Sik; Kwon, Eilhann E.

2017-01-01

This study focuses on the mechanistic understanding of effects of CO 2 on pyrolysis of peat. To do this, three pyrolytic products (i.e., syngas: H 2 and CO, pyrolytic oil (tar), and biochar) were characterized. Thermal cracking of volatile organic carbons (VOCs) generated from pyrolysis of peat was enhanced in the presence of CO 2 . Besides the enhanced thermal cracking of VOCs, unknown reaction between CO 2 and VOCs was also identified. Accordingly, CO 2 played a role in enhancing syngas production and in reducing tar formation in pyrolysis of peat. This study also reveals that peat-biochar produced in CO 2 exhibited a larger surface area than that produced in N 2 . The results shown in this paper would be used for various applications such as energy recovery from peat using a potent greenhouse gas (for example, CO 2 ). - Highlights: • More CO can be produced from pyrolysis of peat in CO 2 than in N 2 . • Less amount of tar produced from pyrolysis of peat in CO 2 than in N 2 . • Surface area of peat-biochar made in CO 2 is larger than that made in N 2 . • CO 2 can modify the quantity/quality of pyrolytic products from peat.

Novel technique for coal pyrolysis and hydrogenation product analysis

Energy Technology Data Exchange (ETDEWEB)

Pfefferle, L.D.

1992-01-01

This report covers the last quarter of the last year of the three-year grant period. In the final project year, we concentrated on the pyrolysis and oxidative pyrolysis of large hydrocarbons and mixtures of large and small hydrocarbons in order to develop the VUV-MS technique for compounds more representative of those in coal pyrolysis applications. Special focus was directed at the pyrolysis and oxidative pyrolysis of benzene and benzene acetylene mixtures. The acetylene/benzene mixtures were used to gain a better understanding of the mechanisms of molecular growth in such systems specifically to look at the kinetics of aryl-aryl reactions as opposed to small molecule addition to phenyl radicals. Sarofim and coworkers at MIT have recently demonstrated the importance of these reactions in coal processing environments. In the past, the growth mechanism for the formation of midsized PAH has been postulated to involve primarily successive acetylene additions to phenyl-type radicals, our work confmns this as an important mechanism especially for smaller PAH but also investigates conditions where biaryl formation can play an important role in higher hydrocarbon formation.

Simulating Biomass Fast Pyrolysis at the Single Particle Scale

Energy Technology Data Exchange (ETDEWEB)

Ciesielski, Peter [National Renewable Energy Laboratory (NREL); Wiggins, Gavin [ORNL; Daw, C Stuart [ORNL; Jakes, Joseph E. [U.S. Forest Service, Forest Products Laboratory, Madison, Wisconsin, USA

2017-07-01

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

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

International Nuclear Information System (INIS)

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

2013-01-01

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

Fermentation, gasification and pyrolysis of carbonaceous residues towards usage in fuel cells

International Nuclear Information System (INIS)

Sequeira, C.A.C.; Brito, P.S.D.; Mota, A.F.; Carvalho, J.L.; Rodrigues, L.F.F.T.T.G.; Santos, D.M.F.; Barrio, D.B.; Justo, D.M.

2007-01-01

In this paper, the technologies of fermentation, gasification and pyrolysis of carbonaceous residues for the production of biohydrogen and other gaseous, liquid or solid fuels, are analysed. The energetic, economic and environmental advantages of linking these energy areas with the fuel cell engines are stressed. In addition, the current status of fuel cell technologies, namely their historic trends, basic electrode mechanisms, cell types, market drivers and leading issues, are reviewed

Development of advanced technologies for biomass pyrolysis

Science.gov (United States)

Xu, Ran

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

Identification of provenance rocks based on EPMA analyses of heavy minerals

Science.gov (United States)

Shimizu, M.; Sano, N.; Ueki, T.; Yonaga, Y.; Yasue, K. I.; Masakazu, N.

2017-12-01

Information on mountain building is significant in the field of geological disposal of high-level radioactive waste, because this affects long-term stability in groundwater flow system. Provenance analysis is one of effective approaches for understanding building process of mountains. Chemical compositions of heavy minerals, as well as their chronological data, can be an index for identification of provenance rocks. The accurate identification requires the measurement of as many grains as possible. In order to achieve an efficient provenance analysis, we developed a method for quick identification of heavy minerals using an Electron Probe Micro Analyzer (EPMA). In this method, heavy mineral grains extracted from a sample were aligned on a glass slide and mounted in a resin. Concentration of 28 elements was measured for 300-500 grains per sample using EPMA. To measure as many grains as possible, we prioritized swiftness of measurement over precision, configuring measurement time of about 3.5 minutes for each grain. Identification of heavy minerals was based on their chemical composition. We developed a Microsoft® Excel® spread sheet input criteria of mineral identification using a typical range of chemical compositions for each mineral. The grains of 110 wt.% total were rejected. The criteria of mineral identification were revised through the comparison between mineral identification by optical microscopy and chemical compositions of grains classified as "unknown minerals". Provenance rocks can be identified based on abundance ratio of identified minerals. If no significant difference of the abundance ratio was found among source rocks, chemical composition of specific minerals was used as another index. This method was applied to the sediments of some regions in Japan where provenance rocks had lithological variations but similar formation ages. Consequently, the provenance rocks were identified based on chemical compositions of heavy minerals resistant to

Cheap carbon sorbents produced from lignite by catalytic pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Kuznetsov, B.N.; Schchipko, M.L. [Inst. of Chemistry of Natural Organic Materials, Akademgorodok, Krasnoyarsk (Russian Federation)

1995-12-01

Some data are presented describing the new technology of carbon sorbent production from powdered lignite in the installation with fluidized bed of catalyst. It was shown the different types of char products with extended pore structure and high sorption ability can be produced from cheap and accessible lignite of Kansk-Achinsk coal pit in pilot installation with fluidized bed of Al-Cu-Cr oxide catalyst or catalytically active slag materials. In comparison with the conventional technologies of pyrolysis the catalytic pyrolysis allows to increase by 3-5 times the process productivity and to decrease significantly the formation of harmful compounds. The latter is accomplished by complete oxidation of gaseous pyrolysis products in the presence of catalysts and by avoiding the formation of pyrolysis tars - the source of cancerogenic compounds. The technology of cheap powdered sorbent production from lignites makes possible to obtain from lignite during the time of pyrolysis only a few seconds char products with porosity up to 0.6 cm{sup 3} /g, and specific surface area more than 400 m{sup 3} /g. Some methods of powdered chars molding into carbon materials with the different shape were proved for producing of firmness sorbents. Cheap carbon sorbents obtained by thermocatalytic pyrolysis can be successfully used in purification of different industrial pollutants as one-time sorbent or as adsorbents of long-term application with periodic regeneration.

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

Science.gov (United States)

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.

Chemical recycling of mixed waste plastics by selective pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Tatsumoto, K.; Meglen, R.; Evans, R. [National Renewable Energy Laboratory, Golden, CO (United States)

1995-05-01

The goal of this work is to use selective pyrolysis to produce high-value chemicals from waste plastics mixtures. Selectivity is achieved by exploiting differences in reaction rates, catalysis, and coreactants. Target wastes are molecular mixtures such as; blends or composites, or mixtures from manufactured products such as; carpets and post-consumer mixed-plastic wastes. The experimental approach has been to use small-scale experiments using molecular beam mass spectrometry (MBMS), which provides rapid analysis of reaction products and permits rapid screening of process parameters. Rapid screening experiments permit exploration of many potential waste stream applications for the selective pyrolysis process. After initial screening, small-scale, fixed-bed and fluidized-bed reactors are used to provide products for conventional chemical analysis, to determine material balances, and to test the concept under conditions that will be used at a larger scale. Computer assisted data interpretation and intelligent chemical processing are used to extract process-relevant information from these experiments. An important element of this project employs technoeconomic assessments and market analyses of durables, the availability of other wastes, and end-product uses to identify target applications that have the potential for economic success.

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

Science.gov (United States)

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.

Fast Pyrolysis of Four Lignins from Different Isolation Processes Using Py-GC/MS

Directory of Open Access Journals (Sweden)

Xiaona Lin

2015-06-01

Full Text Available Pyrolysis is a promising approach that is being investigated to convert lignin into higher value products including biofuels and phenolic chemicals. In this study, fast pyrolysis of four types of lignin, including milled Amur linden wood lignin (MWL, enzymatic hydrolysis corn stover lignin (EHL, wheat straw alkali lignin (AL and wheat straw sulfonate lignin (SL, were performed using pyrolysis gas-chromatography/mass spectrometry (Py-GC/MS. Thermogravimetric analysis (TGA showed that the four lignins exhibited widely different thermolysis behaviors. The four lignins had similar functional groups according to the FTIR analysis. Syringyl, guaiacyl and p-hydroxyphenylpropane structural units were broken down during pyrolysis. Fast pyrolysis product distributions from the four lignins depended strongly on the lignin origin and isolation process. Phenols were the most abundant pyrolysis products from MWL, EHL and AL. However, SL produced a large number of furan compounds and sulfur compounds originating from kraft pulping. The effects of pyrolysis temperature and time on the product distributions from corn stover EHL were also studied. At 350 °C, EHL pyrolysis mainly produced acids and alcohols, while phenols became the main products at higher temperature. No obvious influence of pyrolysis time was observed on EHL pyrolysis product distributions.

Stabilization of Pb(II) accumulated in biomass through phosphate-pretreated pyrolysis at low temperatures

Energy Technology Data Exchange (ETDEWEB)

Li, Saijun; Zhang, Tao; Li, Jianfa, E-mail: ljf@usx.edu.cn; Shi, Lingna; Zhu, Xiaoxiao; Lü, Jinhong; Li, Yimin

2017-02-15

Highlights: • Phosphate-pretreated pyrolysis can stabilize Pb(II) accumulated in biomass. • More than 95% of Pb(II) in celery and wood biomass was stabilized. • Pb from biomass was almost totally retained in char. • Most Pb was transformed into phosphates according to XRD and SEM/EDX analyses. - Abstract: The remediation of heavy metal-contaminated soil and water using plant biomass is considered to be a green technological approach, although the harmless disposal of biomass accumulated with heavy metals remains a challenge. A potential solution to this problem explored in this work involves combining phosphate pretreatment with pyrolysis. Pb(II) was accumulated in celery biomass with superior sorption capacity and also in ordinary wood biomass through biosorption. The Pb(II)-impregnated biomass was then pretreated with phosphoric acid or calcium dihydrogen phosphate (CaP) and pyrolyzed at 350 or 450 °C. Pb(II) from biomass was in turn almost totally retained in chars, and the percentage of DTPA-extractable Pb(II) was reduced to less than 5% of total Pb(II) in chars through CaP pretreatment. Pb(II) stabilization was further confirmed through a sequential extraction test, which showed that more than 95% of Pb(II) was converted into stable species composed mainly of lead phosphates according to X-ray diffraction (XRD) and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analyses. Overall, phosphate-pretreated pyrolysis can stabilize both Pb(II) and degradable biomass, so as to control efficiently the hazards of heavy metal-contaminated biomass.

Bitumen pyrolysis

International Nuclear Information System (INIS)

Braehler, G.; Noll, T.

2014-01-01

In the past bitumen was a preferred matrix for the embedding of low and intermediate level radioactive waste: its geological history promised long term stability in final repositories. A great variety of waste has been embedded: technological waste, spent ion exchange resins, concrete, rubble, etc. Liquid waste like evaporator concentrates can be dried and embedded simultaneously in extruders, allowing simple processes and equipment. Unfortunately, during long term intermediate storage the bituminized waste drums proved out being not as stable as expected: a significant number turned out to be no longer acceptable for final disposal, and some of them even needed repacking to enable further intermediate storage. A method to rework such drums with bituminized radioactive waste seems to be urgently needed. Pyrolysis and pyro-hydrolysis (= pyrolysis with water steam added) have a long history for the treatment of organic waste: spent solvent (TBP), spent ion exchange resins, alpha waste (predominantly PVC), etc. Due to its low process temperature and the endothermic character, such processes offer significant safety advantages, as compared to incineration or dissolving in organic solvents. Results of lab-scale investigations and concepts for facilities are presented. (authors)

Perspectives for pyrolysis oil production and market in Scandinavia

International Nuclear Information System (INIS)

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

1999-01-01

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

Pyrolysis of Rubber in a Screw Reactor

Science.gov (United States)

Lozhechnik, A. V.; Savchin, V. V.

2016-11-01

On the basis of an analysis of thermal methods described in the literature and from the results of experimental investigations of steam conversion, the authors have developed and created a facility for thermal processing of rubber waste. Rubber crumb was used as the raw material; the temperature in the reactor was 500°C; nitrogen, steam, and a mixture of light hydrocarbons (noncondensable part of pyrolysis products) represented the working medium. The pyrolysis yielded 36-38% of a solid fraction, 54-56% of a liquid hydrocarbon fraction, and 6-9% of noncondensable gases. Changes in the composition of the gas mixture have been determined at different stages of processing. Gas chromatography of pyrolysis gases has shown that the basic gases produced by pyrolysis are H2 and hydrocarbons C2H4, C3H6, C3H8, C4H8, C2H6, C3H6O2, and C4H10, and a small amount of H2S, CO, and CO2. Noncondensable gases will be used as a fuel to heat the reactor and to implement the process.

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

DEFF Research Database (Denmark)

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

2013-01-01

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

The rock mechanical stability of the VLJ repository

International Nuclear Information System (INIS)

Kuula, H.; Johansson, E.

1991-03-01

The aim of the study was to determine the rock mechanical stability around the VLJ repository based on the rock mechanical monitoring and rock mechanical modeling. Rock mechanical calculations were made in order to calculate the rock mass displacements and to analyze the stability around the VLJ repository The calculations were performed with three diiferent methods: continuum finite difference code FLAC, distinct element code UDEC and three dimensional distinct element code 3DEC. The first analyses were based on preliminary site investigations. The final modeling was based on investigations and rock mechanical monitoring done during the excavation. Some sensitive analyses were also performed. The modelled rock mass behaviour and the measured behaviour are generally close to each other. Both results show that the VLJ repository is rock mechanically stable. The modelled displacements and stresses were small enough to cause no instability around the rock caverns. The measured values do not indicate any discontinuous deformations like block movements or joint slip. The measured displacements in the extensometers during excavation indicates that the rock mass is even stiffer than anticipated

Hydrogen assisted catalytic biomass pyrolysis for green fuels

DEFF Research Database (Denmark)

Stummann, Magnus Zingler; Høj, Martin; Gabrielsen, Jostein

2017-01-01

due to coking of the catalyst is an inhibitive problem for this technology. The objective of the present work is to produce oxygen free gasoline and diesel from biomass by hydrogen assisted catalytic fast pyrolysis. Fast pyrolysis of beech wood has been performed in high-pressure hydrogen atmosphere...

Co pyrolysis of biomass and PP

International Nuclear Information System (INIS)

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

2010-01-01

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

Oxidative desulfurization of tire pyrolysis oil

Directory of Open Access Journals (Sweden)

Ahmad Shahzad

2016-01-01

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

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Pyrolysis of Cigarette Ingredients Labelled with Stable Isotopes

Directory of Open Access Journals (Sweden)

Stotesbury S

2014-12-01

Full Text Available It is important to know how tobacco additives behave when cigarettes are smoked, whether they transfer intact to the smoke or whether there is any decomposition during smoking. Pyrolysis-GC-MS is a technique that can be focussed upon the effects of combustion from a single material free from interference from the complex mixture of different components present in the smoke. However, because pyrolysis is a model technique, the results need to be validated by comparison with cigarette smoke chemistry. In a previous paper we presented such a method for modelling the smoke chemistry from a burning cigarette using pyrolysis-GC-MS. The transfer and the extent of degradation of anisole, p-anisaldehyde, benzaldehyde, isoamylisovalerate, methyl trans-cinnamate and vanillin within a burning cigarette were estimated using this pyrolysis method. When these data were compared with results from smoke studies from 14C-analogues of the materials, the high levels of transfer predicted by pyrolysis were found to be generally consistent with the smoke chemistry data. However, there were still two outstanding issues. Firstly, there was some ambiguity in the labelled study about whether vanillin actually transferred without degradation or not. Furthermore, the results from the 14C-labelled study showed a greater extent of degradation for p-anisaldehyde than that indicated from the pyrolysis experiments. The purpose of the current study was to present some new information obtained to address these questions by better understanding the effect upon the smoke chemistry from adding vanillin and p-anisaldehyde, and the relationship between the smoke chemistry and the pyrolysis results. Components were identified in the smoke from cigarettes loaded with p-anisaldehyde and vanillin labelled with 18O and 13C. The extent of degradation from each additive was estimated by identifying labelled degradation products in the smoke. Because there was a clear distinction between the

Thermal and catalytic pyrolysis of a mixture of plastics from small waste electrical and electronic equipment (WEEE).

Science.gov (United States)

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.

Experimental Field Tests and Finite Element Analyses for Rock Cracking Using the Expansion of Vermiculite Materials

Directory of Open Access Journals (Sweden)

Chi-hyung Ahn

2016-01-01

Full Text Available In the previous research, laboratory tests were performed in order to measure the expansion of vermiculite upon heating and to convert it into expansion pressure. Based on these test results, this study mainly focuses on experimental field tests conducted to verify that expansion pressure obtained by heating vermiculite materials is enough to break massive and hard granite rock with an intention to excavate the tunnel. Hexahedral granite specimens with a circular hole perforated in the center were constructed for the experimental tests. The circular holes were filled with vermiculite plus thermal conduction and then heated using the cartridge heater. As a result, all of hexahedral granite specimens had cracks in the surface after 700-second thermal heating and were finally spilt into two pieces completely. The specimen of larger size only requires more heating time and expansion pressure. The material properties of granite rocks, which were obtained from the experimental tests, were utilized to produce finite element models used for numerical analyses. The analysis results show good agreement with the experimental results in terms of initial cracking, propagation direction, and expansion pressure.

Kinetic modeling of ethane pyrolysis at high conversion.

Science.gov (United States)

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

Distribution of sulphur into products from waste tire pyrolysis

International Nuclear Information System (INIS)

Susa, D.; Haydary, J.; Markos, J.

2012-01-01

Tire pyrolysis is getting growing attention as an effective waste tire disposal method in comparison to environmentally less friendly methods like dumping or incineration. But the scrap tire sulphur content can be a potential obstacle to scrap tire utilization as a fuel. In this paper the distribution of sulphur into tire pyrolysis yields, solid (char) and liquid (tar), was investigated. The pyrolysis experiments were carried out under different conditions to determine the partitioning of sulphur into pyrolysis products. The influence of different temperatures and reaction times was investigated in a laboratory flow reactor under nitrogen atmosphere. Solid and liquid residues were collected and analyzed by elemental analysis. The sulphur content in residual char and tar was determined using an elemental analyzer and the sulphur forms in tar were characterized by the X-ray photoelectron spectroscopy (XPS). (Authors)

Experimental study of rapid brown coal pyrolysis at high temperature

Energy Technology Data Exchange (ETDEWEB)

Qian, Lin; Sun, Shaozeng; Meng, Shun; Meng, Xianyu; Guo, Yangzhou [Harbin Institute of Technology, Harbin (China). Combustion Engineering Research Inst.

2013-07-01

Rapid coal pyrolysis is a very important step in the early stage of combustion. Rapid pyrolysis experiments of a brown coal at high temperature have been studied on a laminar drop tube furnace. The volatile mass release measured in this study is high for low rank coal. The activation energy and pre-exponential factor of pyrolysis are 19901.22 kJ/mol and 102.71, respectively. The nitrogen distribution between volatile and char is 0.54. With the increase of temperature, the yields of NH{sub 3} decreases, while those of HCN increases, leading the value of HCN/NH{sub 3} to become larger. At high temperature, the main nitrogen- containing species of pyrolysis in volatile is HCN.

Microwave-assisted pyrolysis of biomass for liquid biofuels production

DEFF Research Database (Denmark)

Yin, Chungen

2012-01-01

Production of 2nd-generation biofuels from biomass residues and waste feedstock is gaining great concerns worldwide. Pyrolysis, a thermochemical conversion process involving rapid heating of feedstock under oxygen-absent condition to moderate temperature and rapid quenching of intermediate products......, is an attractive way for bio-oil production. Various efforts have been made to improve pyrolysis process towards higher yield and quality of liquid biofuels and better energy efficiency. Microwave-assisted pyrolysis is one of the promising attempts, mainly due to efficient heating of feedstock by ‘‘microwave...

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

DEFF Research Database (Denmark)

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

2008-01-01

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

Study of mobilization and speciation of trace elements in coal pyrolysis

International Nuclear Information System (INIS)

Ting, B.T.G.

1979-01-01

Various types of coal contain high levels of a number of trace elements. Little is known of the fates of these trace elements during the conversion of coal to liquid and gaseous products. Studies were undertaken of mobilization and speciation of trace elements in coal pyrolysis, one of the major coal conversion processes. The bituminous coal was pyrolyzed to produce liquid and gaseous products. The pyrolysis products were collected in traps in an inert gas stream. In addition mildly hydrogenated coal was prepared by mixing with tetralin, a hydrogen donor solvent, at boiling temperature. In order to characterize each element specifically during pyrolysis, base samples of coal and mildly hydrogenated coal (H-coal) were spiked with heavy metal sulfides, trace metals bound to partially oxidized coal (coal humates), and halide salts prior to carrying out pyrolysis. Eight elements were investigated in this research. They are As, Br, Cl, Co, Cr, Mn, Se, and V. Pre-spiked hydrogenated coal, i.e., pulverized coal spiked with halide salts and heavy metal sulfides then hydrogenated with tetralin, was prepared and studied for the fates of these elements during pyrolysis. Chlorinated and brominated coals were also prepared to compare the volatility differences between organically and inorganically bound halogens during the pyrolysis reaction. These products and the coal char residues were analyzed for the spiked elements mainly by neutron activation analysis for the spiked elements to determine their degree of volatility. Volatility and recovery (mass balance) will be discussed for those elements that appeared highly volatile during pyrolysis. In order to understand the halogenated compounds in the pyrolysis products, gas chromatograms were taken to the collected pyrolysis products of coal, hydrogenated coal, NaCl spiked coal, NaBr spiked coal, chlorinated coal, and brominated coal

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

Science.gov (United States)

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

2018-04-12

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

The identification of synthetic organic pigments in modern paints and modern paintings using pyrolysis-gas chromatography-mass spectrometry.

Science.gov (United States)

Russell, Joanna; Singer, Brian W; Perry, Justin J; Bacon, Anne

2011-05-01

A collection of more than 70 synthetic organic pigments were analysed using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). We report on the analysis of diketo-pyrrolo-pyrrole, isoindolinone and perylene pigments which are classes not previously reported as being analysed by this technique. We also report on a number of azo pigments (2-naphthol, naphthol AS, arylide, diarylide, benzimidazolone and disazo condensation pigments) and phthalocyanine pigments, the Py-GC-MS analysis of which has not been previously reported. The members of each class were found to fragment in a consistent way and the pyrolysis products are reported. The technique was successfully applied to the analysis of paints used by the artist Francis Bacon (1909-1992), to simultaneously identify synthetic organic pigments and synthetic binding media in two samples of paint taken from Bacon's studio and micro-samples taken from three of his paintings and one painting attributed to him.

Demonstration of the waste tire pyrolysis process on pilot scale in a continuous auger reactor

International Nuclear Information System (INIS)

Martínez, Juan Daniel; Murillo, Ramón; García, Tomás; Veses, Alberto

2013-01-01

Highlights: • The continuous pyrolysis of waste tire has been demonstrated at pilot scale in an auger reactor. • More than 500 kg of waste tires were processed in 100 operational hours. • The yields and characteristics of the pyrolysis products remained constant. • Mass and energy balances for an industrial scale plant are provided. • The reaction enthalpy necessary to perform the waste tire pyrolysis was determined. -- Abstract: This work shows the technical feasibility for valorizing waste tires by pyrolysis using a pilot scale facility with a nominal capacity of 150 kW th . 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

Demonstration of the waste tire pyrolysis process on pilot scale in a continuous auger reactor

Energy Technology Data Exchange (ETDEWEB)

Martínez, Juan Daniel, E-mail: juand.martinez@upb.edu.co [Instituto de Carboquímica, ICB-CSIC, Miguel Luesma Castán 4, 50018, Zaragoza (Spain); Grupo de Investigaciones Ambientales, Instituto de Energía, Materiales y Medio Ambiente, Universidad Pontificia Bolivariana, Circular 1 N°70-01, Bloque 11, piso 2, Medellín (Colombia); Murillo, Ramón; García, Tomás; Veses, Alberto [Instituto de Carboquímica, ICB-CSIC, Miguel Luesma Castán 4, 50018, Zaragoza (Spain)

2013-10-15

Highlights: • The continuous pyrolysis of waste tire has been demonstrated at pilot scale in an auger reactor. • More than 500 kg of waste tires were processed in 100 operational hours. • The yields and characteristics of the pyrolysis products remained constant. • Mass and energy balances for an industrial scale plant are provided. • The reaction enthalpy necessary to perform the waste tire pyrolysis was determined. -- Abstract: This work shows the technical feasibility for valorizing waste tires by pyrolysis using a pilot scale facility with a nominal capacity of 150 kW{sub th}. 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.

