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Novel Fast Pyrolysis/Catalytic Technology for the Production of Stable Upgraded Liquids

Description: The objective of the proposed research is the demonstration and development of a novel biomass pyrolysis technology for the production of a stable bio-oil. The approach is to carry out catalytic hydrodeoxygenation (HDO) and upgrading together with pyrolysis in a single fluidized bed reactor with a unique two-level design that permits the physical separation of the two processes. The hydrogen required for the HDO will be generated in the catalytic section by the water-gas shift reaction employing recycled CO produced from the pyrolysis reaction itself. Thus, the use of a reactive recycle stream is another innovation in this technology. The catalysts will be designed in collaboration with BASF Catalysts LLC (formerly Engelhard Corporation), a leader in the manufacture of attrition-resistant cracking catalysts. The proposed work will include reactor modeling with state-of-the-art computational fluid dynamics in a supercomputer, and advanced kinetic analysis for optimization of bio-oil production. The stability of the bio-oil will be determined by viscosity, oxygen content, and acidity determinations in real and accelerated measurements. A multi-faceted team has been assembled to handle laboratory demonstration studies and computational analysis for optimization and scaleup.
Date: January 18, 2013
Creator: Ted Oyama, Foster Agblevor, Francine Battaglia, Michael Klein
Partner: UNT Libraries Government Documents Department

Ex-Situ Catalytic Fast Pyrolysis Technology Pathway

Description: In support of the Bioenergy Technologies Office, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) are undertaking studies of biomass conversion technologies to hydrocarbon fuels to identify barriers and target research toward reducing conversion costs. Process designs and preliminary economic estimates for each of these pathway cases were developed using rigorous modeling tools (Aspen Plus and Chemcad). These analyses incorporated the best information available at the time of development, including data from recent pilot and bench-scale demonstrations, collaborative industrial and academic partners, and published literature and patents. This pathway case investigates converting woody biomass using ex-situ catalytic fast pyrolysis followed by upgrading to gasoline , diesel and jet range blendstocks . Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.
Date: March 31, 2013
Creator: Biddy, Mary J.; Dutta, Abhijit; Jones, Susanne B. & Meyer, Pimphan A.
Partner: UNT Libraries Government Documents Department

Microstructure and Electronic Structures of Er-Doped Si Nano-particles Synthesized by Vapor Phase Pyrolysis

Description: Si nanoparticles are new prospective optoelectronic materials. Unlike bulk Si cry-stals, Si nanoparticles display intriguing room-temperature photoluminescence. A major challenge in the fabrication of Si nanoparticles is the control of their size distribution. The rare-earth element Er has unique photo emission properties, including low pumping power, and a temperature independent, sharp spectrum. The emission wavelength matches the transmission window of optical fibers used in the telecommunications industry. Therefore, the study of Er-doped Si nanoparticles may have practical significance. The goals of the research described in this dissertation are to investigate vapor phase pyrolysis methods and to characterize the microstructure and associated defects, particles size distributions and photoluminescence efficiencies of doped and undoped Si nanoparticles using analytical transmission electron microscopy, high resolution electron microscopy, and optical spectroscopy. Er-doped and undoped Si nanoparticles were synthesized via vapor-phase pyrolysis of disilane at Texas Christian University. To achieve monodisperse size distributions, a process with fast nucleation and slow growth was employed. Disilane was diluted to 0.48% with helium. A horizontal pyrolysis oven was maintained at a temperature of 1000 °C. The oven length was varied from 1.5 cm to 6.0 cm to investigate the influence of oven length on the properties of the nanoparticles. The Si nanoparticles were collected in ethylene-glycol. The doped and undoped Si nanoparticles have a Si diamond cubic crystal structure. Neither Er precipitation, Er oxides or Er silicides were detected in any of the samples. The Er dopant concentration was about 2 atom% for doped samples from the 3.0 and 6.0 cm ovens as determined by quantitative analysis using X-ray energy dispersive spectroscopy. The average Si nanoparticle size increases from 11.3 to 15.2 nm in the doped samples and from 11.1 to 15.7 nm in the undoped samples as the oven length increases from 1.5 to 6.0 cm. HREM data ...
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Date: May 2000
Creator: Chen, Yandong
Partner: UNT Libraries

Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels: Fast Pyrolysis and Hydrotreating Bio-Oil Pathway

Description: This report describes a proposed thermochemical process for converting biomass into liquid transportation fuels via fast pyrolysis followed by hydroprocessing of the condensed pyrolysis oil. As such, the analysis does not reflect the current state of commercially-available technology but includes advancements that are likely, and targeted to be achieved by 2017. The purpose of this study is to quantify the economic impact of individual conversion targets to allow a focused effort towards achieving cost reductions.
Date: November 1, 2013
Creator: Jones, Susanne B.; Meyer, Pimphan A.; Snowden-Swan, Lesley J.; Padmaperuma, Asanga B.; Tan, Eric; Dutta, Abhijit et al.
Partner: UNT Libraries Government Documents Department

Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: 2012 State of Technology and Projections to 2017

Description: This report summarizes the economic impact of the work performed at PNNL during FY12 to improve fast pyrolysis oil upgrading via hydrotreating. A comparison is made between the projected economic outcome and the actual results based on experimental data. Sustainability metrics are also included.
Date: August 27, 2013
Creator: Jones, Susanne B. & Snowden-Swan, Lesley J.
Partner: UNT Libraries Government Documents Department