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

Science.gov (United States)

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

2017-10-01

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

Thermal analysis of charring materials based on pyrolysis interface model

Directory of Open Access Journals (Sweden)

Huang Hai-Ming

2014-01-01

Full Text Available Charring thermal protection systems have been used to protect hypersonic vehicles from high heat loads. The pyrolysis of charring materials is a complicated physical and chemical phenomenon. Based on the pyrolysis interface model, a simulating approach for charring ablation has been designed in order to obtain one dimensional transient thermal behavior of homogeneous charring materials in reentry capsules. As the numerical results indicate, the pyrolysis rate and the surface temperature under a given heat flux rise abruptly in the beginning, then reach a plateau, but the temperature at the bottom rises very slowly to prevent the structural materials from being heated seriously. Pyrolysis mechanism can play an important role in thermal protection systems subjected to serious aerodynamic heat.

Formation of Methoxybenzenes from Cellulose in the Presence of Tetramethylammonium Hydroxide by Pyrolysis

International Nuclear Information System (INIS)

Choi, Sungseen; Kim, Minchul; Kim, Yunki

2013-01-01

Pyrolysis-gas chromatography/mass spectrometry (Pyrolysis-GC/MS) has been extensively used for characterizing the structural information of various macromolecules such as humic substances, woods, and synthetic polymers. Challinor improved the technique by introducing simultaneous pyrolysis and methylation with tetramethylammonium hydroxide (TMAH). As the technique offers a number of advantages over conventional pyrolysis, it has been used widely for the characterization of a wide variety of macro-organic molecules such as polysaccharides. Thermally assisted hydrolysis and methylation of carbohydrates by TMAH has been investigated. This approach has improved the separation by methylation of acidic functional group. Several researchers have demonstrated that the role of TMAH is not only the methylation of the pyrolysis products but also assisting in bond cleavage. Because TMAH possesses a strong basicity, highly basic conditions are likely to induce a variety of reactions. Pyrolysis technique using TMAH renders polar pyrolysis products volatile enough to be eluted from the GC column by subsequent online methylation

Pyrolysis oil from carbonaceous solid wastes in Malaysia

International Nuclear Information System (INIS)

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

2000-01-01

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

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

NARCIS (Netherlands)

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

2016-01-01

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

A novel integrated process of coal pyrolysis and methane CO{sub 2} reforming

Energy Technology Data Exchange (ETDEWEB)

Jing Wang; Pengfei Wang; Lijun Jin; Haoquan Hu [Dalian University of Technology, Dalian (China)

2007-07-01

In the paper, a novel pyrolysis method, namely coal pyrolysis coupling with CO{sub 2} reforming of methane (CRMP) or catalytic pyrolysis of coal coupling with CO{sub 2} reforming of methane (CRMCP), for improving the tar yield of coal pyrolysis was introduced. The behaviours of YM coal in both processes were investigated and compared with pyrolysis under N{sub 2} and H{sub 2}. The results show that the tar yield of coal pyrolysis in both processes obviously increase compared with that in N{sub 2} or H{sub 2}. When YM coal pyrolysis was carried out in stream of mixture gas CH{sub 4}/CO{sub 2} (1:1) with the existence of the catalyst at 0.1 MPa and 800{sup o}C, the tar yield is 2.8 times for CRMP and 4.3 times for CRMCP as that of pyrolysis under N{sub 2} and 1.7 and 2.6 times as that of hydropyrolysis at the same conditions, respectively. Sulfur content of char obtained from CRMP and CRMCP process are lower, especially in CRMP process, than that from N{sub 2} or H{sub 2}. 16 refs., 4 figs., 1 tab.

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

Energy Technology Data Exchange (ETDEWEB)

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

1998-09-01

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

Pyrolysis of superfine pulverized coal. Part 3. Mechanisms of nitrogen-containing species formation

International Nuclear Information System (INIS)

Liu, Jiaxun; Jiang, Xiumin; Shen, Jun; Zhang, Hai

2015-01-01

Highlights: • NH 3 and NO formation mechanisms during superfine pulverized coal pyrolysis are investigated. • Influences of temperature, heating rate, particle size, atmosphere, and acid wash on the NH 3 and NO formation are analyzed. • Transformations of nitrogen-containing structures in coal/char during pyrolysis are recognized through XPS observation. • Relationships among nitrogen-containing gaseous species during pyrolysis are discussed. - Abstract: With more stringent regulations being implemented, elucidating the formation mechanisms of nitrogen-containing species during the initial pyrolysis step becomes important for developing new NO x control strategies. However, there is a lack of agreement on the origins of NO x precursors during coal pyrolysis, in spite of extensive investigations. Hence, it is important to achieve a more precise knowledge of the formation mechanisms of nitrogen-contain species during coal pyrolysis. In this paper, pyrolysis experiments of superfine pulverized coal were performed in a fixed bed at low heating rates. The influences of temperature, coal type, particle size and atmosphere on the NH 3 and NO evolution were discussed. There is a central theme to develop knowledge of the relationship between particle sizes and evolving behaviors of nitrogen-containing species. Furthermore, the catalytic role of inherent minerals in coal was proved to be effective on the partitioning of nitrogen during coal pyrolysis. In addition, the conversion pathways of heteroaromatic nitrogen structures in coal/char during pyrolysis were recognized through the X-ray photoelectron spectroscopy (XPS) analysis. Large quantities of pyridinic and quanternary nitrogen functionalities were formed during the thermal degradation. Finally, the relationships among the nitrogen-containing gaseous species during coal pyrolysis were discussed. In brief, a comprehensive picture of the volatile-nitrogen partitioning during coal pyrolysis is obtained in this

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

Energy Technology Data Exchange (ETDEWEB)

Brady, Patrick D.; Brown, Alexander L.; Mowry, Curtis Dale; Borek, Theodore Thaddeus, III

2011-12-01

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

Summary of Test Results for Daya Bay Rock Samples

International Nuclear Information System (INIS)

Onishi, Celia Tiemi; Dobson, Patrick; Nakagawa, Seiji

2004-01-01

A series of analytical tests was conducted on a suite of granitic rock samples from the Daya Bay region of southeast China. The objective of these analyses was to determine key rock properties that would affect the suitability of this location for the siting of a neutrino oscillation experiment. This report contains the results of chemical analyses, rock property measurements, and a calculation of the mean atomic weight

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

International Nuclear Information System (INIS)

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

2011-01-01

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

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

Science.gov (United States)

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

2017-11-01

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

Pyrolysis of forestry biomass by-products in Greece

Energy Technology Data Exchange (ETDEWEB)

Zabaniotou, A.A. [Aristotle Univ. of Thessaloniki (Greece). Dept. of Chemical Engineering

1999-06-01

This article summarizes the technical characteristics of a biomass pyrolysis pilot plant recently constructed in central Greece. It highlights the considerations involved in achieving successful pyrolysis technology and environmental and developmental goals, by reviewing technical and nontechnical barriers associated with biomass treatment technology in Greece. Data from the start-up phase of the plant operation are presented and some aspects of the process are outlined. The capacity of the plant is 1200--1450 kg/hr, based on wet biomass (Arbutus Unedo) and the pyrolysis temperature is approximately 400 C. Char yield is 14--18% weight on dry basis and is of good quality consisting of 76% C with heat content 6760 kcal/kg. Bio-oil includes 64% C and its heat content is 6250 kcal/kg.

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

International Nuclear Information System (INIS)

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

2017-01-01

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

Pyrolysis and hydropyrolysis performance of Shendong and Pingshuo coal

Energy Technology Data Exchange (ETDEWEB)

Shiping Huang; Bo Wu; Yunpeng Zhao; Lijun Jin; Haoquan Hu [Dalian University of Technology, Dalian (China). Institute of Coal Chemical Engineering

2007-07-01

Pyrolysis and hydropyrolysis of Shendong (SD) and Pingshuo (PS) coal were performed from 500 to 700{sup o}C in a fixed-bed reactor and the product distribution and gas evolution of both processes were analyzed. The results show that, the tar yields of both PS coal and SD coal reach the highest value, about 17 wt% and 13 wt% respectively at temperature 650{sup o}C for pyrolysis. However, the tar yields of PS coal get to the highest value, about 20 wt% at temperature 650{sup o}C, and the tar yields of SD coal are improving with temperature increasing, about 12 wt% at temperature 700{sup o}C for hydropyrolysis. The tar yields of PS coal are higher than those of SD coal at the same conditions for both pyrolysis and hydropyrolysis. The total gas yield of PS coal is higher than that of SD coal for pyrolysis, but lower for hydropyrolysis.

Fast pyrolysis of lignin, macroalgae and sewage sludge

Energy Technology Data Exchange (ETDEWEB)

Trinh, N.T.

2013-04-15

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

Economics of pyrolysis-based energy production and biochar utilization: A case study in Taiwan

International Nuclear Information System (INIS)

Kung, Chih-Chun; McCarl, Bruce A.; Cao, Xiaoyong

2013-01-01

Pyrolysis is an alternative form of renewable energy production and a potential source of greenhouse gas emissions mitigation. This study examines how poplar-based biochar can be applied in Taiwan for electricity generation and for soil improvement and to what extent it brings economic and environmental benefits. It is a preliminary study and focuses on the balances of different economic and environmental items. This paper reports on a case study examination of the economic and greenhouse gas implications of pyrolysis plus biochar utilization. The case study involves using poplar grown on set-aside land in Taiwan with the biochar applied to rice fields. We examine both fast and slow forms of pyrolysis and find how the profitability varies under different price structures. The results show that fast pyrolysis is more profitable than slow pyrolysis under current electricity price, GHG price and crop yield as the slow pyrolysis generates relatively less electricity but lower value product—biochar. We also find that fast pyrolysis and slow pyrolysis offset about 1.4 t and 1.57 t of CO 2 equivalent per ton of raw material, respectively. - Highlights: • Profitability varies due to sales revenue from electricity generation. • Neither fast pyrolysis nor slow pyrolysis is profitable under current electricity price. • Both systems offset about 1.4 t to 1.57 t of CO 2 equivalent per ton of raw material

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

International Nuclear Information System (INIS)

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

2006-01-01

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

High temperature SU-8 pyrolysis for fabrication of carbon electrodes

DEFF Research Database (Denmark)

Hassan, Yasmin Mohamed; Caviglia, Claudia; Hemanth, Suhith

2017-01-01

In this work, we present the investigation of the pyrolysis parameters at high temperature (1100 °C) for the fabrication of two-dimensional pyrolytic carbon electrodes. The electrodes were fabricated by pyrolysis of lithographically patterned negative epoxy based photoresist SU-8. A central...... composite experimental design was used to identify the influence of dwell time at the highest pyrolysis temperature and heating rate on electrical, electrochemical and structural properties of the pyrolytic carbon: Van der Pauw sheet resistance measurements, cyclic voltammetry, electrochemical impedance...... spectroscopy and Raman spectroscopy were used to characterize the pyrolytic carbon. The results show that the temperature increase from 900 °C to 1100 °C improves the electrical and electrochemical properties. At 1100 °C, longer dwell time leads to lower resistivity, while the variation of the pyrolysis...

Volume reduction of ion exchange resin by a pyrolysis technique

International Nuclear Information System (INIS)

Matsuda, M.; Funabashi, K.; Uchida, S.; Kikuchi, M.

1985-01-01

Volume reduction techniques, such as incineration and acid digestion, of spent ion exchange resins from nuclear power plants are being developed with a view toward reducing radioactive waste volume and also making the final waste form more stable. The authors chose pyrolysis as a technique that can be done at low operating temperatures and low gas flow rates in a reactor vessel. Fundamental experiments were performed to clarify the resin pyrolysis characteristics, and the optimum pyrolysis temperature was determined. Consequently, a pilot plant with a treatment capacity of approx. 50 kg/batch was constructed based on the results. Using the pilot plant, the authors are now performing pyrolysis of the resins and solidification of their residues. This report will give the results of fundamental experiments and pilot plant tests

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

Science.gov (United States)

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

Mixtures of rubber tyre and plastic wastes pyrolysis: A kinetic study

International Nuclear Information System (INIS)

Miranda, Miguel; Cabrita, I.; Pinto, Filomena; Gulyurtlu, I.

2013-01-01

The study performed aimed at analysing possible routes for pyrolysis reaction mechanisms of polymeric materials namely RT (rubber tyre) and plastic wastes (PE (polyethylene), PP (polypropylene) and PS (polystyrene)). Consequently, and seeking sustainable transformation of waste streams into valuable chemicals and renewable liquid fuels, mixture of 30% RT, 20% PE, 30% PP and 20% PS was subjected to pyrolysis. Different kinetic models were studied using experimental data. None of the mechanisms found in literature led to a numerical adjustment and different pathways were investigated. Kinetic studies were performed aiming to evaluate direct conversions into new solid, liquid and gaseous products and if parallel reactions and/or reversible elementary steps should be included. Experiments were performed in batch system at different temperatures and reaction times. Kinetic models were evaluated and reaction pathways were proposed. Models reasonably fit experimental data, allow explaining wastes thermal degradation. Kinetic parameters were estimated for all temperatures and dependence of Ea and pre-exponential factor on temperature was evaluated. The rate constant of some reactions exhibited nonlinear temperature dependence on the logarithmic form of Arrhenius law. This fact strongly suggests that temperature has a significant effect on reaction mechanism of pyrolysis of mixtures of rubber tyre and plastic wastes. - Highlights: • Kinetic study of rubber tyre (RT) and different plastic wastes (PE, PP and PS) was performed in batch reactor. • Definition of possible pathways taken into account for the formation of final products. • Kinetic parameters were estimated. • The effect of reaction temperature and reaction time on liquid composition was performed

Spray pyrolysis process for preparing superconductive films

International Nuclear Information System (INIS)

Hsu, H.M.; Yee, I.Y.

1991-01-01

This paper describes a spray pyrolysis method for preparing thin superconductive film. It comprises: preparing a spray pyrolysis solution comprising Bi,Sr,Ca and Cu metals in a solvent; heating a substrate to a first temperature; spraying the solution onto the heated substrate to form a film thereon; heating the film and substrate to a second temperature of about 700 degrees-825 degrees C, the second temperature being higher than the first temperature; heating the film and substrate to a third temperature of about 870 degrees-890 degrees C to melt the film; once the film and substrate reach the third temperature, further heat treating the film and substrate; cooling the film and substrate to ambient temperature. This patent also describes a spray pyrolysis method for preparing thin superconductive films. It comprises: preparing a spray pyrolysis solution comprising Bi, Ca and Cu metals and fluxing agent in a solvent; heating a substrate to a first temperature; spraying the solution onto the heated substrate to form a film thereon; heating the film and substrate to a second temperature about 700 degrees-825 degrees C, the second temperature being higher than the first temperature; heating the film and substrate at a third temperature about 840 degrees-860 degrees C; and cooling the film and substrate to ambient temperature

Co-pyrolysis of coal with organic solids

Energy Technology Data Exchange (ETDEWEB)

Straka, P.; Buchtele, J. [Inst. of Rock Structure and Mechanics, Prague (Czechoslovakia)

1995-12-01

The co-pyrolysis of high volatile A bituminous coal with solid organic materials (proteins, cellulose, polyisoprene, polystyrene, polyethylene-glycolterephtalate-PEGT) at a high temperature conditions was investigated. Aim of the work was to evaluate, firstly, the changes of the texture and of the porous system of solid phase after high temperature treatment in presence of different types of macromolecular solids, secondly, properties and composition of the tar and gas. Considered organic solids are important waste components. During their co-pyrolysis the high volatile bituminous coal acts as a hydrogen donor in the temperature rank 220-480{degrees}C. In the rank 500- 1000{degrees}C the solid phase is formed. The co-pyrolysis was carried out at heating rate 3 K/min. It was found that an amount of organic solid (5-10%) affects important changes in the optical texture forms of solid phase, in the pore distribution and in the internal surface area. Transport large pores volume decreases in presence of PEGT, polystyrene and cellulose and increases in presence of proteins and polyisoprene. (image analysis measurements show that the tendency of coal to create coarse pores during co-pyrolysis is very strong and increases with increasing amount of organic solid in blend). An addition of considered materials changes the sorption ability (methylene blue test, iodine adsorption test), moreover, the reactivity of the solid phase.

Method for Hot Real-Time Sampling of Pyrolysis Vapors

Energy Technology Data Exchange (ETDEWEB)

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

2017-09-29

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

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

Science.gov (United States)

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

2013-02-01

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

Thermodynamic analysis for syngas production from volatiles released in waste tire pyrolysis

International Nuclear Information System (INIS)

Martínez, Juan Daniel; Murillo, Ramón; García, Tomás; Arauzo, Inmaculada

2014-01-01

Highlights: • Pyrolysis experiments have been conducted in a continuous auger reactor. • Pyrolysis temperature influence on composition of both volatiles and char was studied. • A process for syngas production has been proposed from the volatiles. • Equivalence ratio down to 0.4 is a practical limit for syngas production. • The results provide essential data prior to perform any experimental campaign. - Abstract: This paper shows the maximum limit on syngas composition obtained from volatiles released in waste tire pyrolysis when they are submitted to an air–steam partial oxidation process. Thus, from mass and energy balances and a stoichiometric equilibrium model, syngas composition and reaction temperature as well as some process parameters were predicted by varying both the equivalence ratio (ER) and the steam to fuel ratio (SF). In addition, pyrolysis experiments were performed using a continuous auger reactor, and the influence of pyrolysis temperature on composition of both volatiles and char was studied. Consequently, the resulting syngas characteristics were correlated with the pyrolysis temperature. The stoichiometric equilibrium model showed that an ER down to 0.4 is a practical limit to perform the air–steam partial oxidation process. When the process is carried out only with air, volatiles obtained at high pyrolysis temperature lead to lower reaction temperature and higher LHV of syngas in comparison with those found at low pyrolysis temperature. The H 2 production is favored between 0.20 and 0.40 of ER and seems to be more influenced by the H/C ratio than by the water gas-shift reaction. On the other hand, the steam addition shows a more notable effect on the H 2 production for volatiles obtained at the highest pyrolysis temperature (600 °C) in agreement with the lower reaction temperature under these experimental conditions. This thermodynamic analysis provides essential data on the optimization of syngas production from volatiles

Fast pyrolysis of wheat straw combined with SI-MCM-41 catalyst

Energy Technology Data Exchange (ETDEWEB)

Ates, Funda; Putun, Ayse Eren [Anadolu University, Department of Chemical Engineering, Faculty of Engineering and Architecture (Turkey)], e-mail: fdivrikl@anadolu.edu.tr, email: aeputun@anadolu.edu.tr; Tophanecioglu, Sibel [Erkurt Holding (Turkey)], email: sibel8888@gmail.com

2011-07-01

The purpose of this paper is to give the results of an experiment in which the respective results from fast pyrolysis of wheat straw catalyzed with Si-MCM-4, and in the non-catalytic condition were compared. This experiment was carried out in a well-swept fixed-bed reactor with a heating rate of 300 degree C/min and in a nitrogen atmosphere after which, the main characteristics of pyrolyzed feedstock were determined by proximate, ultimate and component analysis. As the results of this experiment show, the maximum oil yield was 31.9% in a non-catalytic pyrolysis procedure and this gas yield increased in the pyrolysis experiment with catalyst, although the bio-oil yield decreased. On the other hand, the use of catalyst had the benefit of reducing the percentage of oxygen, the presence of which in the fuel is not desirable. Through testing pyrolysis oils, it was established that the use of a catalyst in the pyrolysis can improve fuel quality and produce valuable chemicals.

Coal pyrolysis under synthesis gas, hydrogen and nitrogen

Energy Technology Data Exchange (ETDEWEB)

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

2007-02-15

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

The structure and pyrolysis product distribution of lignite from different sedimentary environment

International Nuclear Information System (INIS)

Liu, Peng; Zhang, Dexiang; Wang, Lanlan; Zhou, Yang; Pan, Tieying; Lu, Xilan

2016-01-01

Highlights: • Carbon structure of three lignites was measured by solid "1"3C NMR. • Effect of carbon structure on pyrolysis product distribution was studied. • Tar yield is influenced by aliphatic carbon and oxygen functional group. • C1–C4 content of pyrolysis gas is related to CH_2/CH_3 ratio. - Abstract: Low-temperature pyrolysis is an economically efficient method for lignite to obtain coal tar and improve its combustion calorific value. The research on the distribution of pyrolysis product (especially coal tar yield) plays an important role in energy application and economic development in the now and future. Pyrolysis test was carried out in a tube reactor at 873 K for 15 min. The structure of the lignite was measured by solid "1"3C nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). The thermal analysis was analyzed by thermo-gravimetric (TG) analyzer. The results show that the pyrolysis product distribution is related to the breakage of branch structures of aromatic ring in lignites from different sedimentary environment. The gas yield and composition are related to the decomposition of carbonyl group and the breakage of aliphatic carbon. The tar yield derived from lignite pyrolysis follows the order: Xianfeng lignite (XF, 13.67 wt.%) > Xiaolongtan lignite (XLT, 7.97 wt.%) > Inner Mongolia lignite (IM, 6.30 wt.%), which is mainly influenced by the aliphatic carbon contents, the CH_2/CH_3 ratio and the oxygen functional groups in lignite. The pyrolysis water yield depends on the decomposition of oxygen functional groups. IM has the highest content of oxygen-linked carbon so that the pyrolysis water yield derived from IM is the highest (9.20 wt.%), and is far more than that from the other two lignites.

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

Science.gov (United States)

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

2017-11-01

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

Mutagenic activities of biochars from pyrolysis.

Science.gov (United States)

Piterina, Anna V; Chipman, J Kevin; Pembroke, J Tony; Hayes, Michael H B

2017-08-15

Biochar production, from pyrolysis of lignocellulosic feedstocks, agricultural residues, and animal and poultry manures are emerging globally as novel industrial and commercial products. It is important to develop and to validate a series of suitable protocols for the ecological monitoring of the qualities and properties of biochars. The highly sensitive Salmonella mutagenicity assays (the Ames test) are used widely by the toxicology community and, via the rat liver extract (S9), can reflect the potential for mammalian metabolic activation. We examined the Ames test for analyses of the mutagenic activities of dimethylsulphoxide (DMSO) extracts of biochars using two bacterial models (S. typhimurium strains TA98 and TA100) in the presence and in the absence of the metabolic activation with the S9-mix. Tester strain TA98 was most sensitive in detecting mutagenic biochar products, and the contribution of S9 was established. Temperature and times of pyrolysis are important. Biochar pyrolysed at 400°C for 10min, from a lignocellulose precursor was mutagenic, but not when formed at 800°C for 60min, or at 600°C for 30min. Biochars from poultry litter, and manures of calves fed on grass had low mutagenicities. Biochar from pig manure had high mutagenicity; biochars from manures of cows fed on a grass plus cereals, those of calves fed on mother's milk, and biochars from solid industrial waste had intermediate mutagenicities. The methods outlined can indicate the need for further studies for screening and detection of the mutagenic residuals in a variety of biochar products. Copyright © 2017. Published by Elsevier B.V.

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-12-01

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

Differentiation of pre-existing trapped methane from thermogenic methane in an igneous-intruded coal by hydrous pyrolysis

Science.gov (United States)

Dias, Robert F.; Lewan, Michael D.; Birdwell, Justin E.; Kotarba, Maciej J.

2014-01-01

So as to better understand how the gas generation potential of coal changes with increasing rank, same-seam samples of bituminous coal from the Illinois Basin that were naturally matured to varying degrees by the intrusion of an igneous dike were subjected to hydrous pyrolysis (HP) conditions of 360 °C for 72 h. The accumulated methane in the reactor headspace was analyzed for δ13C and δ2H, and mol percent composition. Maximum methane production (9.7 mg/g TOC) occurred in the most immature samples (0.5 %Ro), waning to minimal methane values at 2.44 %Ro (0.67 mg/g TOC), and rebounding to 3.6 mg/g TOC methane in the most mature sample (6.76 %Ro). Methane from coal with the highest initial thermal maturity (6.76 %Ro) shows no isotopic dependence on the reactor water and has a microbial δ13C value of −61‰. However, methane from coal of minimal initial thermal maturity (0.5 %Ro) shows hydrogen isotopic dependence on the reaction water and has a δ13C value of −37‰. The gas released from coals under hydrous pyrolysis conditions represents a quantifiable mixture of ancient (270 Ma) methane (likely microbial) that was generated in situ and trapped within the rock during the rapid heating by the dike, and modern (laboratory) thermogenic methane that was generated from the indigenous organic matter due to thermal maturation induced by hydrous pyrolysis conditions. These findings provide an analytical framework for better assessment of natural gas sources and for differentiating generated gas from pre-existing trapped gas in coals of various ranks.

Pyrolysis and gasification behavior of black liquor under pressurized conditions

Energy Technology Data Exchange (ETDEWEB)

Whitty, K

1997-11-01

The purpose of this study has been to enhance the understanding of the processes involved in pressurized black liquor gasification. Gasification is known to occur in three stages: drying, pyrolysis and char gasification. The work presented here focuses on the pyrolysis and gasification stages. Experiments were carried out primarily in two laboratory-scale reactors. A pressurized grid heater was used to study black liquor pyrolysis under pressurized conditions. Char yields and the fate of elements in the liquor, as well as the degree of liquor swelling, were measured in this device. A pressurized thermogravimetric reactor was used to measure the rate of the char gasification process under different temperatures and pressures and in various gas atmospheres. Pyrolysis experiments were also carried out in this device, and data on swelling behavior, char yields and component release were obtained 317 refs.

Pyrolysis of forestry biomass by-products in Greece

Energy Technology Data Exchange (ETDEWEB)

Zabaniotou, A.A.

1999-06-01

This article summarizes the technical characteristics of a biomass pyrolysis pilot plant recently constructed in central Greece. It highlights the considerations involved in achieving successful pyrolysis technology and environmental and developmental goals, by reviewing technical and nontechnical barriers associated with biomass treatment technology in Greece. Data from the start-up phase of the plant operation are presented and some aspects of the process are outlined. The capacity of the plant is 1200 1450 kg hr, based on wet biomass (Arbutus Unedo) and the pyrolysis temperature is approximately 400{sup o}C. Char yield is 1418 % weight on dry basis and is of good quality consisting of 76{sup o}C with heat content 6760 kcal kg. Bio-oil includes 63% C and its heat content is 6250 kcal kg. (author)

Fuel production from microwave assisted pyrolysis of coal with carbon surfaces

International Nuclear Information System (INIS)

Mushtaq, Faisal; Mat, Ramli; Ani, Farid Nasir

2016-01-01

Highlights: • MW heating of coal was carried out with uniformly distributed carbon surfaces. • The effects of carbon loading, MW power and N 2 flow rate were investigated. • Heating profile, pyrolysis products are influenced by the process variables. • Highest coal-tar obtained when final temperature sustained for longer duration. • Coal-tar is mainly composed of aromatics and saturated aliphatics hydrocarbons. - Abstract: In this study, coal solids were subjected to Microwave (MW) pyrolysis conditions. Coconut Activated Carbon (CAC) solids used as a MW absorber was distributed uniformly over coal solids to reduce hotspots. Three process parameters; CAC loading, MW power and N 2 flow rate were studies on pyrolysis heating performance. The highest coal-tar yield of 18.59 wt% was obtained with 600 W, 75 wt% CAC loading and 4 Liter per Minute (LPM) of N 2 flow rate. This improved coal-tar yield is mainly of the fact that higher MW power and CAC loading produced sustained pyrolysis conditions for longer duration for the complete conversion of pyrolysis solids. The coal-tar was composed mainly of aromatics (naphthalenes, benzenes and xylene) and saturated aliphatics (alkanes and alkenes) hydrocarbons. The gas produced from pyrolysis of coal is mainly of H 2 40.23–65.22 vol%.

Thermo-Catalytic Pyrolysis of Waste Plastics from End of Life Vehicle

Directory of Open Access Journals (Sweden)

Miskolczi Norbert

2016-01-01

Full Text Available Pyrolysis of waste plastics is widely used recycling method. Owing to the end-of-life vehicles regulations, 95% of passenger cars and vehicles must reused/recovered after the dismantling. Pyrolysis of waste polyethylene and polypropylene obtained from end-of-life vehicles was investigated in a continuously stirred batch reactor using 500 and 600°C temperatures. To ensure the pyrolysis reactions the tested catalysts (5% of ZSM-5, HZSM-5, Ni-ZSM-5 and Fe-ZSM-5 were added directly to the mixtures of raw materials. Products of pyrolysis were separated into gases, pyrolysis oil and heavy oil, which was further analyzed by gas-chromatography, Fourier transformed infrared spectroscopy and other standardized methods. Based on the results it was concluded, that the catalysts significantly increase the yields of volatile products, and modify their composition. Especially the alkane/alkene ratio, the methane concentration and the concentration of branched hydrocarbon could be affected by the applied catalysts. Ni-ZSM-5 catalyst had the highest activity in methane production, while HZSM-5 catalyst proved effective in isomerization reactions. Using H-ZSM-5, Ni-ZSM-5, and Fe-ZSM-5 catalyst notably decreased average molecular weight of pyrolysis oils and significantly higher aromatic content was observed.

'Mister Badger' Pushing Mars Rock

Science.gov (United States)

1976-01-01

Viking's soil sampler collector arm successfully pushed a rock on the surface of Mars during the afternoon of Friday, October 8. The irregular-shaped rock was pushed several inches by the Lander's collector arm, which displaced the rock to the left of its original position, leaving it cocked slightly upward. Photographs and other information verified the successful rock push. Photo at left shows the soil sampler's collector head pushing against the rock, named 'Mister Badger' by flight controllers. Photo at right shows the displaced rock and the depression whence it came. Part of the soil displacement was caused by the collector s backhoe. A soil sample will be taken from the site Monday night, October 11. It will then be delivered to Viking s organic chemistry instrument for a series of analyses during the next few weeks. The sample is being sought from beneath a rock because scientists believe that, if there are life forms on Mars, they may seek rocks as shelter from the Sun s intense ultraviolet radiation.

Novel technique for coal pyrolysis and hydrogenation product analysis. Final technical report

Energy Technology Data Exchange (ETDEWEB)

Pfefferle, L.D.; Boyle, J.

1993-03-15

A microjet reactor coupled to a VUV photoionization time-of-flight mass spectrometer has been used to obtain species measurements during high temperature pyrolysis and oxidation of a wide range of hydrocarbon compounds ranging from allene and acetylene to cyclohexane, benzene and toluene. Initial work focused on calibration of the technique, optimization of ion collection and detection and characterization of limitations. Using the optimized technique with 118 nm photoionization, intermediate species profiles were obtained for analysis of the hydrocarbon pyrolysis and oxidation mechanisms. The ``soft`` ionization, yielding predominantly molecular ions, allowed the study of reaction pathways in these high temperature systems where both sampling and detection challenges are severe. Work has focused on the pyrolysis and oxidative pyrolysis of aliphatic and aromatic hydrocarbon mixtures representative of coal pyrolysis and hydropyrolysis products. The detailed mass spectra obtained during pyrolysis and oxidation of hydrocarbon mixtures is especially important because of the complex nature of the product mixture even at short residence times and low primary reactant conversions. The combustion community has advanced detailed modeling of pyrolysis and oxidation to the C4 hydrocarbon level but in general above that size uncertainties in rate constant and thermodynamic data do not allow us to a priori predict products from mixed hydrocarbon pyrolyses using a detailed chemistry model. For pyrolysis of mixtures of coal-derived liquid fractions with a large range of compound structures and molecular weights in the hundreds of amu the modeling challenge is severe. Lumped models are possible from stable product data.

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

Science.gov (United States)

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

PYROLYSIS OF ZINC CONTAMINATED BIOMASS FROM PHYTOREMEDIATION

OpenAIRE

Özkan, Aysun; Günkaya, Zerrin; Banar, Müfide; Kulaç, Alev; Yalçın, Gülser; Taşpınar, Kadriye; Altay, Abdullah

2015-01-01

The objective of this study was to stabilize of zinc (Zn) from soil to pyrolysis solid product. For this aim, phytoremediation and pyrolysis were sequentially applied. In the first stage of the study, phytoremediation was first applied to zinc contaminated soil via  sunflower (Helianthus annuus), corn (Zea mays) and rape (Brassica napus), After harvesting, the plants were pyrolyzed at 500°C with the heating rate of 35 °C/min in a fixed bed stainless steel (380 S) 240 cm3 reactor. The phytorem...

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

Science.gov (United States)

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

2017-05-01

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

THM-coupled modeling of selected processes in argillaceous rock relevant to rock mechanics

International Nuclear Information System (INIS)

Czaikowski, Oliver

2012-01-01

Scientific investigations in European countries other than Germany concentrate not only on granite formations (Switzerland, Sweden) but also on argillaceous rock formations (France, Switzerland, Belgium) to assess their suitability as host and barrier rock for the final storage of radioactive waste. In Germany, rock salt has been under thorough study as a host rock over the past few decades. According to a study by the German Federal Institute for Geosciences and Natural Resources, however, not only salt deposits but also argillaceous rock deposits are available at relevant depths and of extensions in space which make final storage of high-level radioactive waste basically possible in Germany. Equally qualified findings about the suitability/unsuitability of non-saline rock formations require fundamental studies to be conducted nationally because of the comparatively low level of knowledge. The article presents basic analyses of coupled mechanical and hydraulic properties of argillaceous rock formations as host rock for a repository. The interaction of various processes is explained on the basis of knowledge derived from laboratory studies, and open problems are deduced. For modeling coupled processes, a simplified analytical computation method is proposed and compared with the results of numerical simulations, and the limits to its application are outlined. (orig.)

Calcium-rich biochar from the pyrolysis of crab shell for phosphorus removal.

Science.gov (United States)

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.

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

Directory of Open Access Journals (Sweden)

Jia Hanzhong

2017-09-01

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

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

Science.gov (United States)

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

2017-11-01

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

Investigation of solid organic waste processing by oxidative pyrolysis

Science.gov (United States)

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.

Pyrolysis behaviors and kinetic studies on Eucalyptus residues using thermogravimetric analysis

International Nuclear Information System (INIS)

Chen, Zhihua; Zhu, Quanjie; Wang, Xun; Xiao, Bo; Liu, Shiming

2015-01-01

Highlights: • The first study on pyrolysis characteristics and kinetic of Eucalyptus residues. • Pyrolysis process can be divided into three stages using differential DTG method. • A new modified discrete DAEM showed better than Gaussian DAEM for kinetic studies. • Variations of activation energy reveal the mechanism change during pyrolysis process. - Abstract: The pyrolysis behaviors and kinetics of Eucalyptus leaves (EL), Eucalyptus bark (EB) and Eucalyptus sawdust (ESD) were investigated by using thermogravimetric analysis (TGA) technique. Three stages for EL, EB and ESD pyrolysis have been divided using differential derivative thermogravimetric (DDTG) method and the second stage is the main pyrolysis process with approximately 86.93% (EL), 88.96% (EB) and 97.84% (ESD) weight loss percentages. Kinetic parameters of Gaussian distributed activation energy model (DAEM) for EL, EB and ESD pyrolysis are: distributed centers (E_0) of 141.15 kJ/mol (EL), 149.21 kJ/mol (EB), 175.79 kJ/mol (ESD), standard deviations (σ) of 18.35 kJ/mol (EL), 18.37 kJ/mol (EB), 14.41 kJ/mol (ESD) and pre-exponential factors (A) of 1.15E+10 s"−"1 (EL), 4.34E+10 s"−"1 (EB), 7.44E+12 s"−"1 (ESD). A new modified discrete DAEM was performed and showed excellent fits to experimental data than Gaussian DAEM. According to the modified discrete DAEM, the activation energies are in ranges of 122.67–308.64 kJ/mol, 118.72–410.80 kJ/mol and 108.39–192.93 kJ/mol for EL, EB and ESD pyrolysis, respectively. The pre-exponential factors of discrete DAEM have wide ranges of 4.84E+13–6.12E+22 s"−"1 (EL), 1.91E+12–4.51E+25 s"−"1 (EB) and 63.43–4.36E+11 s"−"1 (ESD). The variation of activation energy versus conversion reveals the mechanism change during pyrolysis process. The kinetic data would be of immense benefit to model, design and develop suitable thermo-chemical systems for the application of Eucalyptus residues.

Pyrolysis oil upgrading for Co-processing in standard refinery units

NARCIS (Netherlands)

De Miguel Mercader, F.

2010-01-01

This thesis considers the route that comprises the upgrading of pyrolysis oil (produced from lingo-cellulosic biomass) and its further co-processing in standard refineries to produce transportation fuels. In the present concept, pyrolysis oil is produced where biomass is available and then

Analysis of volcano rocks by Moessbauer spectroscopy

International Nuclear Information System (INIS)

Sitek, J.; Dekan, J.

2012-01-01

In this work we have analysed the basalt rock from Mount Ba tur volcano situated on the Island of Bali in Indonesia.We compared our results with composition of basalt rocks from some other places on the Earth. (authors)

Theoretical study of rock mass investigation efficiency

International Nuclear Information System (INIS)

Holmen, Johan G.; Outters, Nils

2002-05-01

The study concerns a mathematical modelling of a fractured rock mass and its investigations by use of theoretical boreholes and rock surfaces, with the purpose of analysing the efficiency (precision) of such investigations and determine the amount of investigations necessary to obtain reliable estimations of the structural-geological parameters of the studied rock mass. The study is not about estimating suitable sample sizes to be used in site investigations.The purpose of the study is to analyse the amount of information necessary for deriving estimates of the geological parameters studied, within defined confidence intervals and confidence level In other words, how the confidence in models of the rock mass (considering a selected number of parameters) will change with amount of information collected form boreholes and surfaces. The study is limited to a selected number of geometrical structural-geological parameters: Fracture orientation: mean direction and dispersion (Fisher Kappa and SRI). Different measures of fracture density (P10, P21 and P32). Fracture trace-length and strike distributions as seen on horizontal windows. A numerical Discrete Fracture Network (DFN) was used for representation of a fractured rock mass. The DFN-model was primarily based on the properties of an actual fracture network investigated at the Aespoe Hard Rock Laboratory. The rock mass studied (DFN-model) contained three different fracture sets with different orientations and fracture densities. The rock unit studied was statistically homogeneous. The study includes a limited sensitivity analysis of the properties of the DFN-model. The study is a theoretical and computer-based comparison between samples of fracture properties of a theoretical rock unit and the known true properties of the same unit. The samples are derived from numerically generated boreholes and surfaces that intersect the DFN-network. Two different boreholes are analysed; a vertical borehole and a borehole that is

Pyrolysis of Pine Wood

DEFF Research Database (Denmark)

Fjellerup, Jan Søren; Ahrenfeldt, Jesper; Henriksen, Ulrik Birk

2005-01-01

In this study, pinewood has been pyrolyzed using a fixed heating rate with a variable end-temperature. The pyrolysis process has been simulated using a mechanism with three parallel reactions for the formation of char, gas and tar. First order irreversible kinetics is assumed. This kind of model ...

3D DEM analyses of the 1963 Vajont rock slide

Science.gov (United States)

Boon, Chia Weng; Houlsby, Guy; Utili, Stefano

2013-04-01

The 1963 Vajont rock slide has been modelled using the distinct element method (DEM). The open-source DEM code, YADE (Kozicki & Donzé, 2008), was used together with the contact detection algorithm proposed by Boon et al. (2012). The critical sliding friction angle at the slide surface was sought using a strength reduction approach. A shear-softening contact model was used to model the shear resistance of the clayey layer at the slide surface. The results suggest that the critical sliding friction angle can be conservative if stability analyses are calculated based on the peak friction angles. The water table was assumed to be horizontal and the pore pressure at the clay layer was assumed to be hydrostatic. The influence of reservoir filling was marginal, increasing the sliding friction angle by only 1.6˚. The results of the DEM calculations were found to be sensitive to the orientations of the bedding planes and cross-joints. Finally, the failure mechanism was investigated and arching was found to be present at the bend of the chair-shaped slope. References Boon C.W., Houlsby G.T., Utili S. (2012). A new algorithm for contact detection between convex polygonal and polyhedral particles in the discrete element method. Computers and Geotechnics, vol 44, 73-82, doi.org/10.1016/j.compgeo.2012.03.012. Kozicki, J., & Donzé, F. V. (2008). A new open-source software developed for numerical simulations using discrete modeling methods. Computer Methods in Applied Mechanics and Engineering, 197(49-50), 4429-4443.

Pyrolysis of Pine Wood, Experiments and Theory

DEFF Research Database (Denmark)

Fjellerup, Jan Søren; Ahrenfeldt, Jesper; Henriksen, Ulrik Birk

In this study, pinewood has been pyrolyzed using a fixed heating rate with a variable end-temperature. The pyrolysis process has been simulated using a mechanism with three parallel reactions for the formation of char, gas and tar. First order irreversible kinetics is assumed. This kind of model...... may predict the variation of product yield with operating conditions such as temperature and heating rate. The system of coupled differential equations describing the pyrolysis process is solved using the software DYMOLA. Various literature values for kinetic parameters have been compared...

THE ROLE OF INTRAMOLECULAR TIES ENERGY IN THE PYROLYSIS PROCESS OF PET

Directory of Open Access Journals (Sweden)

P. Iu. Salikov

2014-01-01

Full Text Available Summary. Recycling plastic waste to focus on. The main type of used products made of polyethylene terephthalate (PET is a container from the various types of beverages. There was considered a possibility of waste of PET (bottles, bottles, packaging containers by pyrolysis. Most of the proposed methods are not suitable for recycling (recycling of waste consumption contamination. Purpose - to develop technological foundations and optimum modes waste PET to obtain useful secondary products, taking into account the energy of chemical intramolecular bonds. Applied scientific basis of recycling PET into useful forms of secondary products, in particular the establishment of the collapse of the intramolecular bonds, depending on the temperature of the pyrolysis method of mathematical processing - differentiation of polynomial equations change in the degree of pyrolysis temperature-dependent. The optimum modes of processing. The block diagram of apparatus for processing contaminated waste PET pyrolysis methods of control processing in accordance with the specified composition of secondary products. The possibility of controlling the amount and types of fuel components of secondary products due to measurable parameters of the pyrolysis process. The effective temperature pyrolysis of waste PET with the CCA-tures energy intramolecular bonds.

Ecotoxicological characterization of biochars: role of feedstock and pyrolysis temperature.

Science.gov (United States)

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; pmanagement recommendations. Copyright © 2014 Elsevier B.V. All rights reserved.

The analysis of creep characteristics of the surrounding rock of the carbonaceous rock tunnel based on Singh-Mitchell model

Science.gov (United States)

Luo, Junhui; Mi, Decai; Ye, Qiongyao; Deng, Shengqiang; Zeng, Fuquan; Zeng, Yongjun

2018-01-01

Carbonaceous rock has the characteristics of easy disintegration, softening, swelling and environmental sensitivity, which belongs to soft surrounding rock, and the deformation during excavation and long-term stability of the surrounding rock of carbonaceous rock tunnel are common problems in the construction of carbonaceous rock tunnel. According to the above, the Monitor and measure the displacement, temperature and osmotic pressure of the surrounding carbonaceous rock of the tunnel of Guangxi Hebai highway. Then it based on the obtaining data to study the creep mechanism of surrounding rock using Singh-Mitchell model and predict the deformation of surrounding rock before the tunnel is operation. The results show that the Singh-Mitchell creep model can effectively analyse and predict the deformation development law of surrounding rock of tunnel without considering temperature and osmotic pressure, it can provide reference for the construction of carbonaceous rock tunnel and the measures to prevent and reinforce it..

Renewable energy source from pyrolysis of solid wastes

International Nuclear Information System (INIS)

Md Kawser Jamil; Farid Nasir Ani

2000-01-01

Malaysia is blessed with a significant renewable energy resource base such as solar energy and biomass. To continue with its industrial development, Malaysia must manages energy supply its c prudently in order to avoid becoming an energy importer supply. Most significantly renewable energy from biomass such as rice husks, wood wastes, oil palm wastes, rubber wastes and other agricultural wastes. Beside rice and timber. Malaysia produces a huge amount of palm oil and natural rubber. These generate a significant amount of solid wastes in the forms of oil palm shell and rubber. These wastes are producing pollution and emission problems in Malaysia which is causing an environmental issue. Besides energy is not recovered efficiently from these waste resources. From the elemental composition and thermogravimetric studies of the wastes, it appeared that the wastes could be used as an alternative value-added source of energy. For this purpose a fast pyrolysis of 300 mi-n lone, and 50 mm diameter stainless-steel reactor was designed and fabricated. The grounded, sieved and dried solid feed particles underwent pyrolysis reactor at moderate temperature and were converted into pyrolytic oil, solid char and cas. Oil and char were collected while the cas was flared. The oil was characterised by GC-MS technique. Detailed analysis of the oil showed that there was no concentration of biologically active polycyclic aromatic species in the oil. The fuel properties of the derived oils were also analysed and compared to diesel fuel. (Author)

Rapid molecular screening of black carbon (biochar) thermosequences obtained from chestnut wood and rice straw: A pyrolysis-GC/MS study

International Nuclear Information System (INIS)

Kaal, Joeri; Schneider, Maximilian P.W.; Schmidt, Michael W.I.

2012-01-01

Rice straw and chestnut wood were heated between 200 and 1000 °C (T CHAR ) to produce Black C ‘thermosequences’. The molecular properties of the charred residues were assessed by pyrolysis-GC/MS to investigate the relation between charring intensity and pyrolysis fingerprint. Samples obtained at T CHAR > 500 °C (wood) or >700 °C (straw) gave low quality pyrograms and poor reproducibility because of high thermal stability, but pyrolysis-GC/MS allowed to track the thermal degradation of the main biocomponents (polysaccharides, lignin, methylene chain-based aliphatics, triterpenoids, chlorophyll and proteins) in the lower temperature range, mostly occurring between T CHAR 250 and 500 °C. With increasing T CHAR , the charred residues of these biocomponents lose characteristic functional groups, aromatise and finally condense into non-pyrolysable biomass. The proportions of the pyrolysis products of unspecific origin (benzene, toluene, PAHs, etc.), increase with charring intensity, while the ratios that reflect the abundance of alkyl cross-linkages between aromatic moieties (e.g. benzene/toluene, naphthalene/alkylnaphthalene) decrease. These results provide the guidelines to using pyrolysis-GC/MS for the molecular characterisation of different components in Black C and biochar, which is an important parameter for predicting Black C/biochar behaviour in soil. Results are consistent with earlier studies of these samples using the BPCA (benzenepolycarboxylic acid) method and the ring current-induced 13 C benzene chemical shift NMR (Nuclear Magnetic Resonance) approach. Pyrolysis-GC/MS provides more information on molecular structures in the low temperature range (T CHAR ≤ 500 °C) while the BPCA and NMR ring current methods provide more reliable estimations of charring intensity, especially at higher temperatures (T CHAR ≥ 500 °C). -- Highlights: ► Charred rice straw and chestnut wood (200–1000 °C) analysed by pyrolysis-GC/MS. ► Pyrolysis-GC/MS allows

Seismic response of rock joints and jointed rock mass

International Nuclear Information System (INIS)

Ghosh, A.; Hsiung, S.M.; Chowdhury, A.H.

1996-06-01

Long-term stability of emplacement drifts and potential near-field fluid flow resulting from coupled effects are among the concerns for safe disposal of high-level nuclear waste (HLW). A number of factors can induce drift instability or change the near-field flow patterns. Repetitive seismic loads from earthquakes and thermal loads generated by the decay of emplaced waste are two significant factors. One of two key technical uncertainties (KTU) that can potentially pose a high risk of noncompliance with the performance objectives of 10 CFR Part 60 is the prediction of thermal-mechanical (including repetitive seismic load) effects on stability of emplacement drifts and the engineered barrier system. The second KTU of concern is the prediction of thermal-mechanical-hydrological (including repetitive seismic load) effects on the host rock surrounding the engineered barrier system. The Rock Mechanics research project being conducted at the Center for Nuclear Waste Regulatory Analyses (CNWRA) is intended to address certain specific technical issues associated with these two KTUs. This research project has two major components: (i) seismic response of rock joints and a jointed rock mass and (ii) coupled thermal-mechanical-hydrological (TMH) response of a jointed rock mass surrounding the engineered barrier system (EBS). This final report summarizes the research activities concerned with the repetitive seismic load aspect of both these KTUs

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

KAUST Repository

Imran, Ali

2015-11-24

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

Sugarcane Bagasse Pyrolysis in a Carbon Dioxide Atmosphere with Conventional and Microwave-Assisted Heating

Energy Technology Data Exchange (ETDEWEB)

Lin, Bo-Jhih; Chen, Wei-Hsin, E-mail: weihsinchen@gmail.com [Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan, Taiwan (China)

2015-02-04

Pyrolysis is an important thermochemical method to convert biomass into bio-oil. In this study, the pyrolysis of sugarcane bagasse in a CO{sub 2} atmosphere under conventional and microwave-assisted heating is investigated to achieve CO{sub 2} utilization. In the microwave pyrolysis, charcoal is used as the microwave absorber to aid in pyrolysis reactions. The results indicate that the yields of pyrolysis products are greatly influenced by the heating modes. In the conventional heating, the prime product is bio-oil and its yield is in the range of 51–54 wt%, whereas biochar is the major product in microwave-assisted heating and its yield ranges from 61 to 84 wt%. Two different absorber blending ratios of 0.1 and 0.3 are considered in the microwave pyrolysis. The solid yield decreases when the absorber blending ratio decreases from 0.3 to 0.1, while the gas and liquid yields increase. This is attributed to more energy consumed for bagasse pyrolysis at the lower blending ratio. Hydrogen is produced under the microwave pyrolysis and its concentration is between 2 and 12 vol%. This arises from the fact that the secondary cracking of vapors and the secondary decomposition of biochar in an environment with microwave irradiation is easier than those with conventional heating.

Study on the Inference Factors of Huangling Coking Coal Pyrolysis

Science.gov (United States)

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%.

Catalytic pyrolysis of LDPE using modified vermiculite as a catalyst

International Nuclear Information System (INIS)

Bezerra, Franciel Aureliano; Figueiredo, Aneliese Lunguinho; Araujo, Antonio Souza de; Guedes, Ana Paula de Melo Alves

2016-01-01

Low density polyethylene (LDPE) is one of the most commonly-used polymers currently, and the great quantity of this polymer produced results in tons of waste that must be treated. We studied the thermocatalytic pyrolysis of LDPE with a modified clay vermiculite catalyst as an alternative for treatment of waste. The clay was treated with a solution of nitric acid at different concentrations and calcined at 400 °C. The materials were characterized by X-ray diffraction, thermogravimetry, nitrogen adsorption, and energy dispersive spectroscopy. Thermal and thermocatalytic pyrolysis were carried out in a microreactor coupled with GC/MS at 500 °C. The aim of the polymeric waste pyrolysis is the obtainment of light hydrocarbons (C<16), which can be used in the chemical and petrochemical industry, through breaks in the polymer chain. The results were satisfactory, with an increase in yield for light hydrocarbons by using catalysts reaching up to 71.4% of products with C<16, whereas thermal pyrolysis resulted in only 25.8%. (author)

Recent advances in analysis and prediction of Rock Falls, Rock Slides, and Rock Avalanches using 3D point clouds

Science.gov (United States)

Abellan, A.; Carrea, D.; Jaboyedoff, M.; Riquelme, A.; Tomas, R.; Royan, M. J.; Vilaplana, J. M.; Gauvin, N.

2014-12-01

The acquisition of dense terrain information using well-established 3D techniques (e.g. LiDAR, photogrammetry) and the use of new mobile platforms (e.g. Unmanned Aerial Vehicles) together with the increasingly efficient post-processing workflows for image treatment (e.g. Structure From Motion) are opening up new possibilities for analysing, modeling and predicting rock slope failures. Examples of applications at different scales ranging from the monitoring of small changes at unprecedented level of detail (e.g. sub millimeter-scale deformation under lab-scale conditions) to the detection of slope deformation at regional scale. In this communication we will show the main accomplishments of the Swiss National Foundation project "Characterizing and analysing 3D temporal slope evolution" carried out at Risk Analysis group (Univ. of Lausanne) in close collaboration with the RISKNAT and INTERES groups (Univ. of Barcelona and Univ. of Alicante, respectively). We have recently developed a series of innovative approaches for rock slope analysis using 3D point clouds, some examples include: the development of semi-automatic methodologies for the identification and extraction of rock-slope features such as discontinuities, type of material, rockfalls occurrence and deformation. Moreover, we have been improving our knowledge in progressive rupture characterization thanks to several algorithms, some examples include the computing of 3D deformation, the use of filtering techniques on permanently based TLS, the use of rock slope failure analogies at different scales (laboratory simulations, monitoring at glacier's front, etc.), the modelling of the influence of external forces such as precipitation on the acceleration of the deformation rate, etc. We have also been interested on the analysis of rock slope deformation prior to the occurrence of fragmental rockfalls and the interaction of this deformation with the spatial location of future events. In spite of these recent advances

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

Science.gov (United States)

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

2017-10-01

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

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

KAUST Repository

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

2015-01-01

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

Catalytic oxidative pyrolysis of spent organic ion exchange resins from nuclear power plants

International Nuclear Information System (INIS)

Sathi Sasidharan, N.; Deshingkar, D.S.; Wattal, P.K.; Shirsat, A.N.; Bharadwaj, S.R.

2005-08-01

The spent IX resins from nuclear power reactors are highly active solid wastes generated during operations of nuclear reactors. Catalytic oxidative pyrolysis of these resins can lead to high volume reduction of these wastes. Low temperature pyrolysis of transition metal ion loaded IX resins in presence of nitrogen was carried out in order to optimize catalyst composition to achieve maximum weight reduction. Thermo gravimetric analysis of the pyrolysis residues was carried out in presence of air in order to compare the oxidative characteristics of transition metal oxide catalysts. Copper along with iron, chromium and nickel present in the spent IX resins gave the most efficient catalyst combination for catalytic and oxidative pyrolysis of the residues. During low temperature catalytic pyrolysis, 137 Cesium volatility was estimated to be around 0.01% from cationic resins and around 0.1% from anionic resins. During oxidative pyrolysis at 700 degC, nearly 10 to 40% of 137 Cesium was found to be released to off gases depending upon type of resin and catalyst loaded on to it. The oxidation of pyrolytic residues at 700 degC gave weight reduction of 15% for cationic resins and 93% for anionic resins. Catalytic oxidative pyrolysis is attractive for reducing weight and volume of spent cationic resins from PHWRs and VVERs. (author)

Microwave pyrolysis for conversion of materials to energy : A review

International Nuclear Information System (INIS)

Mokhtar, M.; Omar, R.; MOhammad Salleh, M.A.; Idris, A.

2009-01-01

Full text: The disposal of wastes in Malaysia is becoming a serious problem in many industrialized and public sectors. This is due to the high production of waste such as municipal solid waste, sludge from waste water treatment plants, agricultural waste and other used non-biodegradable products such as plastics and tyres. These wastes although are reused as compost, fuel, recycled and so on, there are still abundant left. These leftovers pose problems such as heavy metal leaching, leachates, green house gas emissions and mosquito breeding grounds. The disposal cost of these wastes sometimes can be costly at up to RM 2,200/ ton such as petroleum sludge by Kualiti Alam. Several methods have been used to convert these residues to energy via thermal treatment such as combustion, incineration and gasification. However, pyrolysis becomes one of the popular methods as the alternative to the wastes disposal recently. Not only energy (as gas) is produced, by-products such as chemical feedstock and solid absorbent can be produced. The use of microwave for pyrolysis, although relatively new for waste treatment, has several advantages compared to conventional heating. This includes easy control of the heating process, time saving, higher heating efficiency, etc. Tyre microwave pyrolysis plant in UK is known as the earliest plant using microwave technology to breakdown polymer in used tyres. Since 1990s, there are many patents for microwave pyrolysis. The processes are based on microwave pyrolysis of waste include coffee hulls, wood, coal, sewage sludge, hospital waste, plastic wastes, corn cobs and rice straw. The most important factors influencing the yield of product during the pyrolysis is temperature in range from 500 to 1000 degree Celsius according to product preference. High temperature favors gas products; whereas lower temperature favors liquid products. Comparatively, microwave pyrolysis produced gas with higher hydrogen and carbon monoxide (syngas) content compared

Pyrolysis of softwood carbohydrates in a fluidized bed reactor.

Science.gov (United States)

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

2008-09-01

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

Thermogravimetric analysis and fast pyrolysis of Milkweed.

Science.gov (United States)

Kim, Seung-Soo; Agblevor, Foster A

2014-10-01

Pyrolysis of Milkweed was carried out in a thermogravimetric analyzer and a bubbling fluidized bed reactor. Total liquid yield of Milkweed pyrolysis was between 40.74% and 44.19 wt% between 425 °C and 550 °C. The gas yield increased from 27.90 wt% to 33.33 wt% with increasing reaction temperature. The higher heating values (HHV) of the Milkweed bio-oil were relatively high (30.33-32.87 MJ/kg) and varied with reaction temperature, feeding rate and fluidization velocity. The selectivity for CO2 was highest within non-condensable gases, and the molar ratio of CO2/CO was about 3 at the different reaction conditions. The (13)C NMR analysis, of the bio-oil showed that the relative concentration carboxylic group and its derivatives was higher at 425 °C than 475 °C, which resulted in slightly higher oxygen content in bio-oil. The pH of aqueous phase obtained at 475 °C was 7.37 which is the highest reported for any lignocellulosic biomass pyrolysis oils. Copyright © 2014 Elsevier Ltd. All rights reserved.

Life cycle assessment of gasoline and diesel produced via fast pyrolysis and hydroprocessing

International Nuclear Information System (INIS)

Hsu, David D.

2012-01-01

Pyrolysis of biomass followed by hydroprocessing may provide infrastructure-compatible transportation fuels. In this work, a life cycle assessment (LCA) of the production of gasoline and diesel from forest residues via fast pyrolysis and hydroprocessing, from production of the feedstock to end use of the fuel in a vehicle, is performed. The fast pyrolysis and subsequent hydrotreating and hydrocracking processes are based on a Pacific Northwest National Laboratory design report. Stages other than biofuels conversion, including forest residue production and harvesting, preprocessing, feedstock transportation, fuel distribution, and vehicle operation, are based on previous work. Probability distribution functions are assumed for parameters involved in the pyrolysis process for Monte Carlo uncertainty analysis. This LCA for the production of gasoline and diesel via pyrolysis and upgrading assumes grid electricity is used and supplemental natural gas is supplied to the hydrogen plant. Gasoline and diesel produced via pyrolysis are estimated to have greenhouse gas (GHG) emissions of CO 2 equivalent of 117 g km −1 and 98 g km −1 , respectively, and net energy value (NEV) of 1.09 MJ km −1 and 0.92 MJ km −1 , respectively. All values from the uncertainty analysis have lower GHG emissions and higher NEV than conventional gasoline in 2005. Grid electricity and natural gas used account for 81% of the net GHG emissions in the base case. An evaluation of a case with biomass-derived electricity shows significant improvement in GHG emissions. -- Highlights: ► We conduct a life cycle assessment of a biomass-to-fuels pyrolysis pathway. ► Pyrolysis fuels are estimated to emit fewer greenhouse gases than conventional gasoline. ► Fewer greenhouse gases would be emitted if the pyrolysis process generated its own electricity from biomass.

Specialists' workshop on fast pyrolysis of biomass

Energy Technology Data Exchange (ETDEWEB)

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 as 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)

Physicochemical properties of bio-oil and biochar produced by fast pyrolysis of stored single-pass corn stover and cobs.

Science.gov (United States)

Shah, Ajay; Darr, Matthew J; Dalluge, Dustin; Medic, Dorde; Webster, Keith; Brown, Robert C

2012-12-01

Short harvest window of corn (Zea mays) stover necessitates its storage before utilization; however, there is not enough work towards exploring the fast pyrolysis behavior of stored biomass. This study investigated the yields and the physicochemical properties (proximate and ultimate analyses, higher heating values and acidity) of the fast pyrolysis products obtained from single-pass stover and cobs stored either inside a metal building or anaerobically within plastic wraps. Biomass samples were pyrolyzed in a 183 cm long and 2.1cm inner diameter free-fall fast pyrolysis reactor. Yields of bio-oil, biochar and non-condensable gases from different biomass samples were in the ranges of 45-55, 25-37 and 11-17 wt.%, respectively, with the highest bio-oil yield from the ensiled single-pass stover. Bio-oils generated from ensiled single-pass cobs and ensiled single-pass stover were, respectively, the most and the least acidic with the modified acid numbers of 95.0 and 65.2 mg g(-1), respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Slow pyrolysis of pistachio shell

Energy Technology Data Exchange (ETDEWEB)

Apaydin-Varol, Esin; Putun, Ersan; Putun, Ayse E [Anadolu University, Eskisehir (Turkey). Department of Chemical Engineering

2007-08-15

In this study, pistachio shell is taken as the biomass sample to investigate the effects of pyrolysis temperature on the product yields and composition when slow pyrolysis is applied in a fixed-bed reactor at atmospheric pressure to the temperatures of 300, 400, 500, 550, 700{sup o}C. The maximum liquid yield was attained at about 500-550{sup o}C with a yield of 20.5%. The liquid product obtained under this optimum temperature and solid products obtained at all temperatures were characterized. As well as proximate and elemental analysis for the products were the basic steps for characterization, column chromatography, FT-IR, GC/MS and SEM were used for further characterization. The results showed that liquid and solid products from pistachio shells show similarities with high value conventional fuels. 31 refs., 9 figs., 1 tab.

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

Energy Technology Data Exchange (ETDEWEB)

Diebold, J P [Thermalchemie, Inc., Lakewood, CO (United States)

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 to 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.

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

Science.gov (United States)

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

2018-07-01

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

Co-pyrolysis characteristics and kinetics of coal and plastic blends

International Nuclear Information System (INIS)

Zhou Limin; Luo Taian; Huang Qunwu

2009-01-01

Co-pyrolysis behaviors of different plastics (high density polyethylene, low density polyethylene and polypropylene), low volatile coal (LVC) and their mixtures were investigated by TGA. Experiments were conducted under N 2 atmosphere at heating rate of 20 deg. C/min from room temperature to 750 deg. C. The results showed that the thermal degradation temperature range of plastic was 438-521 deg. C, while that of coal (LVC) was 174-710 deg. C. Plastics showed similar pyrolysis characteristics due to similar chemical bonds in their molecular structures. The overlapping degradation temperature interval between coal and plastic provide an opportunity for free radicals from coal pyrolysis to participate in the reactions of plastic decomposition. The difference of weight loss percent (ΔW) between experimental and theoretical ones, calculated as an algebraic sum of those from each separated component, ΔW is 2.0-2.7% at the pyrolysis temperature higher than 530 deg. C, which indicates that the synergistic effect during pyrolysis occurs mainly in the high temperature region. The kinetic studies were performed according to Coats and Redfern method for first-order reaction. It was found that for plastics (HDPE, LDPE and PP), the pyrolysis process can be described by one first-order reaction. However, for LVC and LVC/plastic blends, this process can be described by three and four consecutive first-order reactions, respectively. The estimated kinetic parameters viz., activation energies and pre-exponential factors for coal, plastic and their blends, were found to be in the range of 35.7-572.8 kJ/mol and 27-1.7 x 10 38 min -1 , respectively

Flash pyrolysis fuel oil: BIO-POK

Energy Technology Data Exchange (ETDEWEB)

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

1995-12-31

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

Flash pyrolysis fuel oil: BIO-POK

Energy Technology Data Exchange (ETDEWEB)

Gust, S [Neste Oy, Porvoo (Finland)

1996-12-31

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

Catalytic Pyrolysis of Waste Plastic Mixture

Science.gov (United States)

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

2018-03-01

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

Lidar-Based Rock-Fall Hazard Characterization of Cliffs

Science.gov (United States)

Collins, Brian D.; Greg M.Stock,

2017-01-01

Rock falls from cliffs and other steep slopes present numerous challenges for detailed geological characterization. In steep terrain, rock-fall source areas are both dangerous and difficult to access, severely limiting the ability to make detailed structural and volumetric measurements necessary for hazard assessment. Airborne and terrestrial lidar survey methods can provide high-resolution data needed for volumetric, structural, and deformation analyses of rock falls, potentially making these analyses straightforward and routine. However, specific methods to collect, process, and analyze lidar data of steep cliffs are needed to maximize analytical accuracy and efficiency. This paper presents observations showing how lidar data sets should be collected, filtered, registered, and georeferenced to tailor their use in rock fall characterization. Additional observations concerning surface model construction, volumetric calculations, and deformation analysis are also provided.

Numerical modelling of pyrolysis in normal and reduced oxygen concentration

International Nuclear Information System (INIS)

Kacem, Ahmed

2016-01-01

The predictive capability of computational fluid dynamics (CFD) fire models depends on the accuracy with which the source term due to fuel pyrolysis can be determined. The pyrolysis rate is a key parameter controlling fire behavior, which in turn drives the heat feedback from the flame to the fuel surface. In the present study an in-depth pyrolysis model of a semi-transparent solid fuel (here, clear polymethyl methacrylate or PMMA) with spectrally-resolved radiation and a moving gas/solid interface was coupled with the CFD code ISIS of the IRSN which included turbulence, combustion and radiation for the gas phase. A combined genetic algorithm/pyrolysis model was used with Cone Calorimeter data from a pure pyrolysis experiment to estimate a unique set of kinetic parameters for PMMA pyrolysis. In order to validate the coupled model, ambient air flaming experiments were conducted on square slabs of PMMA with side lengths of 10, 20 and 40 cm. From measurements at the center of the slab, it was found that i) for any sample size, the experimental regression rate becomes almost constant with time, and ii) although the radiative and total heat transfers increase significantly with the sample size, the radiative contribution to the total heat flux remains almost constant (∼80%). Coupled model results show a fairly good agreement with the literature and with current measurements of the heat fluxes, gas temperature and regressing surface rate at the center of the slabs. Discrepancies between predicted and measured total pyrolysis rate are observed, which result from the underestimation of the flame heat flux feedback at the edges of the slab, as confirmed by the comparison between predicted and observed topography of burned samples. Predicted flame heights based on a threshold temperature criterion were found to be close to those deduced from the correlation of Heskestad. Finally, in order to predict the pyrolysis of PMMA under reduced ambient oxygen concentration, a two

Energy and resource utilization of deinking sludge pyrolysis

International Nuclear Information System (INIS)

Lou, Rui; Wu, Shubin; Lv, Gaojin; Yang, Qing

2012-01-01

The thermochemical conversion technique was applied in deinking sludge from the pulp and papermaking industrial to indagate the utilization of sludge biomass to energy, and the pyrolysis characteristics and pyrolytic products of deinking sludge were studied with thermogravimetric analysis (TGA) and pyrolysis coupled with gas chromatograph–mass spectrometer (Py-GC/MS). The static tubular furnace as an applied industrial research was used to study deinking sludge pyrolysis. The solid, gas and liquid of products was characterized by electron probe microanalysis (EPMA), gas chromatograph (GC) and gas chromatograph–mass (GC/MS), respectively. The results revealed that the weight-loss process of deinking sludge was a non-isothermal reaction and composed of four stages, i.e. dewater stage, volatile releasing stage, carbon burnout stage and some calcium carbonate decomposition. Pyrolytic products from deinking sludge in the static tubular furnace were comprised of the gaseous (29.78%), condensed liquid (bio-oil, 24.41%) and solid residues (45.81%). The volatiles from deinking sludge pyrolyzing were almost aromatic hydrocarbons, i.e. styrene, toluene and benzene and few acids and the solid was calcium carbonate (CaCO 3 ) that can be reused as paper filler. Deinking sludge was converted into high-grade fuel and chemicals by means of thermochemical conversion techniques, hence, pyrolysis of paper deinking sludge had a promising development on the comprehensive utilization.

Combined heat and power from the intermediate pyrolysis of biomass materials: performance, economics and environmental impact

International Nuclear Information System (INIS)

Yang, Y.; Brammer, J.G.; Wright, D.G.; Scott, J.A.; Serrano, C.; Bridgwater, A.V.

2017-01-01

Highlights: • Performance of the Pyrolysis and CHP systems is studied and evaluated. • Overall CHP efficiency of the 1000 kg/h Pyro-CHP system is 42.5%. • Levelised Energy Cost is high, but the optimistic scenario is potentially profitable. • Life-cycle GHG analysis shows strong positive environmental benefits. - Abstract: Combined heat and power from the intermediate pyrolysis of biomass materials offers flexible, on-demand renewable energy with some significant advantages over other renewable routes. To maximise the deployment of this technology an understanding of the dynamics and sensitivities of such a system is required. In the present work the system performance, economics and life-cycle environmental impact is analysed with the aid of the process simulation software Aspen Plus. Under the base conditions for the UK, such schemes are not currently economically competitive with energy and char products produced from conventional means. However, under certain scenarios as modelled using a sensitivity analysis this technology can compete and can therefore potentially contribute to the energy and resource sustainability of the economy, particularly in on-site applications with low-value waste feedstocks. The major areas for potential performance improvement are in reactor cost reductions, the reliable use of waste feedstocks and a high value end use for the char by-product from pyrolysis.

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Migmatitic rocks southwest of the Barberton greenstone belt

International Nuclear Information System (INIS)

Robb, L.J.; Anhaeusser, C.R.

1981-01-01

A geologic survey was done on the migmatitic rocks southwest of the Barberton greenstone belt. A table is given on the chemical analyses of components from migmatic outcrops in this area, as well as on the chemical analyses of some selected rock types found in greenstone xenoliths, together with leuco-biotite tomalite/tronomjemite gneisses in the area surrounding the Boesmanskop syenite pluton. Isotope dating was also used in the survey

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

Science.gov (United States)

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.

Geochemical evaluation of Pabdeh Formation in Nosrat field, southeast Persian Gulf using Rock- Eval VI pyrolysis

Directory of Open Access Journals (Sweden)

mohammad sadeghi

2015-02-01

Full Text Available The present study was performed on 59 drillhole cuttings from Pabdeh Formation in Nosrat oil field using Rock- Eval VI pryrolysis. Geochemical analysis indicated that Pabdeh Formation possesses poor to good hydrocarbon potential. Plotting S1 against TOC suggests that samples were not affected by polluting substances such as crude oil and lubricants while drilling operation. Jones organic fancies diagram shows B-BC area indicating that Pabdeh Formation was deposited in marine anoxic to oxic environments. HI vesus Tmax shows that most samples initially have had type II kerogen and now reflecting a mixture of type II to III kerogen (capable of generating oil that have already entered oil generation window. In addition, S1+S2 versus TOC plot also suggests that Pabdeh Formation can be considered as a capable hydrocarbon generating source rock in the study area.

Pyrolysis in Groningen, Netherlands. Feasibility study on a transition coalition

International Nuclear Information System (INIS)

Siemons, R.V.

2005-01-01

Results of a study on the technical, economical and financial feasibility of a pyrolysis factory for the processing and energetic application of biomass wastes in the Dutch province Groningen are presented and discussed. Also, attention is paid to the implementation of the planned pyrolysis factory in one or more transition programmes. [nl

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

Science.gov (United States)

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 Softwood Carbohydrates in a Fluidized Bed Reactor

Directory of Open Access Journals (Sweden)

Dmitry Yu. Murzin

2008-09-01

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

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

Directory of Open Access Journals (Sweden)

Heidi S. Nygård

2015-07-01

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

Rock mechanics stability at Olkiluoto, Haestholmen, Kivetty and Romuvaara

International Nuclear Information System (INIS)

Johansson, E.; Rautakorpi, J.

2000-02-01

Posiva Oy is studying the suitability of the Finnish bedrock for the geological disposal of spent nuclear fuel at four sites, Olkiluoto in Eurajoki, Haestholmen in Loviisa, Kivetty in Aeaenekoski and Romuvaara in Kuhmo. To enable the rock properties to be specified in great detail, the site-selection research programme has included rock mechanics investigations such as the measurement of in-situ rock stress and laboratory tests on rock samples. This report presents the results of the rock mechanics analyses performed on the main rock types at the Olkiluoto, Romuvaara, Kivetty and Haestholmen sites. The objective of this study was to assess the near-field stability of the final disposal tunnels and deposition holes at each of the investigation sites. Two empirical methods and a numerical method based on three-dimensional element code (3DEC) were used the analysis tools. A statistical approach was used to select the necessary input data and to specify the cases being analysed. The stability of the KBS-3 and MLH (Medium Long Hole) repository concepts during the pre-closure and post-closure phases was analysed. The repository depths investigated lay between 300 m and 700 m. The empirical methods are based on the study of the ratios between rock strength and the in-situ stress which could result in possible fracturing of the rock mass. Interpretation of the numerical analyses is based on the assumption of an elastic distribution of stress around the disposal tunnel and the deposition hole and the brittle rock strength criterion. The results obtained in this study indicate that in general, the rock mechanics conditions during the pre-closure and post-closure phases at each of the investigated sites remain good and stable between the studied depth levels, especially when the deposition rooms are oriented in a direction parallel to the major in-situ stress. If the disposal tunnels are orientated in a direction perpendicular to the major in-situ stress, the resultant

Pyrolysis and kinetic analyses of a perennial grass (Saccharum ravannae L.) from north-east India: Optimization through response surface methodology and product characterization.

Science.gov (United States)

Saikia, Ruprekha; Baruah, Bhargav; Kalita, Dipankar; Pant, Kamal K; Gogoi, Nirmali; Kataki, Rupam

2018-04-01

The objective of the present investigation was to optimize the pyrolysis condition of an abundantly available and low cost perennial grass of north-east India Saccharum ravannae L. (S. ravannae) using response surface methodology based on central composite design. Kinetic study of the biomass was conducted at four different heating rates of 10, 20, 40 and 60 °C min -1 and results were interpreted by Friedman, Kissinger Akira Sunnose and Flynn-Wall-Ozawa methods. Average activation energy 151.45 kJ mol -1 was used for evaluation of reaction mechanism following Criado master plot. Maximum bio-oil yield of 38.1 wt% was obtained at pyrolysis temperature of 550 °C, heating rate of 20 °C min -1 and nitrogen flow rate of 226 mL min -1 . Study on bio-oil quality revealed higher content of hydrocarbon, antioxidant property, total phenolic content and metal chelating capacity. These opened up probable applications of S. ravannae bio-oil in different fields including fuel, food industry and biomedical domain. Copyright © 2018 Elsevier Ltd. All rights reserved.

Predictive modelling of noise level generated during sawing of rocks

Indian Academy of Sciences (India)

This paper presents an experimental and statistical study on noise level generated during of rock sawing by circular diamond sawblades. Influence of the operating variables and rock properties on the noise level are investigated and analysed. Statistical analyses are then employed and models are built for the prediction of ...

Novel sorbent materials for environmental remediation via Pyrolysis of biomass

Science.gov (United States)

Zabaniotou, Anastasia

2013-04-01

One of the major challenges facing society at this moment is the transition from a non-sustainable, fossil resources-based economy to a sustainable bio-based economy. By producing multiple products, a biorefinery can take advantage of the differences in biomass components and intermediates and maximize the value derived from the biomass feedstock. The high-value products enhance profitability, the high-volume fuel helps meet national energy needs, and the power production reduces costs and avoids greenhouse-gas emissions From pyrolysis, besides gas and liquid products a solid product - char, is derived as well. This char contains the non converted carbon and can be used for activated carbon production and/or as additive in composite material production. Commercially available activated carbons are still considered expensive due to the use of non-renewable and relatively expensive starting material such as coal. The present study describes pyrolysis as a method to produce high added value carbon materials such as activated carbons (AC) from agricultural residues pyrolysis. Olive kernel has been investigated as the precursor of the above materials. The produced activated carbon was characterized by proximate and ultimate analyses, BET method and porosity estimation. Furthermore, its adsorption of pesticide compound in aqueous solution by was studied. Pyrolysis of olive kernel was conducted at 800 oC for 45min in a fixed reactor. For the production of the activated carbon the pyrolytic char was physically activated under steam in the presence of CO2 at 970oC for 3 h in a bench scale reactor. The active carbons obtained from both scales were characterized by N2 adsorption at 77 K, methyl-blue adsorption (MB adsorption) at room temperature and SEM analysis. Surface area and MB adsorption were found to increase with the degree of burn-off. The surface area of the activated carbons was found to increase up to 1500 m2/g at a burn-off level of 60-65wt.%, while SEM analysis

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

Directory of Open Access Journals (Sweden)

Fernandez-Lopez Maria

2017-01-01

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

Kinetic study and syngas production from pyrolysis of forestry waste

International Nuclear Information System (INIS)

Hu, Mian; Wang, Xun; Chen, Jian; Yang, Ping; Liu, Cuixia; Xiao, Bo; Guo, Dabin

2017-01-01

Highlights: • Pyrolysis process can be divided into three stages using differential DTG method. • A modified discrete DAEM model fitted experimental data well. • Fe/biochar catalyst showed a good performance on catalytic reforming process. - Abstract: Kinetic study and syngas production from pyrolysis of forestry waste (pine sawdust (PS)) were investigated using a thermogravimetric analyzer (TGA) and a fixed-bed reactor, respectively. In TGA, it was found that the pyrolysis of PS could be divided into three stages and stage II was the major mass reduction stage with mass loss of 73–74%. The discrete distributed activation energy model (DAEM) with discrete 200 first-order reactions was introduced to study the pyrolysis kinetic. The results indicated that the DAEM with 200 first-order reactions could approximate the pyrolysis process with an excellent fit between experimental and calculated data. The apparent activation energies of PS ranged from 147.86 kJ·mol −1 to 395.76 kJ·mol −1 , with corresponding pre-exponential factors of 8.30 × 10 13 s −1 to 3.11 × 10 25 s −1 . In the fixed-bed reactor, char supported iron catalyst was prepared for tar cracking. Compared with no catalyst which the gas yield and tar yield were 0.58 N m 3 /kg biomass and 201.23 g/kg biomass, the gas yield was markedly increased to 1.02 N m 3 /kg biomass and the tar yield was decreased to only 26.37 g/kg biomass in the presence of char supported iron catalyst. These results indicated that char supported iron catalyst could potentially be used to catalytically decompose tar molecules in syngas generated via biomass pyrolysis.

Catalytic Fast Pyrolysis: A Review

Directory of Open Access Journals (Sweden)

Theodore Dickerson

2013-01-01

Full Text Available Catalytic pyrolysis is a promising thermochemical conversion route for lignocellulosic biomass that produces chemicals and fuels compatible with current, petrochemical infrastructure. Catalytic modifications to pyrolysis bio-oils are geared towards the elimination and substitution of oxygen and oxygen-containing functionalities in addition to increasing the hydrogen to carbon ratio of the final products. Recent progress has focused on both hydrodeoxygenation and hydrogenation of bio-oil using a variety of metal catalysts and the production of aromatics from bio-oil using cracking zeolites. Research is currently focused on developing multi-functional catalysts used in situ that benefit from the advantages of both hydrodeoxygenation and zeolite cracking. Development of robust, highly selective catalysts will help achieve the goal of producing drop-in fuels and petrochemical commodities from wood and other lignocellulosic biomass streams. The current paper will examine these developments by means of a review of existing literature.

Yields from pyrolysis of refinery residue using a batch process

Directory of Open Access Journals (Sweden)

S. Prithiraj

2017-12-01

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

Kinetic Study of the Catalytic Pyrolysis of Oil-Containing Waste

Directory of Open Access Journals (Sweden)

Kirill Chalov

2016-10-01

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

Structural investigations of neuromelanin by pyrolysis-gas chromatography/mass spectrometry

International Nuclear Information System (INIS)

Dzierzega-Lecznar, A.; Kurkiewicz, S.; Stepien, K.; Chodurek, E.; Riederer, P.; Gerlach, M.

2006-01-01

Pyrolysis combined with gas chromatography and mass spectrometry (Py-GC/MS) was applied for structural investigations of the human substantia nigra neuromelanin. Using synthetic neuromelanins, we have demonstrated that Py-GC/MS is suitable for identification and differentiation of both eumelanin (dopamine-derived) and pheomelanin (cysteinyldopamine-derived) component of the pigment. Structural information on melanin monomers was inferred from their pyrolytic markers. When the human neuromelanin was subjected to pyrolysis, none of the heterocyclic, sulfur-containing markers of pheomelanin component was detected among the thermal degradation products. We have concluded that nigral pigment isolated from normal brain tissue does not contain benzothiazine-type monomers, and that cysteinyldopamine-originated units may be incorporated into the polymer in uncyclized form. The most abundant pyrolysis product was identified as limonene, which indicates that nigral pigment is tightly associated with an isoprenoid-type compound. Pyrolysis in the presence of the methylating reagent allowed identification of high levels of saturated and monounsaturated straight-chain C14-C18 fatty acid species chemically bound to the pigment macromolecule. (author)

Pyrolysis characteristics and kinetics of aquatic biomass using thermogravimetric analyzer.

Science.gov (United States)

Wu, Kejing; Liu, Ji; Wu, Yulong; Chen, Yu; Li, Qinghai; Xiao, Xin; Yang, Mingde

2014-07-01

The differences in pyrolysis process of three species of aquatic biomass (microalgae, macroalgae and duckweed) were investigated by thermogravimetric analysis (TGA). Three stages were observed during the pyrolysis process and the main decomposition stage could be divided further into three zones. The pyrolysis characteristics of various biomasses were different at each zone, which could be attributed to the differences in their components. A stepwise procedure based on iso-conversional and master-plots methods was used for the kinetic and mechanism analysis of the main decomposition stage. The calculation results based on the kinetic model was in good agreement with the experimental data of weight loss, and each biomass had an increasing activation energy of 118.35-156.13 kJ/mol, 171.85-186.46 kJ/mol and 258.51-268.71 kJ/mol in zone 1, 2 and 3, respectively. This study compares the pyrolysis behavior of various aquatic biomasses and provides basis for further applications of the biomass thermochemical conversion. Copyright © 2014. Published by Elsevier Ltd.

The IPRP (Integrated Pyrolysis Regenerated Plant) technology: From concept to demonstration

International Nuclear Information System (INIS)

D’Alessandro, Bruno; D’Amico, Michele; Desideri, Umberto; Fantozzi, Francesco

2013-01-01

Highlights: ► IPRP technology development for distributed conversion of biomass and wastes. ► IPRP demonstrative unit combines a rotary kiln pyrolyzer to a 80 kWe microturbine. ► Main performances and critical issues are pointed out for different residual fuels. -- Abstract: The concept of integrated pyrolysis regenerated plant (IPRP) is based on a Gas Turbine (GT) fuelled by pyrogas produced in a rotary kiln slow pyrolysis reactor, where waste heat from GT is used to sustain the pyrolysis process. The IPRP plant provides a unique solution for microscale (below 250 kW) power plants, opening a new and competitive possibility for distributed biomass or wastes to energy conversion systems. The paper summarizes the state of art of the IPRP technology, from preliminary numerical simulation to pilot plant facility, including some new available data on pyrolysis gas from laboratory and pilot plants.

Evaluating the susceptibility of pyrolysis of monosaccharide, disaccharide, and polysaccharide to CO_2

International Nuclear Information System (INIS)

Lee, Jechan; Tsang, Yiu Fai; Oh, Jeong-Ik; Lee, Sang-Ryong; Kwon, Eilhann E.

2017-01-01

Highlights: • Two-stage pyrolyzer gives a deep insight into sensitivity of biomass structure to CO_2. • The influence of CO_2 in pyrolysis of biomass occurs selectively. • Hemicellulose and lignin are highly sensitive to CO_2 in pyrolysis. • Thermal cracking of VOCs can be expedited by using CO_2 in pyrolysis. - Abstract: This study is aiming at exploring the genuine role of CO_2 in pyrolysis of lignocellulosic biomass by investigating the susceptibility of pyrolysis of monosaccharide (e.g., xylose and glucose), disaccharide (e.g., sucrose), and polysaccharide (e.g., woody biomass) to CO_2. To do this, the thermal degradation of these four biomass samples was characterized in N_2 and CO_2. The thermal characterization results reveal that the physical aspects of biomass decomposition (i.e., thermal degradation rate and residual mass difference) associated with CO_2 were nearly the same; however, the chemical aspects were significantly different. In other words, CO_2 enhanced thermal cracking of volatile organic compounds (VOCs) generated from thermal degradation of biomass. In addition, our experiment results show that xylose (a major constituent of hemicellulose) and lignin exhibited a high sensitivity to CO_2 in pyrolysis.

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

Science.gov (United States)

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

2016-11-01

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

TG study on pyrolysis of biomass and its three components under syngas

Energy Technology Data Exchange (ETDEWEB)

Gang Wang; Wen Li; Baoqing Li; Haokan Chen [Chinese Academy of Sciences, Taiyuan (China). State Key Laboratory of Coal Conversion

2008-04-15

Pyrolysis of sawdust and its three components (cellulose, hemicellulose and lignin) were performed in a thermogravimetric analyzer (TGA92) under syngas and hydrogen. The effect of different heating rates (5, 10, 15 and 20{sup o}C/min) on the pyrolysis of these samples were examined. The pyrolysis tests of the synthesized samples (a mixture of the three components with different ratios) were also done under syngas. The distributed activation energy model (DAEM) was used to study the pyrolysis kinetics. It is found that syngas could replace hydrogen in hydropyrolysis process of biomass. Among the three components, hemicellulose would be the easiest one to be pyrolyzed and then would be cellulose, while lignin would be the most difficult one. Heating rate could not only affect the temperature at which the highest weight loss rate reached, but also affect the maximum value of weight loss rate. Both lignin and hemicellulose used in the experiments could affect the pyrolysis characteristic of cellulose while they could not affect each other obviously in the pyrolysis process. Values of k{sub 0} (frequency factor) change very greatly with different E (activation energy) values. The E values of sawdust range from 161.9 to 202.3 kJ/mol, which is within the range of activation energy values for cellulose, hemicellulose and lignin. 22 refs., 4 figs., 2 tabs.

Potential pyrolysis pathway assessment for microalgae-based aviation fuel based on energy conversion efficiency and life cycle

International Nuclear Information System (INIS)

Guo, Fang; Wang, Xin; Yang, Xiaoyi

2017-01-01

Highlights: • High lipid content in microalgae increases energy conversion efficiency. • Indirect pathway has the highest mass ratio, energy ratio and energy efficiency. • The Isochrysis indirect pathway produces most kerosene component precursor. • The Isochrysis indirect pyrolysis pathway shows the best performance in LCA. - Abstract: Although the research of microalgae pyrolysis has been conducted for many years, there is a lack of investigations on energy efficiency and life cycle assessment. In this study, we investigated the biocrude yield and energy efficiency of direct pyrolysis, microalgae residue pyrolysis after lipid extraction (indirect pyrolysis), and different microalgae co-pyrolysis. This research also investigated the life cycle assessment of the three different pyrolysis pathways. A system boundary of Well-to-Wake (WTWa) was defined and included sub-process models, such as feedstock production, fuel production and pump-to-wheels (PTW) stages. The pathway of Isochrysis indirect pyrolysis shows the best performance in the mass ratio and energy ratio, produces the most kerosene component precursor, has the lowest WTWa total energy input, fossil fuel consumption and greenhouse gas emissions, and resultes in the best energy efficiency. All the evidence indicates that Isochrysis R2 pathway is a potential and optimal pyrolysis pathway to liquid biofuels. The mass ratio of pyrolysis biocrude is shown to be the decisive factor for different microalgae species. The sensitivity analysis results also indicates that the life cycle indicators are particularly sensitive to the mass ratio of pyrolysis biocrude for microalgae-based hydrotreated pyrolysis aviation fuel.

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

Science.gov (United States)

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

2014-08-01

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

Bioremediation in fractured rock: 2. Mobilization of chloroethene compounds from the rock matrix

Science.gov (United States)

Shapiro, Allen M.; Tiedeman, Claire; Imbrigiotta, Thomas; Goode, Daniel J.; Hsieh, Paul A.; Lacombe, Pierre; DeFlaun, Mary F.; Drew, Scott R.; Curtis, Gary P.

2018-01-01

A mass balance is formulated to evaluate the mobilization of chlorinated ethene compounds (CE) from the rock matrix of a fractured mudstone aquifer under pre- and postbioremediation conditions. The analysis relies on a sparse number of monitoring locations and is constrained by a detailed description of the groundwater flow regime. Groundwater flow modeling developed under the site characterization identified groundwater fluxes to formulate the CE mass balance in the rock volume exposed to the injected remediation amendments. Differences in the CE fluxes into and out of the rock volume identify the total CE mobilized from diffusion, desorption, and nonaqueous phase liquid dissolution under pre- and postinjection conditions. The initial CE mass in the rock matrix prior to remediation is estimated using analyses of CE in rock core. The CE mass mobilized per year under preinjection conditions is small relative to the total CE mass in the rock, indicating that current pump-and-treat and natural attenuation conditions are likely to require hundreds of years to achieve groundwater concentrations that meet regulatory guidelines. The postinjection CE mobilization rate increased by approximately an order of magnitude over the 5 years of monitoring after the amendment injection. This rate is likely to decrease and additional remediation applications over several decades would still be needed to reduce CE mass in the rock matrix to levels where groundwater concentrations in fractures achieve regulatory standards.

Carbon abatement via treating the solid waste from the Australian olive industry in mobile pyrolysis units: LCA with uncertainty analysis.

Science.gov (United States)

El Hanandeh, Ali

2013-04-01

The olive oil industry in Australia has been growing at a rapid rate over the past decade. It is forecast to continue growing due to the steady increase in demand for olive oil and olive products in the local and regional market. However, the olive oil extraction process generates large amounts of solid waste called olive husk which is currently underutilized. This paper uses life-cycle methodology to analyse the carbon emission reduction potential of utilizing olive husk as a feedstock in a mobile pyrolysis unit. Four scenarios, based on different combinations of pyrolysis technologies (slow versus fast) and end-use of products (land application versus energy utilization), are constructed. The performance of each scenario under conditions of uncertainty was also investigated. The results show that all scenarios result in significant carbon emission abatement. Processing olive husk in mobile fast pyrolysis units and the utilization of bio-oil and biochar as substitutes for heavy fuel oil and coal is likely to realize a carbon offset greater than 32.3 Gg CO2-eq annually in 90% of the time. Likewise, more than 3.2 Gg-C (11.8 Gg CO2-eq) per year could be sequestered in the soil in the form of fixed carbon if slow mobile pyrolysis units were used to produce biochar.

Solar Assisted Fast Pyrolysis: A Novel Approach of Renewable Energy Production

Directory of Open Access Journals (Sweden)

Mohammad U. H. Joardder

2014-01-01

Full Text Available Biofuel produced by fast pyrolysis from biomass is a promising candidate. The heart of the system is a reactor which is directly or indirectly heated to approximately 500°C by exhaust gases from a combustor that burns pyrolysis gas and some of the by-product char. In most of the cases, external biomass heater is used as heating source of the system while internal electrical heating is recently implemented as source of reactor heating. However, this heating system causes biomass or other conventional forms of fuel consumption to produce renewable energy and contributes to environmental pollution. In order to overcome these, the feasibility of incorporating solar energy with fast pyrolysis has been investigated. The main advantages of solar reactor heating include renewable source of energy, comparatively simpler devices, and no environmental pollution. A lab scale pyrolysis setup has been examined along with 1.2 m diameter parabolic reflector concentrator that provides hot exhaust gas up to 162°C. The study shows that about 32.4% carbon dioxide (CO2 emissions and almost one-third portion of fuel cost are reduced by incorporating solar heating system. Successful implementation of this proposed solar assisted pyrolysis would open a prospective window of renewable energy.

Pyrolysis Process and Characteristics of Products from Sawdust Briquettes

Directory of Open Access Journals (Sweden)

Hua Yang

2016-01-01

Full Text Available The pyrolysis of briquettes made from biomass is an available and economic technological route for the production of briquette charcoal, but by-products (tar and gas cannot be brought into full utilization, leading to the waste of resources and the addition of environmental concerns. Temperature is the most important parameter that affects the distributions and properties of briquette charcoal. This work investigated the three kinds of products of the pyrolysis of sawdust briquette in a fixed bed across a wide temperature range (250 to 950 °C. The purpose of this experiment was to study the pyrolysis process and the properties of the resulting products (briquette charcoal, liquid, and gas of sawdust briquettes and explore the optimum operating temperature to generate good quality briquette charcoal, liquid, and gaseous products simultaneously. According to the results, the optimum pyrolysis temperature range was 450 to 650 °C, for which the briquette charcoal produced within this range had the highest calorific value (2,9.14 to 30.21 MJ/kg. Meanwhile, the liquid product is considered to be useful for liquid fuels or valuable chemical materials, and the low heating value of the gaseous product was 11.79 to 14.85 MJ/Nm3 in this temperature range.

Product Characterization and Kinetics of Biomass Pyrolysis in a Three-Zone Free-Fall Reactor

Directory of Open Access Journals (Sweden)

Natthaya Punsuwan

2014-01-01

Full Text Available Pyrolysis of biomass including palm shell, palm kernel, and cassava pulp residue was studied in a laboratory free-fall reactor with three separated hot zones. The effects of pyrolysis temperature (250–1050°C and particle size (0.18–1.55 mm on the distribution and properties of pyrolysis products were investigated. A higher pyrolysis temperature and smaller particle size increased the gas yield but decreased the char yield. Cassava pulp residue gave more volatiles and less char than those of palm kernel and palm shell. The derived solid product (char gave a high calorific value of 29.87 MJ/kg and a reasonably high BET surface area of 200 m2/g. The biooil from palm shell is less attractive to use as a direct fuel, due to its high water contents, low calorific value, and high acidity. On gas composition, carbon monoxide was the dominant component in the gas product. A pyrolysis model for biomass pyrolysis in the free-fall reactor was developed, based on solving the proposed two-parallel reactions kinetic model and equations of particle motion, which gave excellent prediction of char yields for all biomass precursors under all pyrolysis conditions studied.

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

International Nuclear Information System (INIS)

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

2013-01-01

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

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

Science.gov (United States)

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

2013-08-06

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

Evaluation of the nature, origin and potentiality of the subsurface Middle Jurassic and Lower Cretaceous source rocks in Melleiha G-1x well, North Western Desert, Egypt

Directory of Open Access Journals (Sweden)

Mohamed M. El Nady

2015-09-01

Full Text Available The present work aims to evaluate the nature and origin of the source rock potentiality of subsurface Middle Jurassic and Lower Cretaceous source rocks in Melleiha G-1x well. This target was achieved throughout the evaluation of total organic carbon, rock Eval pyrolysis and vitrinite reflectance for fifteen cutting samples and three extract samples collected from Khatatba, Alam El Bueib and Kharita formations in the studied well. The result revealed that the main hydrocarbon of source rocks, for the Middle Jurassic (Khatatba Fm. is mainly mature, and has good capability of producing oil and minor gas. Lower Cretaceous source rocks (Alam El Bueib Fm. are mature, derived from mixed organic sources and have fair to good capability to generate gas and oil. Kharita Formation of immature source rocks originated from terrestrial origin and has poor to fair potential to produce gas. This indicates that Khatatba and Alam El Bueib formations take the direction of increasing maturity far away from the direction of biodegradation and can be considered as effective source potential in the Melleiha G-1x well.

Comparative study on pyrolysis of lignocellulosic and algal biomass using a thermogravimetric and a fixed-bed reactor.

Science.gov (United States)

Yuan, Ting; Tahmasebi, Arash; Yu, Jianglong

2015-01-01

Pyrolysis characteristics of four algal and lignocellulosic biomass samples were studied by using a thermogravimetric analyzer (TGA) and a fixed-bed reactor. The effects of pyrolysis temperature and biomass type on the yield and composition of pyrolysis products were investigated. The average activation energy for pyrolysis of biomass samples by FWO and KAS methods in this study were in the range of 211.09-291.19kJ/mol. CO2 was the main gas component in the early stage of pyrolysis, whereas H2 and CH4 concentrations increased with increasing pyrolysis temperature. Bio-oil from Chlorellavulgaris showed higher content of nitrogen containing compounds compared to lignocellulosic biomass. The concentration of aromatic organic compounds such as phenol and its derivatives were increased with increasing pyrolysis temperature up to 700°C. FTIR analysis results showed that with increasing pyrolysis temperature, the concentration of OH, CH, CO, OCH3, and CO functional groups in char decreased sharply. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Science.gov (United States)

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

2010-12-01

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

Kinetic study of the catalytic pyrolysis of elephant grass using Ti-MCM-41

Energy Technology Data Exchange (ETDEWEB)

Fontes, Maria do Socorro Braga; Melo, Dulce Maria de Araujo; Rodrigues, Glicelia, E-mail: socorro.fontes@yahoo.com.br [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Barros, Joana Maria de Farias [Universidade Federal de Campina Grande (UFCG), Cuite, PB (Brazil). Dept. de Quimica; Braga, Renata Martins [Universidade Federal da Paraiba (UFPB/CEAR/DEER), Joao Pessoa, PB (Brazil). Centro de Energias Alternativas e Renovaveis. Dept. de Engenharia de Energia Renovaveis

2014-08-15

This work aimed to study the kinetics of thermal and catalytic pyrolysis using Ti-MCM-41 as catalyst in order to assess the catalytic pyrolysis efficiency compared to thermal pyrolysis of elephant grass. Ti-MCM-41 molecular sieve was synthesized by hydrothermal method from hydrogel with the following molar composition: 1.00 CTMABr: 4.00 SiO{sub 2}:X TiO{sub 2}: 1 + X Na{sub 2}O: 200.00 H{sub 2}O, which structure template used was cetyltrimethylammonium bromide (CTMABr). The materials synthesized were characterized by X-ray diffraction, IR spectroscopy, thermogravimetric analysis and specific area by the BET method, for subsequent application in the biomass pyrolysis process. The kinetic models proposed by Vyazovkin and Flynn-Wall were used to determine the apparent activation energy involved in the thermal and catalytic pyrolysis of elephant grass and the results showed that the catalyst used was effective in reducing the apparent activation energy involved in the thermal decomposition of elephant grass. (author)

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

Science.gov (United States)

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

2016-01-01

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

Effects of biopretreatment on pyrolysis behaviors of corn stalk by methanogen.

Science.gov (United States)

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

2014-07-01

The study investigated the effects of methanogen pretreatment on pyrolysis behaviors of corn stalk (CS) by using Py-GC/MS analysis and thermogravimetric analysis. Results indicated that biopretreatment changed considerably the pyrolysis behaviors of CS from four weight loss stages to two weight loss stages. Increasing biopretreatment time from 5 days to 25 days enhanced the kinds and contents of chemicals in volatile products. In pyrolysis products, the contents of sugars, linear ketones and furans decreased from 1.43%, 12.60% and 7.38% to 1.25%, 10.22% and 3.25%, respectively, and the contents of phenols increased from 15.08% to 27.84%. The most content change from 6.83% to 13.63% indicated that methanogen pretreatment improved the pyrolysis selectivity of CS to product the 4-VP, but it was disadvantageous to 5-hydroxymethyl furfural, levoglucose and furfural. The changes of chemical compositions and structure of CS after biopretreatment were the main reason of the differences. Copyright © 2014 Elsevier Ltd. All rights reserved.

Correlation Between Pyrolysis Atmosphere and Carbon Molecular Sieve Membrane Performance Properties

KAUST Repository

Kiyono, Mayumi; Koros, William J.; Williams, Paul J.

2011-01-01

Carbon molecular sieve (CMS) membranes have attractive separation performance properties, greatly exceeding an "upper bound" trade-off curve of polymeric membrane performance. CMS membranes are prepared by pyrolyzing polymers, well above their glass transition temperatures. Multiple factors, such as polymer precursor and pyrolysis protocol, are known to affect the separation performance. In this study, a correlation observed between pyrolysis atmosphere and CMS separation performance properties is discussed. Specifically, oxygen exposure during the pyrolysis process is the focus. The theory and details of the oxygen exposure and development of a new CMS preparation method using oxygen as a "dopant" will be described with a strong correlation observed with separation performance for CMS membranes prepared with various polymer precursors. In addition, study of possible mass transfer limitations on the oxygen "doping" process will be described to clarify the basis for the equilibrium-based interpretation of doping data. The method is also explored by changing the pyrolysis temperature. © 2011 Elsevier B.V.

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

Science.gov (United States)

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.

Studies on liquefaction and pyrolysis of peat and biomass at KTH

International Nuclear Information System (INIS)

Bjoernbom, E.; Sjoestrom, K.; Hoernel, C.; Zanzi, R.; Bjoernbom, P.

1996-01-01

A brief review of the study on thermochemical conversion of solid fuels is done. The study have been performed in the Royal Institute of Technology, Stockholm, since the outbreak of energy crisis in the seventies. The main problems connected with utilisation of peat for energy are: 90% moisture content in the deposits and 35-40% oxygen content in the dry substance. Simultaneous dewatering and liquefaction of peat have been achieved by the Bjoerbom method. The wet peat has been treated with CO and H 2 O without preliminary drying, using water as a medium agent. After treatment water has been phase-separated from the heavy oil product. Another approach is de-oxygenation of peat prior to liquefaction. A significant part of oxygen in peat and biomass can be removed by thermal decomposition of the fuels prior to liquefaction and removal of carbon dioxide and water from the organic matter in them. The products obtained after de-oxygenation demand low consumption of external hydrogenation agent because they are rich in hydrogen. Some criteria for selection of peat as a raw material for liquefaction are given. The equipment and experimental procedure for pyrolysis of peat and biomass are described. A free fall tubular reactor with max operating pressure of 5 MPa and temperature of 1100 o C has been used. The effect of treatment conditions under the rapid pyrolysis in the free fall reactor on the yield and the reactivity of char obtained after the final pyrolysis is shown. Peat and wood are transformed into pyrolysis products for less than 1 second; 35-50% of the moisture- and ash-free peat and 70% of the wood have been converted into gaseous products.The char obtained in the rapid pyrolysis contains a fraction which can be further de-volatilized by slow pyrolysis for a few minutes - time much longer than the time for formation of primary products. High reactivity of char is favoured by lower pyrolysis temperature, shorter residence time and larger particle size of the fuel

Influence of reaction conditions on fast pyrolysis of macroalge

International Nuclear Information System (INIS)

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

2010-01-01

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

Origin and distribution of the organic matter in the distal lobe of the Congo deep-sea fan - A Rock-Eval survey

Science.gov (United States)

Baudin, François; Stetten, Elsa; Schnyder, Johann; Charlier, Karine; Martinez, Philippe; Dennielou, Bernard; Droz, Laurence

2017-08-01

The Congo River, the second largest river in the world, is a major source of organic matter for the deep Atlantic Ocean because of the connection of its estuary to the deep offshore area by a submarine canyon which feeds a vast deep-sea fan. The lobe zone of this deep-sea fan is the final receptacle of the sedimentary inputs presently channelled by the canyon and covers an area of 2500 km². The quantity and the source of organic matter preserved in recent turbiditic sediments from the distal lobe of the Congo deep-sea fan were assessed using Rock-Eval pyrolysis analyses. Six sites, located at approximately 5000 m water-depth, were investigated. The mud-rich sediments of the distal lobe contain high amounts of organic matter ( 3.5 to 4% Corg), the origin of which is a mixture of terrestrial higher-plant debris, soil organic matter and deeply oxidized phytoplanktonic material. Although the respective contribution of terrestrial and marine sources of organic matter cannot be precisely quantified using Rock-Eval analyses, the terrestrial fraction is dominant according to similar hydrogen and oxygen indices of both suspended and bedload sediments from the Congo River and that deposited in the lobe complex. The Rock-Eval signature supports the 70% to 80% of the terrestrial fraction previously estimated using C/N and δ13Corg data. In the background sediment, the organic matter distribution is homogeneous at different scales, from a single turbiditic event to the entire lobe, and changes in accumulation rates only have a limited effect on the quantity and quality of the preserved organic matter. Peculiar areas with chemosynthetic bivalves and/or bacterial mats, explored using ROV Victor 6000, show a Rock-Eval signature similar to background sediment. This high organic carbon content associated to high sedimentation rates (> 2 to 20 mm.yr-1) in the Congo distal lobe complex implies a high burial rate for organic carbon. Consequently, the Congo deep-sea fan represents an

Analysis and comparison of biomass pyrolysis/gasification condensates: Final report

Energy Technology Data Exchange (ETDEWEB)

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 longer 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.

Performance of rotary kiln reactor for the elephant grass pyrolysis.

Science.gov (United States)

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.

Biomass pyrolysis/gasification for product gas production: the overall investigation of parametric effects

International Nuclear Information System (INIS)

Chen, G.; Andries, J.; Luo, Z.; Spliethoff, H.

2003-01-01

The conventional biomass pyrolysis/gasification process for production of medium heating value gas for industrial or civil applications faces two disadvantages, i.e. low gas productivity and the accompanying corrosion of downstream equipment caused by the high content of tar vapour contained in the gas phase. The objective of this paper is to overcome these disadvantages, and therefore, the effects of the operating parameters on biomass pyrolysis are investigated in a laboratory setup based on the principle of keeping the heating value of the gas almost unchanged. The studied parameters include reaction temperature, residence time of volatile phase in the reactor, physico-chemical pretreatment of biomass particles, heating rate of the external heating furnace and improvement of the heat and mass transfer ability of the pyrolysis reactor. The running temperature of a separate cracking reactor and the geometrical configuration of the pyrolysis reactor are also studied. However, due to time limits, different types of catalysts are not used in this work to determine their positive influences on biomass pyrolysis behaviour. The results indicate that product gas production from biomass pyrolysis is sensitive to the operating parameters mentioned above, and the product gas heating value is high, up to 13-15 MJ/N m 3

Pyrolysis of Spent Ion Exchange Resins

International Nuclear Information System (INIS)

Braehler, Georg; Slametschka, Rainer

2012-09-01

Ion exchangers (IEX in international language) are used to remove radionuclides from the primary coolant in all nuclear power stations with a water cooling circuit. This is done by continuously removing a volume of coolant from the primary circuit and passing it through coolers, filters and the ion exchange beds. Cation and anion exchangers, in the form of coarse-grained resin beads in pressurized-water reactors and as finely ground powdered resins in boiling water reactors, are used. The trend for new power stations is to exploit all the possibilities for avoiding the generation of contaminated liquids and then to clean, as far as possible, the solutions that are nevertheless generated using ion exchange for it to be possible to dispose of them as non-radioactive waste. This relieves the burden on evaporator facilities, or means that these can even be dispensed with entirely. Regeneration is possible in principle, but little use is made of it. As the regeneration usual in conventional technologies is not employed in nuclear power stations, it is necessary to dispose of this material as radioactive waste. On the international level, a great number of processes are offered that are intended to meet the relevant national regulations, and these will be discussed in brief with their advantages and disadvantages. The aim is then to find a process which reduces the volume, yields an inert or mineralized product, works at temperatures of no more than approximately 600 deg. C and can be run in a simple facility. Originally, the pyrolysis process was developed to treat liquid organic waste from reprocessing. A typical application is the decomposition of spent solvent (TBP, tributyl phosphate, mixed with kerosene). In this process TBP is pyrolyzed together with calcium hydroxide in a fluidized bed facility at temperatures of around 500 deg. C, the calcium hydroxide reacts with the phosphate groups directly to form calcium pyrophosphate which contains all the radioactivity

Coal pyrolysis and char burnout under conventional and oxy-fuel conditions

Energy Technology Data Exchange (ETDEWEB)

Al-Makhadmeh, L.; Maier, J.; Scheffknecht, G. [Stuttgart Univ. (Germany). Institut fuer Verfahrenstechnik und Dampfkesselwesen

2009-07-01

Coal utilization processes such as combustion or gasification generally involve several steps i.e., the devolatilization of organic materials, homogeneous reactions of volatile matter with the reactant gases, and heterogeneous reactions of the solid (char) with the reactant gases. Most of the reported work about coal pyrolysis and char burnout were performed at low temperatures under environmental conditions related to the air firing process with single particle tests. In this work, coal combustion under oxy-fuel conditions is investigated by studying coal pyrolysis and char combustion separately in practical scales, with the emphasis on improving the understanding of the effect of a CO{sub 2}-rich gas environment on coal pyrolysis and char burnout. Two coals, Klein Kopje a medium volatile bituminous coal and a low-rank coal, Lausitz coal were used. Coal pyrolysis in CO{sub 2} and N{sub 2} environments were performed for both coals at different temperatures in an entrained flow reactor. Overall mass release, pyrolysis gas concentrations, and char characterization were performed. For char characterization ultimate analysis, particle size, and BET surface area were measured. Chars for both coals were collected at 1150 C in both CO{sub 2} and N{sub 2} environments. Char combustion was performed in a once-through 20 kW test facility in O{sub 2}/CO{sub 2} and O{sub 2}/N{sub 2} atmospheres. Besides coal quality, oxygen partial pressure was chosen as a variable to study the effect of the gas environment on char burnout. In general, it is found that the CO{sub 2} environment and coal rank have a significant effect on coal pyrolysis and char burnout. (orig.)

Experimental and modeling study on pyrolysis of n-decane initiated by nitromethane

KAUST Repository

Jia, Zhenjian

2016-01-15

Initiator could accelerate the rate of hydrocarbon pyrolysis and reduce the required material temperatures for a hypersonic aircraft heat exchanger/reactor. Nitroalkanes were proposed as the effective initiator because of the lower CN bond dissociation energy. In order to investigate the initiation mechanism of nitroalkanes on hydrocarbon pyrolysis, the pyrolysis of n-decane, nitromethane and their binary mixture were carried out at 30, 150 and 760 Torr in a flow reactor with synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). The identified and quantified pyrolysis species include C1C2 alkanes, C2C10 alkenes, C3C6 dialkenes, C2C3 alkynes, nitrogen oxides such as NO and NO2, benzene, and radicals including CH3, C3H3, and C3H5, which shed light on the mechanism of n-decane and nitromethane pyrolysis, as well as the interactions of these two fuels. The experimental results indicate that the addition of nitromethane decreases the initial decomposition temperature of n-decane, and a stronger promotion effect could be obtained as the experimental pressure increases. The distributions of alkanes, alkenes, dialkenes, alkynes and benzene are also influenced by the addition of nitromethane. A detailed kinetic model with 266 species and 1648 reactions was developed and validated against the mole fraction profiles of reactants, major products and important intermediates during the pyrolysis of each fuel and their binary mixture. The satisfactory model prediction to the experimental measurements permits the analysis of the kinetic effect of nitromethane initiation on the pyrolysis of n-decane. So that, the increase of the conversion rate at a lower temperature, the selectivity of decomposition products, and reduction of benzene formation are better understood.

Formation of N{sub 2} during the fixed-bed pyrolysis of coals

Energy Technology Data Exchange (ETDEWEB)

Wu, Zhiheng; Ohtsuka, Yasuo [Tohoku Univ., Sendai (Japan); Furimsky, E. [Natural Resources Canada, Ottawa, Ontario (Canada)

1995-12-31

Research on the fate of the nitrogen in coal during pyrolysis has attracted increased attention, since it is related with the NO{sub x} and N{sub 2}O emissions during subsequent combustion. It has been reported that coal nitrogen is initially released as tar, which is then converted to HCN and NH{sub 3} through secondary decomposition reactions. However, little attention to N{sub 2} has been paid so far. We have recently found that N{sub 2} is the dominant product in slow heating rate pyrolysis of a subbituminous coal, and that the finely dispersed iron catalyst promotes drastically the formation of N{sub 2} from a brown coal. If coal nitrogen can be removed efficiently as N{sub 2} during pyrolysis, this method would contribute to the reduction of the NO{sub x} and N{sub 2}O emissions, since such pollutants originate mostly from coal nitrogen. Therefore the present study aims at making clear the influence of coal type, pyrolysis conditions, demineralization, and iron catalyst on the formation of N{sub 2} during the fix-bed pyrolysis of several coals with different ranks.

High-speed pyrolysis with circulating heat carriers; Schnell-Pyrolyse mit zirkulierenden Waermetraegern

Energy Technology Data Exchange (ETDEWEB)

Schmalfeld, J; Albrecht, J; Solmaz, S; Zentner, U [Lurgi Energie und Umwelt GmbH, Frankfurt am Main (Germany)

1998-09-01

Yields and product compositions of pyrolysis reactions depend on the mode of heat supply, the temperature level, and the time of residue at reaction temperature. Using hot circulating granular materials mixed with solid or liquid materials (e.g. biogenic or hydrocarbon-rich residues and waste materials or refinery residues), the following important processes can be investigated: Separation of pyrolysis reaction and heat supply - accurate, optimal temperature levels for pyrolysis, e.g. between 5000 and 850 degrees centigrade - undiluted, unmixed pyrolysis gas - short times of residue of the pyrolysis gas for suppression of secondary reactions. (orig.) [Deutsch] Ausbeuten und Produktzusammensetzung von Pyrolyse-Reaktionen werden weitestgehend durch die Art und Weise der Waermezufuhr, das Temperaturniveau und die Verweilzeit bei Reaktionstemperatur bestimmt. Mit Hilfe des Prinzips heisser, umlaufender, koerniger Waermetraeger in Vermischung - fuer die Pyrolyse-Reaktion - mit festen oder fluessigen Einsatzstoffen (z.B. biogene oder kohlenwasserstoffreiche Rest-/Abfallstoffe, Raffinerie-Rueckstaende) lassen sich folgende wichtige, haeufig gewuenschte Vorgaenge realisieren: - Trennung von Pyrolyse-Reaktion und Waermeversorgung - Temperaturgenaue Pyrolyse-Reaktion auf gewuenschtem, optimalem Niveau waehlbar zwischen z.B. 5000 C und 850 C - Erhalt eines unverduennten, unvermischten Pyrolysegases - Kurze Verweilzeiten des Pyrolysegases zur Unterdrueckung von Sekundaerreaktionen. (orig.)

Fast Pyrolysis of Four Lignins from Different Isolation Processes Using Py-GC/MS

OpenAIRE

Lin, Xiaona; Sui, Shujuan; Tan, Shun; Pittman, Charles; Sun, Jianping; Zhang, Zhijun

2015-01-01

Pyrolysis is a promising approach that is being investigated to convert lignin into higher value products including biofuels and phenolic chemicals. In this study, fast pyrolysis of four types of lignin, including milled Amur linden wood lignin (MWL), enzymatic hydrolysis corn stover lignin (EHL), wheat straw alkali lignin (AL) and wheat straw sulfonate lignin (SL), were performed using pyrolysis gas-chromatography/mass spectrometry (Py-GC/MS). Thermogravimetric analysis (TGA) showed that the...

Treatment of Lignin and Waste residues by Flash Pyrolysis

DEFF Research Database (Denmark)

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

pyrolysis properties were compared with the pyrolysis properti es of wood and straw. The PCR treatment of sewage sludge provides an oil that can be used for energy pur poses and a solid residue rich in in organic nutrients that may be used as fertilizer product. By fast pyroly sis of lignin from the IBUS...... be operated at low rotational speed was constructed. The new rotor systems should make it easier to make an up-scaling of the process....

The Evritania (Greece) demonstration plant of biomass pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Zabaniotou, A.A.; Karabela, A.J. [Aristotle University of Thessaloniki (Greece). Dept. of Chemical Engineering and Chemical Process Engineering Research Institute

1999-06-01

This paper is focused on describing the Evritania demonstration plant for pyrolysis of forestry biomass. This plant was constructed in the village of Voulpi, district of Evritania, in central Greece, in 1995, with a threefold purpose; development of know-how, forest fire prevention and rural development. The products are charcoal and bio-oil. The plant capacity is 1200-1450 kg/h of wet biomass and the pyrolysis temperature is approx. 400 deg C. The raw material used is Arbutus unedo, which is an evergreen broad-leaf tree which covers the area. Other agricultural waste could also be used, such as olive pits and cuttings, almond shells and cotton kernels. The paper includes the conceptual process flow sheet, the changes and improvements made during the trial phase, data from the start-up phase, and product characteristics. Comparison of the process with the Alten process is presented. Additionally, comparisons are made of product characteristics with those from other pyrolysis processes. In general, the results obtained are encouraging even though several improvements of the pilot plant are required. (author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-09-29

Pyrolysis oils contain more than 400 compounds, up to 60% of which do not re-volatilize for subsequent chemical analysis. Vapor chemical composition is also complicated as additional condensation reactions occur during quenching and collection of the product. Due to the complexity of the pyrolysis oil, and a desire to catalytically upgrade the vapor composition before condensation, online real-time analytical techniques such as Molecular Beam Mass Spectrometry (MBMS) are of great use. However, in order to properly sample hot pyrolysis vapors at the pilot scale, many challenges must be overcome.

Use of a Deuterated Internal Standard with Pyrolysis-GC/MS Dimeric Marker Analysis to Quantify Tire Tread Particles in the Environment

Directory of Open Access Journals (Sweden)

Julie M. Panko

2012-11-01

Full Text Available Pyrolysis(pyr-GC/MS analysis of characteristic thermal decomposition fragments has been previously used for qualitative fingerprinting of organic sources in environmental samples. A quantitative pyr-GC/MS method based on characteristic tire polymer pyrolysis products was developed for tread particle quantification in environmental matrices including soil, sediment, and air. The feasibility of quantitative pyr-GC/MS analysis of tread was confirmed in a method evaluation study using artificial soil spiked with known amounts of cryogenically generated tread. Tread concentration determined by blinded analyses was highly correlated (r2 ³ 0.88 with the known tread spike concentration. Two critical refinements to the initial pyrolysis protocol were identified including use of an internal standard and quantification by the dimeric markers vinylcyclohexene and dipentene, which have good specificity for rubber polymer with no other appreciable environmental sources. A novel use of deuterated internal standards of similar polymeric structure was developed to correct the variable analyte recovery caused by sample size, matrix effects, and ion source variability. The resultant quantitative pyr-GC/MS protocol is reliable and transferable between laboratories.

Use of a deuterated internal standard with pyrolysis-GC/MS dimeric marker analysis to quantify tire tread particles in the environment.

Science.gov (United States)

Unice, Kenneth M; Kreider, Marisa L; Panko, Julie M

2012-11-08

Pyrolysis(pyr)-GC/MS analysis of characteristic thermal decomposition fragments has been previously used for qualitative fingerprinting of organic sources in environmental samples. A quantitative pyr-GC/MS method based on characteristic tire polymer pyrolysis products was developed for tread particle quantification in environmental matrices including soil, sediment, and air. The feasibility of quantitative pyr-GC/MS analysis of tread was confirmed in a method evaluation study using artificial soil spiked with known amounts of cryogenically generated tread. Tread concentration determined by blinded analyses was highly correlated (r2 ≥ 0.88) with the known tread spike concentration. Two critical refinements to the initial pyrolysis protocol were identified including use of an internal standard and quantification by the dimeric markers vinylcyclohexene and dipentene, which have good specificity for rubber polymer with no other appreciable environmental sources. A novel use of deuterated internal standards of similar polymeric structure was developed to correct the variable analyte recovery caused by sample size, matrix effects, and ion source variability. The resultant quantitative pyr-GC/MS protocol is reliable and transferable between laboratories.

Evaluating the effect of potassium on cellulose pyrolysis reaction kinetics

International Nuclear Information System (INIS)

Trendewicz, Anna; Evans, Robert; Dutta, Abhijit; Sykes, Robert; Carpenter, Daniel; Braun, Robert

2015-01-01

This paper proposes modifications to an existing cellulose pyrolysis mechanism in order to include the effect of potassium on product yields and composition. The changes in activation energies and pre-exponential factors due to potassium were evaluated based on the experimental data collected from pyrolysis of cellulose samples treated with different levels of potassium (0–1% mass fraction). The experiments were performed in a pyrolysis reactor coupled to a molecular beam mass spectrometer (MBMS). Principal component analysis (PCA) performed on the collected data revealed that cellulose pyrolysis products could be divided into two groups: anhydrosugars and other fragmentation products (hydroxyacetaldehyde, 5-hydroxymethylfurfural, acetyl compounds). Multivariate curve resolution (MCR) was used to extract the time resolved concentration score profiles of principal components. Kinetic tests revealed that potassium apparently inhibits the formation of anhydrosugars and catalyzes char formation. Therefore, the oil yield predicted at 500 ° C decreased from 87.9% from cellulose to 54.0% from cellulose with 0.5% mass fraction potassium treatment. The decrease in oil yield was accompanied by increased yield of char and gases produced via a catalyzed dehydration reaction. The predicted char and gas yield from cellulose were 3.7% and 8.4%, respectively. Introducing 0.5% mass fraction potassium treatment resulted in an increase of char yield to 12.1% and gas yield to 33.9%. The validation of the cellulose pyrolysis mechanism with experimental data from a fluidized-bed reactor, after this correction for potassium, showed good agreement with our results, with differences in product yields of up to 5%

Pyrolysis of Waste Castor Seed Cake: A Thermo-Kinetics Study

Directory of Open Access Journals (Sweden)

Abdullahi Muhammad Sokoto

2018-03-01

Full Text Available Biomass pyrolysis is a thermo-chemical conversion process that is of both industrial and ecological importance. The efficient chemical transformation of waste biomass to numerous products via pyrolysis reactions depends on process kinetic rates; hence the need for kinetic models to best design and operate the pyrolysis. Also, for an efficient design of an environmentally sustainable pyrolysis process of a specific lignocellulosic waste, a proper understanding of its thermo-kinetic behavior is imperative. Thus, pyrolysis kinetics of castor seed de-oiled cake (Ricinus communis using thermogravimetric technique was studied. The decomposition of the cake was carried out in a nitrogen atmosphere with a flow rate of 100mL min-1 from ambient temperature to 900 °C. The results of the thermal profile showed moisture removal and devolatilization stages, and maximum decomposition of the cake occurred at a temperature of 200-400 °C. The kinetic parameters such as apparent activation energy, pre-exponential factor, and order of reaction were determined using Friedman (FD, Kissinger-Akahira-Sunose (KAS, and Flynn-Wall-Ozawa (FWO kinetic models. The average apparent activation energy values of 124.61, 126.95 and 129.80 kJmol-1 were calculated from the slopes of the respective models. The apparent activation energy values obtained depends on conversion, which is an evidence of multi-step kinetic process during the pyrolytic decomposition of the cake. The kinetic data would be of immense benefit to model, design and develop a suitable thermo-chemical system for the conversion of waste de-oil cake to energy carrier.

Aespoe Hard Rock Laboratory. Prototype Repository. Analyses of microorganisms, gases and water chemistry in buffer and backfill, 2009

Energy Technology Data Exchange (ETDEWEB)

Lydmark, Sara (Microbial Analytics Sweden AB (Sweden))

2010-09-15

The Prototype repository is an international project to build and study a full-scale model of the planned Swedish final repository for spent nuclear fuel. The Prototype repository differs from a real storage in that it is drained. For example, this makes the swelling pressure lower in the Prototype repository compared with a real storage. The project is being conducted at the Aespoe Hard Rock Laboratory (HRL) in crystalline rock at a depth of approximately 450 m. A monitoring programme is investigating the evolution of the water chemistry, gas, and microbial activity at the site, and one of the specific aims is to monitor the microbial consumption of oxygen in situ in the Prototype repository. This document describes the results of the analyses of microbes, gases, and chemistry inside and outside the Prototype in 2009. Hydrogen, helium, nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, and ethene were analysed in the following sampling points in the Prototype repository: KBU10001, KBU10002, KBU10004, KBU10006, KBU10008, KFA01 and KFA04. Where the sampling points in the Prototype delivered pore water, the water was analysed for amount of ATP (i.e., the biovolume), cultivable heterotrophic aerobic bacteria (CHAB), sulphate-reducing bacteria (SRB), methane-oxidizing bacteria (MOB), autotrophic acetogens (AA) and in some cases iron-reducing bacteria (IRB). Cultivation methods were also compared with qPCR molecular techniques to evaluate these before next year's decommission of the Prototype repository. The collected pore water from the Prototype repository was subject to chemistry analysis (as many analyses were conducted as the amount of water allowed). In addition, groundwater from two borehole sections in the rock surrounding the Prototype was analysed regarding its gas composition, microbiology and redox. Chemistry data from a previous investigation of the groundwater outside the Prototype repository were compared with the pore water

Aespoe Hard Rock Laboratory. Prototype Repository. Analyses of microorganisms, gases and water chemistry in buffer and backfill, 2009

International Nuclear Information System (INIS)

Lydmark, Sara

2010-09-01

The Prototype repository is an international project to build and study a full-scale model of the planned Swedish final repository for spent nuclear fuel. The Prototype repository differs from a real storage in that it is drained. For example, this makes the swelling pressure lower in the Prototype repository compared with a real storage. The project is being conducted at the Aespoe Hard Rock Laboratory (HRL) in crystalline rock at a depth of approximately 450 m. A monitoring programme is investigating the evolution of the water chemistry, gas, and microbial activity at the site, and one of the specific aims is to monitor the microbial consumption of oxygen in situ in the Prototype repository. This document describes the results of the analyses of microbes, gases, and chemistry inside and outside the Prototype in 2009. Hydrogen, helium, nitrogen, oxygen, carbon monoxide, carbon dioxide, methane, ethane, and ethene were analysed in the following sampling points in the Prototype repository: KBU10001, KBU10002, KBU10004, KBU10006, KBU10008, KFA01 and KFA04. Where the sampling points in the Prototype delivered pore water, the water was analysed for amount of ATP (i.e., the biovolume), cultivable heterotrophic aerobic bacteria (CHAB), sulphate-reducing bacteria (SRB), methane-oxidizing bacteria (MOB), autotrophic acetogens (AA) and in some cases iron-reducing bacteria (IRB). Cultivation methods were also compared with qPCR molecular techniques to evaluate these before next year's decommission of the Prototype repository. The collected pore water from the Prototype repository was subject to chemistry analysis (as many analyses were conducted as the amount of water allowed). In addition, groundwater from two borehole sections in the rock surrounding the Prototype was analysed regarding its gas composition, microbiology and redox. Chemistry data from a previous investigation of the groundwater outside the Prototype repository were compared with the pore water chemistry

Bioremediation in Fractured Rock: 2. Mobilization of Chloroethene Compounds from the Rock Matrix.

Science.gov (United States)

Shapiro, Allen M; Tiedeman, Claire R; Imbrigiotta, Thomas E; Goode, Daniel J; Hsieh, Paul A; Lacombe, Pierre J; DeFlaun, Mary F; Drew, Scott R; Curtis, Gary P

2018-03-01

A mass balance is formulated to evaluate the mobilization of chlorinated ethene compounds (CE) from the rock matrix of a fractured mudstone aquifer under pre- and postbioremediation conditions. The analysis relies on a sparse number of monitoring locations and is constrained by a detailed description of the groundwater flow regime. Groundwater flow modeling developed under the site characterization identified groundwater fluxes to formulate the CE mass balance in the rock volume exposed to the injected remediation amendments. Differences in the CE fluxes into and out of the rock volume identify the total CE mobilized from diffusion, desorption, and nonaqueous phase liquid dissolution under pre- and postinjection conditions. The initial CE mass in the rock matrix prior to remediation is estimated using analyses of CE in rock core. The CE mass mobilized per year under preinjection conditions is small relative to the total CE mass in the rock, indicating that current pump-and-treat and natural attenuation conditions are likely to require hundreds of years to achieve groundwater concentrations that meet regulatory guidelines. The postinjection CE mobilization rate increased by approximately an order of magnitude over the 5 years of monitoring after the amendment injection. This rate is likely to decrease and additional remediation applications over several decades would still be needed to reduce CE mass in the rock matrix to levels where groundwater concentrations in fractures achieve regulatory standards. © 2017, National Ground Water Association.

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

Science.gov (United States)

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

2018-05-18

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

The study of catalytic properties and phase composition of pyrolysis products of molybdophosphoric heteropolyacid. Communication 3. Environmental effect on the HPA pyrolysis

International Nuclear Information System (INIS)

Bondareva, V.M.; Andrushkevich, T.V.; Maksimovskaya, R.I.; Plyasova, L.M.; Litvak, G.S.; Burgina, E.B.

1997-01-01

Character of pyrolysis of molybdophosphonic heteropolyacid (HPA) (H 3 PMo 12 O 40 x13H 2 O) in different media (air, hydrogen, oxygen, helium, water vapour, as well reactive mixture containing acrolein) is studied within the temperature range of 200-700 deg C. With application of methods of X-ray analysis in situ, NMR 31 R and IR-spectroscopy it is shown that phase formation by HPA pyrolysis depends on the media, oxidation-reduction properties and availability of water vapour therein. 27 refs.; 5 figs

Production of bran castor biochar through slow pyrolysis

Science.gov (United States)

Pissinati de Rezende, E. I.; Mangrich, A. S.; Batista, M. G. F.; Toledo, J. M. S.; Novotny, E. H.

2012-04-01

Pyrolysis is a thermal process of great importance in the present context, since it constitutes a significant alternative to adequate use of organic waste. The principal products obtained in the pyrolysis of discarded biomass are bio-oil, biogas and biochar. Biochar, in turn, may play a relevant role when applied to the soil to sequester carbon and as a soil conditioner, a material comparable to organic matter of Indians Black Earths from the Amazon Region [1]. Seeking to determine the best methods of preparation of biochar, we studied the pyrolysis of bran castor residue of the Brazilian biodiesel industry. Eight samples, from FM1 to FM8, were prepared in a factorial design 23 using two temperature (300 and 350 °C), two heating velocity (5 and 10 °C min-1) and two period of heating (30 and 60 min). The eight samples were studied using the spectroscopy: EPR, FTIR, RMN, XPS, and elemental analysis. By elemental analysis, the samples that keep for lower temperature of pyrolysis, 300 °C, showed H/C and N/C ratios greater than the samples of 350 °C. That higher value can be attributed to chemical structure more aliphatic than aromatic mainly in the FM7 sample (V = 10 °C min-1, T = 300 °C, P = 30 min). The greater N/C ratio correlated with a superior amount of nitrogenous functions, presenting by both FM7 and FM4 samples, as determined by 13C NMR spectroscopy with absorptions in 175 ppm (amide) and 55 ppm (N-alkyl).

Pyrolysis of rice husk and corn stalk in auger reactor:Part 1. Characterization of char and gas at various temperatures

OpenAIRE

Yu, Yang; Yang, Yang; Cheng, Zhicai; Blanco, Paula H.; Liu, Ronghou; Bridgwater, A.V.; Cai, Junmeng

2016-01-01

In this study, rice husk and corn stalk have been pyrolyzed in an auger pyrolysis reactor at pyrolysis temperatures of 350, 400, 450, 500, 550, and 600 °C in order to investigate the effect of the pyrolysis temperature on the pyrolysis performance of the reactor and physicochemical properties of pyrolysis products (this paper focuses on char and gas). The results have shown that the pyrolysis temperature significantly affects the mass yields and properties of the pyrolysis products. The mass ...

In line wood plastic composite pyrolyses and HZSM-5 conversion of the pyrolysis vapors

International Nuclear Information System (INIS)

Lin, Xiaona; Zhang, Zhijun; Tan, Shun; Wang, Fengqiang; Song, Yongming; Wang, Qingwen; Pittman, Charles U.

2017-01-01

Graphical abstract: HZSM-5 can be used to catalytic convert Wood Fiber-Polypropylene or Wood Fiber-Polypropylene pyrolysis vapors into aromatic compounds in reasonable selectivities. This provides a recycling utilization WPCs wastes method. - Highlights: • Converting wood/plastic composites (WPC) wastes into aromatics. • Recycling WPC by fast pyrolysis coupled with vapor catalytic cracking. • Selective production of aromatics from WPCs and their components over HZSM-5. • Acid site concentration inside zeolite was critical for maximizing aromatic yield. • Synergistic effects between wood and plastics enhanced aromatics production. - Abstract: Wood powder-high density polyethylene (WPE) and wood powder-polypropylene (WPP) composites were pyrolyzed at 550 °C in the presence of HZSM-5 catalysts using analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Immediately passing the pyrolysis vapors through the HZSM-5 changed the product distribution by producing aromatic hydrocarbons and eliminating tar formation. Zeolite HZSM-5 was employed with three different silica-to-alumina ratios (25, 50, 260). The influence of catalysts on the yields of aliphatic and aromatic hydrocarbons, furan derivatives, lignin-derived compounds and acetic acid was studied. High yields of aliphatic hydrocarbons formed in WPE or WPP pyrolysis alone. The highest yields of aromatic hydrocarbons from WPE or WPP pyrolysis vapors over HZSM-5 occurred with a zeolite framework Si/Al ratio of 25 (more acid sites), suggesting that the concentration of acid sites inside the zeolite was critical for maximizing aromatic yield. Exposing vapors to HZSM-5 increased the hydrocarbon yields and reduced the amount of acetic acid produced, resulting in increased calorific value. The yields of typical aromatics from catalytic pyrolysis of WPP mixture and composites were higher than those of the calculated values of poplar wood and PP catalytic pyrolysis individually, indicating that a

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Estimation of apparent kinetic parameters of polymer pyrolysis with complex thermal degradation behavior

International Nuclear Information System (INIS)

Srimachai, Taranee; Anantawaraskul, Siripon

2010-01-01

Full text: Thermal degradation behavior during polymer pyrolysis can typically be described using three apparent kinetic parameters (i.e., pre-exponential factor, activation energy, and reaction order). Several efficient techniques have been developed to estimate these apparent kinetic parameters for simple thermal degradation behavior (i.e., single apparent pyrolysis reaction). Unfortunately, these techniques cannot be directly extended to the case of polymer pyrolysis with complex thermal degradation behavior (i.e., multiple concurrent reactions forming single or multiple DTG peaks). In this work, we proposed a deconvolution method to determine the number of apparent reactions and estimate three apparent kinetic parameters and contribution of each reaction for polymer pyrolysis with complex thermal degradation behavior. The proposed technique was validated with the model and experimental pyrolysis data of several polymer blends with known compositions. The results showed that (1) the number of reaction and (2) three apparent kinetic parameters and contribution of each reaction can be estimated reasonably. The simulated DTG curves with estimated parameters also agree well with experimental DTG curves. (author)

Development of slow pyrolysis business operations in Finland - Hidaspyro

Energy Technology Data Exchange (ETDEWEB)

Fagernas, L. [VTT Technical Research Centre of Finland, Espoo (Finland)], email: leena.fagernas@vtt.fi

2012-07-01

Birch distillate, a by-product in slow pyrolysis process of charcoal production, was found to be a promising source for biological pesticides. However, product commercialization was problematic, for EU registration is costly, and composition, active ingredients and ecotoxicological properties were not known. In addition, constant quality and process optimisation were needed. More collaboration between SMEs and research institutes was required. The primary aim was to support and develop slow pyrolysis business operations of SMEs in Finland by generating knowledge that was needed.

Ion microprobe analyses of aluminous lunar glasses - A test of the 'rock type' hypothesis

Science.gov (United States)

Meyer, C., Jr.

1978-01-01

Previous soil survey investigations found that there are natural groupings of glass compositions in lunar soils and that the average major element composition of some of these groupings is the same at widely separated lunar landing sites. This led soil survey enthusiasts to promote the hypothesis that the average composition of glass groupings represents the composition of primary lunar 'rock types'. In this investigation the trace element composition of numerous aluminous glass particles was determined by the ion microprobe method as a test of the above mentioned 'rock type' hypothesis. It was found that within any grouping of aluminous lunar glasses by major element content, there is considerable scatter in the refractory trace element content. In addition, aluminous glasses grouped by major elements were found to have different average trace element contents at different sites (Apollo 15, 16 and Luna 20). This evidence argues that natural groupings in glass compositions are determined by regolith processes and may not represent the composition of primary lunar 'rock types'.

Techno-economic evaluation of high temperature pyrolysis processes for mixed plastic waste.

NARCIS (Netherlands)

Westerhout, R.W.J.; Westerhout, R.W.J.; van Koningsbruggen, M.P.; van der Ham, Aloysius G.J.; Kuipers, J.A.M.; van Swaaij, Willibrordus Petrus Maria

1998-01-01

Three pyrolysis processes for Mixed Plastic Waste (MPW) with different reactors (Bubbling Fluidized Bed, Circulating Fluidized Bed and Rotating Cone Reactor, respectively BFB, CFB and RCR) were designed and evaluated. The estimated fixed capital investment for a 50 kton/year MPW pyrolysis plant

Physical Matrix Characterisation: Studies of Crystalline Rocks and Consolidated Clays by PMMA Method and Electron Microscopy as Support of Diffusion Analyses

Energy Technology Data Exchange (ETDEWEB)

Siitari-Kauppi, M.; Leskinen, A.; Kelokaski, A.; Togneri, L.; Alonso, U.; Missana, T.; Garcia-Gutierrez, M.; Patelli, A.

2007-07-01

Crystalline rock and consolidated clay are both considered adequate host rocks for a high-level radioactive waste deep geological repository (HLWR). Over the extended periods of HLWR operation, long-lived radionuclides (RN) may be released from the fuel and migrate to the geo/biosphere. To predict the fate of contaminants and to assess the safety of the host rock, it is very important to determine transport parameters, as diffusion coefficients, and to relate them to the physical properties of the barriers, as connected porosity. In heterogeneous materials, it is also a major task to describe the transport at the mineral scale evaluating diffusion coefficients and mineral-specific porosities on single minerals. The main objective of this study was to determine within granite and consolidated clay, the connective porosity and mineral-specific porosities by poly-methylmethacrylate (PMMA) autoradiography method. Scanning electron microscopy and energy-dispersive X-ray analyses (FESEM/EDS) were performed in order to study the pore apertures of porous regions in greater detail and to identify the corresponding minerals. By the novel application of the nuclear ion beam technique Rutherford Backscattering Spectrometry (RBS) apparent diffusion coefficients were determined at mineral scale. Finally, the porosity results were used to evaluate the effective diffusion coefficients and retention parameters of single minerals in different granite samples and consolidated clays. (Author) 42 refs.

TG-FTIR analysis of biomass pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Bassilakis, R.; Carangelo, R.M.; Wojtowicz, M.A. [Advanced Fuel Research Inc., Hartford, CT (United States)

2001-10-09

A great need exists for comprehensive biomass-pyrolysis models that could predict yields and evolution patterns of selected volatile products as a function of feedstock characteristics and process conditions. A thermogravimetric analyzer coupled with Fourier transform infrared analysis of evolving products (TG-FTIR) can provide useful input to such models in the form of kinetic information obtained under low heating rate conditions. In this work, robust TG-FTIR quantification routes were developed for infrared analysis of volatile products relevant to biomass pyrolysis. The analysis was applied to wheat straw, three types of tobacco (Burley, Oriental, and Bright) and three biomass model compounds (xylan, chlorogenic acid, and D-glucose). Product yields were compared with literature data, and species potentially quantifiable by FT-IR are reviewed. Product-evolution patterns are reported for all seven biomass samples. 41 refs., 7 figs., 2 tabs.

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Pyrolysis of Medium Density Fiberboard (MDF) wastes in a screw reactor

International Nuclear Information System (INIS)

Ferreira, Suelem Daiane; Altafini, Carlos Roberto; Perondi, Daniele; Godinho, Marcelo

2015-01-01

Highlights: • Medium Density Fiberboard wastes were pirolized in an auger reactor. • Experiments were carried out at two reaction temperatures and three solid residence times. • Yields were influenced by pyrolysis temperature, as well as by solid residence time. • Higher temperature produced more bio-oil rather than char generation. • Chars superficial area were compatibles with those of commercial activated carbons. - Abstract: Medium Density Fiberboard (MDF) wastes were undergoes via a thermal treatment through of a pyrolysis process. Pyrolysis was carried out in a pilot scale reactor with screw conveyor at two reaction temperatures (450 and 600 °C) and, for each one, three solid residence times (9, 15 and 34 min) were evaluated. Products (char/bio-oil/fuel gas) of the pyrolysis process were characterized and quantified. Results revealed that the products yields were influenced by pyrolysis temperature, as well as by solid residence time. Char yield ranged between 17.3 and 39.7 (wt.%), the bio-oil yield ranged between 23.9 and 40.0 (wt.%), while the fuel gas yield ranged between 34.6 and 50.7 (wt.%). The samples surface area at 450 and 600 °C in 15-min residence time were surprisingly high, 415 and 593 m 2 g −1 , respectively, which are compatible with the superficial area of commercial activated carbons. Energetic efficiency of process was estimated from energetic content present in the reaction products and the energetic content of MDF wastes, and the following results were obtained: 41.4% (fuel gas), 35.5% (char) and 29.2% (bio-oil). The contribution of this work is the development of a detailed study of the MDF pyrolysis in a pilot reactor with screw conveyor that supports the biorefineries concept

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

Energy Technology Data Exchange (ETDEWEB)

Fletcher, Thomas; Pugmire, Ronald

2015-01-01

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

Estimation of risks by chemicals produced during laser pyrolysis of tissues

Science.gov (United States)

Weber, Lothar W.; Spleiss, Martin

1995-01-01

Use of laser systems in minimal invasive surgery results in formation of laser aerosol with volatile organic compounds of possible health risk. By use of currently identified chemical substances an overview on possibly associated risks to human health is given. The class of the different identified alkylnitriles seem to be a laser specific toxicological problem. Other groups of chemicals belong to the Maillard reaction type, the fatty acid pyrolysis type, or even the thermally activated chemolysis. In relation to the available different threshold limit values the possible exposure ranges of identified substances are discussed. A rough estimation results in an exposure range of less than 1/100 for almost all substances with given human threshold limit values without regard of possible interactions. For most identified alkylnitriles, alkenes, and heterocycles no threshold limit values are given for lack of, until now, practical purposes. Pyrolysis of anaesthetized organs with isoflurane gave no hints for additional pyrolysis products by fragment interactions with resulting VOCs. Measurements of pyrolysis gases resulted in detection of small amounts of NO additionally with NO2 formation at plasma status.

Constraining the age of rock art by dating a rockfall event using sediment and rock-surface luminescence dating techniques

DEFF Research Database (Denmark)

Chapot, Melissa; Sohbati, Reza; Murray, A.S.

2012-01-01

Optically stimulated luminescence (OSL) is used to determine the age of a rockfall event that removed part of the pictograph figures at the Great Gallery rock art panel in Canyonlands National Park, Utah, USA. Analyses from the outer millimeter of the buried surface of a rockfall boulder and quartz...... rock art with a controversial and unknown origin....

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

International Nuclear Information System (INIS)

Pattiya, Adisak; Sukkasi, Sittha; Goodwin, Vituruch

2012-01-01

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

Deactivation and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes

International Nuclear Information System (INIS)

Lopez, A.; Marco, I. de; Caballero, B.M.; Adrados, A.; Laresgoiti, M.F.

2011-01-01

Highlights: → Pyrolysis transforms plastic wastes in valuable liquids and gases useful as fuels or source of chemicals. → The use of ZSM-5 zeolite in pyrolysis favours the production of gases and of lighter and more aromatic liquids. → ZSM-5 zeolite is almost completely deactivated after one plastics pyrolysis experiment. → ZSM-5 zeolite used in plastic wastes pyrolysis can be regenerated by burning the deposited coke in an air stream. → Regenerated ZSM-5 recovers its activity and produces liquids and gases equivalent to those obtained with fresh catalyst. - Abstract: In this work, a study of the regeneration and reuse of ZSM-5 zeolite in the pyrolysis of a plastic mixture has been carried out in a semi-batch reactor at 440 deg. C. The results have been compared with those obtained with fresh-catalyst and in non-catalytic experiments with the same conditions. The use of fresh catalyst produces a significant change in both the pyrolysis yields and the properties of the liquids and gases obtained. Gases more rich in C3-C4 and H 2 are produced, as well as lower quantities of aromatic liquids if compared with those obtained in thermal decomposition. The authors have proved that after one pyrolysis experiment the zeolite loses quite a lot of its activity, which is reflected in both the yields and the products quality; however, this deactivation was found to be reversible since after regeneration heating at 550 deg. C in oxygen atmosphere, this catalyst recovered its initial activity, generating similar products and in equivalent proportions as those obtained with fresh catalyst.

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

Science.gov (United States)

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

2018-05-01

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

CHARACTERISTICS OF CORN STALK HEMICELLULOSE PYROLYSIS IN A TUBULAR REACTOR

OpenAIRE

Gao-Jin Lv; Shu-Bin Wu; Rui Lou

2010-01-01

Pyrolysis characteristics of corn stalk hemicellulose were investigated in a tubular reactor at different temperatures, with focus mainly on the releasing profiles and forming behaviors of pyrolysis products (gas, char, and tar). The products obtained were further identified using various approaches (including GC, SEM, and GC-MS) to understand the influence of temperature on product properties and compositions. It was found that the devolatilization of hemicellulose mainly occurred at low tem...

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

Science.gov (United States)

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.

Catalytic hydrotreatment of pyrolysis liquids and fractions : Catalyst Development and Process Studies

NARCIS (Netherlands)

Yin, Wang

2017-01-01

The use of sustainable and renewable lignocellulosic biomass is of particular interest to (partly) replace fossil resources. Fast pyrolysis is a promising technology to convert lignocellulosic biomass to a liquid energy carrier. The products, also known as fast pyrolysis liquids (PLs), have a higher

Production of Lunar Oxygen Through Vacuum Pyrolysis

National Research Council Canada - National Science Library

Matchett, John

2006-01-01

.... The vacuum pyrolysis method of oxygen production from lunar regolith presents a viable option for in situ propellant production because of its simple operation involving limited resources from earth...

Catalytic pyrolysis of Laminaria japonica over nanoporous catalysts using Py-GC/MS

Directory of Open Access Journals (Sweden)

Jeon Jong-Ki

2011-01-01

Full Text Available Abstract The catalytic pyrolysis of Laminaria japonica was carried out over a hierarchical meso-MFI zeolite (Meso-MFI and nanoporous Al-MCM-48 using pyrolysis gas chromatography/mass spectrometry (Py-GC/MS. The effect of the catalyst type on the product distribution and chemical composition of the bio-oil was examined using Py-GC/MS. The Meso-MFI exhibited a higher activity in deoxygenation and aromatization during the catalytic pyrolysis of L. japonica. Meanwhile, the catalytic activity of Al-MCM-48 was lower than that of Meso-MFI due to its weak acidity.

Characterization of Hydrotreated Fast Pyrolysis Liquids

NARCIS (Netherlands)

Oasmaa, A.; Kuoppala, E.; Ardiyanti, A.; Venderbosch, R. H.; Heeres, H. J.

This paper focuses on analytical methods to determine the composition of hydrotreated fast pyrolysis liquids. With this information, it is possible to gain insights in the chemical transformations taking place during catalytic hydrotreatment (hydrogenation and/or hydrodeoxygenation, H DO) of

High-pressure pyrolysis and oxidation of ethanol

DEFF Research Database (Denmark)

Hashemi, Hamid; Christensen, Jakob M.; Glarborg, Peter

2018-01-01

against the present data as well as ignition delay times and flame speed measurements from literature. The model predicted the onset of fuel conversion and the composition of products from the flow reactor experiments fairly well. It also predicted well ignition delays above 900 K whereas it overpredicted...... reported flame speeds slightly. The results of sensitivity analyses revealed the importance of the reaction between ethanol and the hydroperoxyl radical for ignition at high pressure and intermediate temperatures. An accurate determination of the rate coefficients for this reaction is important to improve......The pyrolysis and oxidation of ethanol has been investigated at temperatures of 600–900 K, a pressure of 50 bar and residence times of 4.3–6.8 s in a laminar flow reactor. The experiments, conducted with mixtures highly diluted in nitrogen, covered fuel-air equivalence ratios (Φ) of 0.1, 1.0, 43...

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-10-03

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

A Comparison of Flame Spread Characteristics over Solids in Concurrent Flow Using Two Different Pyrolysis Models

Directory of Open Access Journals (Sweden)

Ya-Ting Tseng

2011-01-01

Full Text Available Two solid pyrolysis models are employed in a concurrent-flow flame spread model to compare the flame structure and spreading characteristics. The first is a zeroth-order surface pyrolysis, and the second is a first-order in-depth pyrolysis. Comparisons are made for samples when the spread rate reaches a steady value and the flame reaches a constant length. The computed results show (1 the mass burning rate distributions at the solid surface are qualitatively different near the flame (pyrolysis base region, (2 the first-order pyrolysis model shows that the propagating flame leaves unburnt solid fuel, and (3 the flame length and spread rate dependence on sample thickness are different for the two cases.

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

NARCIS (Netherlands)

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

2014-01-01

Performance of a novel alumina-supported sodium carbonate catalyst was studied to produce a valuable bio-oil from catalytic flash pyrolysis of lignocellulosic biomass. Post treatment of biomass pyrolysis vapor was investigated in a catalyst fixed bed reactor at the downstream of the pyrolysis

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

KAUST Repository

Imran, Ali

2014-11-01

Performance of a novel alumina-supported sodium carbonate catalyst was studied to produce a valuable bio-oil from catalytic flash pyrolysis of lignocellulosic biomass. Post treatment of biomass pyrolysis vapor was investigated in a catalyst fixed bed reactor at the downstream of the pyrolysis reactor. In-situ catalytic upgrading of biomass pyrolysis vapor was conducted in an entrained flow pyrolysis reactor by feeding a premixed feedstock of the catalyst and biomass. Na2CO3/gamma-Al2O3 was very effective for de-oxygenation of the pyrolysis liquid and oxygen content of the bio-oil was decreased from 47.5 wt.% to 16.4 wt.%. An organic rich bio-oil was obtained with 5.8 wt.% water content and a higher heating value of 36.1 MJ/kg. Carboxylic acids were completely removed and the bio-oil had almost a neutral pH. This bio-oil of high calorific low, low water and oxygen content may be an attractive fuel precursor. In-situ catalytic upgrading of biomass pyrolysis vapor produced a very similar quality bio-oil compared to post treatment of pyrolysis vapors, and shows the possible application of Na2CO3/gamma-Al2O3 in a commercial type reactor system such as a fluidized bed reactor. (C) 2014 Elsevier B.V. All rights reserved.

Back-analysing rock mass modulus from monitoring data of two tunnels in Sydney, Australia

Directory of Open Access Journals (Sweden)

Robert Bertuzzi

2017-10-01

Full Text Available This paper presents two case studies where the rock mass modulus and in situ stress are estimated from the monitoring data obtained during the construction of underground excavations in Sydney, Australia. The case studies comprise the widening of existing twin road tunnels within Hawkesbury sandstone and the excavation of a large cavern within Ashfield shale. While back-analysis from detailed systematic monitoring has been previously published, this paper presents a relatively simple methodology to derive rock mass modulus and in situ stress from the relatively simple displacement data routinely recorded during tunnelling.

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

Science.gov (United States)

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

Slow and pressurized co-pyrolysis of coal and agricultural residues

International Nuclear Information System (INIS)

Aboyade, Akinwale O.; Carrier, Marion; Meyer, Edson L.; Knoetze, Hansie; Görgens, Johann F.

2013-01-01

Highlights: ► Evaluation of co-pyrolysis of coal and biomass in pressurized packed bed reactor. ► Relative influence of coal–biomass mix ratio, temperature and pressure also investigated. ► Results show significant synergy or chemical interactions in the vapor phase. ► Synergistic interactions did not influence distribution of lumped solid liquid and gas products. - Abstract: The distribution of products from the slow heating rate pyrolysis of coal, corn residues (cobs and stover), sugarcane bagasse and their blends were investigated by slow pressurized pyrolysis in a packed bed reactor. A factorial experimental design was implemented to establish the relative significance of coal–biomass mix ratio, temperature and pressure on product distribution. Results showed that the yield and composition of tar and other volatile products were mostly influenced by mix ratio, while temperature and pressure had a low to negligible significance under the range of conditions investigated. Analysis of the composition of condensates and gas products obtained showed that there was significant synergy or chemical interactions in the vapor phase during co-pyrolysis of coal and biomass. However, the interactions did not significantly affect the relative distribution of the lumped solid, liquid and gas products obtained from the blends, beyond what would be expected assuming additive behavior from the contributing fuels.

Thermogravimetric-Mass Spectrometric Study of the Pyrolysis Behavior of PVC

Institute of Scientific and Technical Information of China (English)

SUN Qing-lei; SHI Xin-gang; LIN Yun-liang; ZHU He; WANG Xiao; CHENG Chuan-ge; LIU Jian-hua

2007-01-01

The pyrolysis characteristics of PVC were systematically investigated using a Netzschne TG thermo-balance coupled to a quadrupole mass spectrometer. The pyrolysis conditions were 0.1 MPa of Ar, a heating rate of 10 ℃/min and a final temperature of 1000 ℃. Both the thermogravimetric properties and the simultaneous evolution of gaseous products during pyrolysis were studied. The TG/DTG results showed that as the pyrolysis temperature increases the weight loss and weight loss rate of PVC increases. Near 412 ℃ the weight loss rate attained its peak value. At higher temperatures the rate of loss gradually decreases. The gases evolved during thermogravimetric analysis were analyzed by a mass spectrometer, monitoring the relative intensity of HCl, C6H6, light hydrocarbon and chlorine-containing gases. The evolution curves showed that HCl, C6H6, light hydrocarbon and chlorine-containing gases all peak at about 416 ℃. This is consistent with the fact that the weight loss curves also peak at about 412 ℃. The extensive HCl evolution is consistent with the high chlorine content of PVC. The formation of these gases can be explained by considering these reactions: dehydrochlorination, intramolecular cyclization and the addition of HCl to unsaturated hydrocarbons.

Production and characterization of bio-oil from catalytic biomass pyrolysis

Directory of Open Access Journals (Sweden)

Antonakou Eleni V.

2006-01-01

Full Text Available Biomass flash pyrolysis is a very promising thermochemical process for the production of bio-fuels and/or chemicals. However, large-scale applications are still under careful consideration, because of the high bio-liquid upgrading cost. In this paper the production of bio-liquids from biomass flash pyrolysis in a single stage catalytic process is being investigated using a novel once through fluid bed reactor. This biomass pyrolysis unit was constructed in Chemical Process Engineering Research Institute and comprises of a catalyst regenerator, a biomass-vibrating hopper, a fluidization reactor (that consists of an injector and a riser reactor, a product stripper along with a hot cyclone and a filter housing and finally a product condensation/recovery section. The unit can process up to 20 g/min. of biomass (50-800 mm and can circulate up to 300 g/min. of catalyst or inert material. The experiments performed in the pilot plant showed that the unit operates without problems and with satisfactory mass balances in a wide range of experimental conditions both in the absence and presence of catalyst. With the incorporation of an FCC catalyst in the pyrolysis, the physical properties of the bio-oil produced changed, while more stable bio-oil was produced. .

Production of activated carbon by using pyrolysis process in an ammonia atmosphere

Science.gov (United States)

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.

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

Science.gov (United States)

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

2015-02-01

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

Pyrolysis of olive residue/low density polyethylene mixture:Part I Thermogravimetric kinetics

Institute of Scientific and Technical Information of China (English)

无

2008-01-01

This paper demonstrates the thermal pyrolysis of olive residue, low density polyethylene (LDPE) and olive residue/LDPE mixture in an inert atmosphere of N2 using thermogravimetric analysis (TGA). Measurements were carried out in the temperature range 300K~973K at heating rates of 2K/min, 10K/min, 20K/min and 50K/min. Based on the results obtained, three temperature regimes were selected for studying the non-isothermal kinetics of olive residue/LDPE mixture. The first two were dominated by the olive residue pyrolysis, while the third was linked to the LDPE pyrolysis, which occurred at much higher temperatures. Discrepancies between the experimental and calculated TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. The maximum degradation temperatures of each component in the mixture were higher than those the individual components;thus an increase in thermal stability was expected. The kinetic parameters associated with thermal degradation were determined using Friedman isoconversional method.

Five Years of Analyses of Volatiles, Isotopes and Organics in Gale Crater Materials

Science.gov (United States)

McAdam, A.; Mahaffy, P. R.; Andrejkovicova, S. C.; Archer, P. D., Jr.; Atreya, S. K.; Buch, A.; Coll, P. J.; Conrad, P. G.; Eigenbrode, J. L.; Farley, K. A.; Flesch, G.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Hogancamp, J. V.; House, C. H.; Knudson, C. A.; Lewis, J. M.; Malespin, C.; Martin, P. M.; Millan, M.; Ming, D. W.; Morris, R. V.; Navarro-Gonzalez, R.; Steele, A.; Stern, J. C.; Summons, R. E.; Sutter, B.; Szopa, C.; Teinturier, S.; Trainer, M. G.; Webster, C. R.; Wong, G. M.

2017-12-01

Over the last five years, the Curiosity rover has explored a variety of fluvial, lacustrine and aeolian sedimentary rocks, and soils. The Sample Analysis at Mars (SAM) instrument has analysed 3 soil and 12 rock samples, which exhibit significant chemical and mineralogical diversity in over 200 meters of vertical section. Here we will highlight several key insights enabled by recent measurements of the chemical and isotopic composition of inorganic volatiles and organic compounds detected in Gale Crater materials. Until recently samples have evolved O2 during SAM evolved gas analyses (EGA), attributed to the thermal decomposition of oxychlorine phases. A lack of O2 evolution from recent mudstone samples may indicate a difference in the composition of depositional or diagenetic fluids, and can also have implications for the detection of organic compounds since O2 can combust organics to CO2 in the SAM ovens. Recent mudstone samples have also shown little or no evolution of NO attributable to nitrate salts, possibly also as a result of changes in the chemical composition of fluids [1]. Measurements of the isotopic composition of sulfur, hydrogen, nitrogen, chlorine, and carbon in methane evolved during SAM pyrolysis are providing constraints on the conditions of possible paleoenvironments [e.g., 2, 3]. There is evidence of organic C from both EGA and GCMS measurements of Gale samples [e.g., 4, 5]. Organic sulfur volatiles have been detected in several samples, and the first opportunistic derivatization experiment produced a rich dataset indicating the presence of several organic compounds [6, 7]. A K-Ar age has been obtained from the Mojave mudstone, and the age of secondary materials formed by aqueous alteration is likely history and habitability. [1] Sutter et al. (2017) LPSC 3009. [2] Franz et al., this mtg. [3] Stern et al., this mtg. [4] Ming et al. (2014) Science 343. [5] Freissinet et al. (2015) JGR 120. [6] Eigenbrode et al. (2016) AGU P21D-08. [7] Freissinet

Rock slope instabilities in Norway: First systematic hazard and risk classification of 22 unstable rock slopes

Science.gov (United States)

Böhme, Martina; Hermanns, Reginald L.; Oppikofer, Thierry; Penna, Ivanna

2016-04-01

Unstable rock slopes that can cause large failures of the rock-avalanche type have been mapped in Norway for almost two decades. Four sites have earlier been characterized as high-risk objects based on expertise of few researchers. This resulted in installing continuous monitoring systems and set-up of an early-warning system for those four sites. Other unstable rock slopes have not been ranked related to their hazard or risk. There are ca. 300 other sites known of which 70 sites were installed for periodic deformation measurements using multiple techniques (Global Navigation Satellite Systems, extensometers, measurement bolts, and others). In 2012 a systematic hazard and risk classification system for unstable rock slopes was established in Norway and the mapping approach adapted to that in 2013. Now, the first 22 sites were classified for hazard, consequences and risk using this classification system. The selection of the first group of sites to be classified was based on an assumed high hazard or risk and importance given to the sites by Norwegian media and the public. Nine of the classified 22 unstable rock slopes are large sites that deform inhomogeneously or are strongly broken up in individual blocks. This suggests that different failure scenarios are possible that need to be analyzed individually. A total of 35 failure scenarios for those nine unstable rock slopes were considered. The hazard analyses were based on 9 geological parameters defined in the classification system. The classification system will be presented based on the Gamanjunni unstable rock slope. This slope has a well developed back scarp that exposes 150 m preceding displacement. The lateral limits of the unstable slope are clearly visible in the morphology and InSAR displacement data. There have been no single structures observed that allow sliding kinematically. The lower extend of the displacing rock mass is clearly defined in InSAR data and by a zone of higher rock fall activity. Yearly

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

Science.gov (United States)

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.

Effects of heating rate on slow pyrolysis behavior, kinetic parameters and products properties of moso bamboo.

Science.gov (United States)

Chen, Dengyu; Zhou, Jianbin; Zhang, Qisheng

2014-10-01

Effects of heating rate on slow pyrolysis behaviors, kinetic parameters, and products properties of moso bamboo were investigated in this study. Pyrolysis experiments were performed up to 700 °C at heating rates of 5, 10, 20, and 30 °C/min using thermogravimetric analysis (TGA) and a lab-scale fixed bed pyrolysis reactor. The results show that the onset and offset temperatures of the main devolatilization stage of thermogravimetry/derivative thermogravimetry (TG/DTG) curves obviously shift toward the high-temperature range, and the activation energy values increase with increasing heating rate. The heating rate has different effects on the pyrolysis products properties, including biochar (element content, proximate analysis, specific surface area, heating value), bio-oil (water content, chemical composition), and non-condensable gas. The solid yields from the fixed bed pyrolysis reactor are noticeably different from those of TGA mainly because the thermal hysteresis of the sample in the fixed bed pyrolysis reactor is more thorough. Copyright © 2014 Elsevier Ltd. All rights reserved.

Measurements of temperature of the tungsten hexa-ethoxide pyrolysis flame using IR camera

CSIR Research Space (South Africa)

Mudau, AE

2010-09-01

Full Text Available In laser pyrolysis, temperature measurement and control plays a vital role during the development of nanoparticles. Authors present the results of temperature measurements using infrared camera on a tungsten hexa-ethoxide pyrolysis flame used...

The release of nitrogen in coal combustion and pyrolysis

International Nuclear Information System (INIS)

Varey, J.E.; Hindmarsh, C.J.; Thomas, K.M.

1994-01-01

Environmental aspects of coal utilization are a major concern. Recent advances in the development of low NO x burners and the emerging technologies of fluidized bed combustion have led to the identification of coal char nitrogen as the major contributor to the nitrogen oxides released during combustion. The temperature programmed combustion and pyrolysis of a series of coals covering a wide range of rank have been investigated. In addition, maceral concentrates have been investigated to assess the variation in the combustion behavior and the release of nitrogen in the pyrolysis and combustion of macerals. This investigation has involved the use of thermogravimetric analysis - mass spectrometry (TG-MS) with two sampling options: (1) ∼1cm from the sample and (2) at the exit of the TG. The former allows reactive species to be identified in the combustion of the coals. These temperature programmed combustion results have been compared with similar measurements carried out at the exit of the TG where the products are at equilibrium. In addition, pyrolysis studies have been carried out under similar conditions. The results show that reactive intermediate species such as HCN, (CN) 2 , COS etc. can be detected in the combustion products. The evolution of these species during combustion are compared with the pyrolysis products of the coal. The results are discussed in relation to the structure of the coals and the conversion of volatile species and char nitrogen to nitrogen oxides

Experimental investigation of flash pyrolysis oil droplet combustion

DEFF Research Database (Denmark)

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

2013-01-01

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

Kinetic Study on Pyrolysis of Oil Palm Frond

International Nuclear Information System (INIS)

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

2016-01-01

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

Pyrolysis and Gasification Kinetics of Large Biomass Particles

Energy Technology Data Exchange (ETDEWEB)

Svenson, Jenny; Hagstroem, Magnus; Andersson, Patrik U.; Loenn, Benny; Pettersson, Jan B.C. [Goteborg Univ. (Sweden). Dep. of Chemistry, Atmospheric Science; Davidsson, Kent O. [Chalmers Univ. of Technology, Goeteborg (Sweden). Energy Conversion

2004-05-01

The aim of the project is to provide experimental data on single biomass particle pyrolysis that have an applied as well as a fundamental bearing. Transport phenomena and kinetics on the single particle level are characterized, including heat and mass transport processes. New experimental techniques and methods are applied and developed within the project. A single-particle reactor has been developed for the investigations, and several detection techniques including fast thermogravimetric analysis, molecular beam mass spectrometry, laser spectroscopy, video recording and pyrometry are applied. The experimental data are used to develop robust models for pyrolysis and gasification, which are essential components in the design of gasification and combustion reactors.

Life Cycle Assessment of Gasoline and Diesel Produced via Fast Pyrolysis and Hydroprocessing

Energy Technology Data Exchange (ETDEWEB)

Hsu, D. D.

2011-03-01

In this work, a life cycle assessment (LCA) estimating greenhouse gas (GHG) emissions and net energy value (NEV) of the production of gasoline and diesel from forest residues via fast pyrolysis and hydroprocessing, from production of the feedstock to end use of the fuel in a vehicle, is performed. The fast pyrolysis and hydrotreating and hydrocracking processes are based on a Pacific Northwest National Laboratory (PNNL) design report. The LCA results show GHG emissions of 0.142 kg CO2-equiv. per km traveled and NEV of 1.00 MJ per km traveled for a process using grid electricity. Monte Carlo uncertainty analysis shows a range of results, with all values better than those of conventional gasoline in 2005. Results for GHG emissions and NEV of gasoline and diesel from pyrolysis are also reported on a per MJ fuel basis for comparison with ethanol produced via gasification. Although pyrolysis-derived gasoline and diesel have lower GHG emissions and higher NEV than conventional gasoline does in 2005, they underperform ethanol produced via gasification from the same feedstock. GHG emissions for pyrolysis could be lowered further if electricity and hydrogen are produced from biomass instead of from fossil sources.

Jobs and Economic Development Impact (JEDI) User Reference Guide: Fast Pyrolysis Biorefinery Model

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yimin [National Renewable Energy Lab. (NREL), Golden, CO (United States); Goldberg, Marshall [MRG and Associates, Nevada City, CA (United States)

2015-02-01

This guide -- the JEDI Fast Pyrolysis Biorefinery Model User Reference Guide -- was developed to assist users in operating and understanding the JEDI Fast Pyrolysis Biorefinery Model. The guide provides information on the model's underlying methodology, as well as the parameters and data sources used to develop the cost data utilized in the model. This guide also provides basic instruction on model add-in features and a discussion of how the results should be interpreted. Based on project-specific inputs from the user, the JEDI Fast Pyrolysis Biorefinery Model estimates local (e.g., county- or state-level) job creation, earnings, and output from total economic activity for a given fast pyrolysis biorefinery. These estimates include the direct, indirect and induced economic impacts to the local economy associated with the construction and operation phases of biorefinery projects.Local revenue and supply chain impacts as well as induced impacts are estimated using economic multipliers derived from the IMPLAN software program. By determining the local economic impacts and job creation for a proposed biorefinery, the JEDI Fast Pyrolysis Biorefinery Model can be used to field questions about the added value biorefineries might bring to a local community.

Hydrodeoxygenation of pyrolysis oil fractions: process understanding and quality assessment through co-processing in refinery units

NARCIS (Netherlands)

De Miguel Mercader, F.; de Miguel Mercader, Ferran; Groeneveld, M.J.; Kersten, Sascha R.A.; Geantet, Christophe; Toussaint, Guy; Way, Nico W.J.; Schaverien, Colin J.; Hogendoorn, Kees

2011-01-01

Hydrodeoxygenation (HDO) of pyrolysis oil fractions was studied to better understand the HDO of whole pyrolysis oil and to assess the possibility to use individual upgrading routes for these fractions. By mixing pyrolysis oil and water in a 2:1 weight ratio, two fractions were obtained: an oil

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

Science.gov (United States)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

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

Directory of Open Access Journals (Sweden)

Phil Badger

2011-02-01

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

Application of multivariate statistical analyses in the interpretation of geochemical behaviour of uranium in phosphatic rocks in the Red Sea, Nile Valley and Western Desert, Egypt

International Nuclear Information System (INIS)

El-Arabi, A.M.Abd El-Gabar M.; Khalifa, Ibrahim H.

2002-01-01

Factor and cluster analyses as well as the Pearson correlation coefficient have been applied to geochemical data obtained from phosphorite and phosphatic rocks of Duwi Formation exposed at the Red Sea coast, Nile Valley and Western Desert. Sixty-six samples from a total of 71 collected samples were analysed for SiO 2 , TiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO, MgO, Na 2 O, K 2 O, P 2 O 5 , Sr, U and Pb by XRF and their mineral constituents were determined by the use of XRD techniques. In addition, the natural radioactivity of the phosphatic samples due to their uranium, thorium and potassium contents was measured by gamma-spectrometry.The uranium content in the phosphate rocks with P 2 O 5 >15% (average of 106.6 ppm) is higher than in rocks with P 2 O 5 2 O 5 and CaO, whereas it is not related to changes in SiO 2 , TiO 2 , Al 2 O 3 , Fe 2 O 3 , MgO, Na 2 O and K 2 O concentrations.Factor analysis and the Pearson correlation coefficient revealed that uranium behaves geochemically in different ways in the phosphatic sediments and phosphorites in the Red Sea, Nile Valley and Western Desert. In the Red Sea and Western Desert phosphorites, uranium occurs mainly in oxidized U 6+ state where it seems to be fixed by the phosphate ion, forming secondary uranium phosphate minerals such as phosphuranylite.In the Nile Valley phosphorites, ionic substitution of Ca 2+ by U 4+ is the main controlling factor in the concentration of uranium in phosphate rocks. Moreover, fixation of U 6+ by phosphate ion and adsorption of uranium on phosphate minerals play subordinate roles