Direct Aromaization of Methane

Description: The thermal decomposition of methane offers significant potential as a means of producing higher unsaturated and aromatic hydrocarbons when the extent of reaction is limited. Work in the literature previous to this project had shown that cooling the product and reacting gases as the reaction proceeds would significantly reduce or eliminate the formation of solid carbon or heavier (Clo+) materials. This project studied the effect and optimization of the quenching process as a means of increasing the amount of value added products during the pyrolysis of methane. A reactor was designed to rapidly quench the free-radical combustion reaction so as to maximize the yield of aromatics. The use of free-radical generators and catalysts were studied as a means of lowering the reaction temperature. A lower reaction temperature would have the benefits of more rapid quenching as well as a more feasible commercial process due to savings realized in energy and material of construction costs. It was the goal of the project to identify promising routes from methane to higher hydrocarbons based on the pyrolysis of methane.
Date: January 15, 1997
Creator: Marcelin, George
Partner: UNT Libraries Government Documents Department

The Consequences of Surface Confinement on Free Radical Chemistry

Description: Mass transport limitations impact the thermochemical processing of fossil and renewable energy resources, which involves the breakdown of cross-linked, macromolecular networks. To Investigate the molecular level details of the consequences of molecular confinement on high temperature (275-500°C) free-radical reaction pathways, we have been examining the pyrolysis of model compounds attached to the surface of non-porous silica nanoparticles through a thermally robust Si-O-C<sub>aryl</sub>, tetha. Pyrolysis of silica-immobilized diphenylalkanes and related ethers have been studied in detail and compared with the corresponding behavior in fluid phases. The diffusional constraints can lead to reduced rates of radical termination on the surface, and enhancement of neophyl-like rearrangements, cyclization-dehydrogenation pathways, and <i>ipso-</i> aromatic substitutions. Furthermore, studies of two-component surfaces have revealed the importance of a radical relay mechanism involving rapid serial hydrogen transfer steps resulting from the molecular pre-organization on the low fractal dimension silica surface. Key findings are reviewed in this paper, and the implications of these results for fuel processing are described.
Date: August 22, 1999
Creator: Birtt, P.F. & Buchanan, A.C., III
Partner: UNT Libraries Government Documents Department

Entrained-Flow, Fast Ablative Pyrolysis of Biomass - Annual Report, 1 December 1984 - 31 December 1985

Description: The ablative, fast pyrolysis system was relocated to SERI's new, permanent Field Test Laboratory. Pyrolysis system modifications were made to increase the energy available to the vortex reactor and to enhance the collection efficiency of primary pyrolysis vapors. Mathematical modeling of the vapor cracker has resulted in the ability to accurately predict experimental results with respect to the thermal cracking of the primary vapors, the generation of noncondensible gases, and the gas composition. The computer algorithm of this model can be readily used to perform experimental simulation and/or reactor scale-up due to its fundamental nature. Preliminary screening tests with pure ZSM-5 zeolite catalyst, supplied by Mobil Research and Development Corporation, have shown promise for the conversion of primary pyrolysis oil vapors to aromatic hydrocarbons; i.e., gasoline.
Date: July 1, 1986
Creator: Diebold, J. P.; Scahill, J. W. & Evans, R. J.
Partner: UNT Libraries Government Documents Department

In-Situ Catalytic Fast Pyrolysis Technology Pathway

Description: In support of the Bioenergy Technologies Office, the National Renewable Energy Laboratory (NREL) and the Pacific Northwest National Laboratory (PNNL) are undertaking studies of biomass conversion technologies to hydrocarbon fuels to identify barriers and target research toward reducing conversion costs. Process designs and preliminary economic estimates for each of these pathway cases were developed using rigorous modeling tools (Aspen Plus and Chemcad). These analyses incorporated the best information available at the time of development, including data from recent pilot and bench-scale demonstrations, collaborative industrial and academic partners, and published literature and patents. This pathway case investigates converting woody biomass using in-situ catalytic fast pyrolysis followed by upgrading to gasoline, diesel, and jet range blendstocks. Technical barriers and key research needs that should be pursued for this pathway to be competitive with petroleum-derived blendstocks have been identified.
Date: March 31, 2013
Creator: Biddy, Mary J.; Dutta, Abhijit; Jones, Susanne B. & Meyer, Pimphan A.
Partner: UNT Libraries Government Documents Department

The thermal decomposition behavior of ammonium perchlorate and of an ammonium-perchlorate-based composite propellant

Description: The thermal decomposition of ammonium perchlorate (AP) and ammonium-perchlorate-based composite propellants is studied using the simultaneous thermogravimetric modulated beam mass spectrometry (STMBMS) technique. The main objective of the present work is to evaluate whether the STMBMS can provide new data on these materials that will have sufficient detail on the reaction mechanisms and associated reaction kinetics to permit creation of a detailed model of the thermal decomposition process. Such a model is a necessary ingredient to engineering models of ignition and slow-cookoff for these AP-based composite propellants. Results show that the decomposition of pure AP is controlled by two processes. One occurs at lower temperatures (240 to 270 C), produces mainly H{sub 2}O, O{sub 2}, Cl{sub 2}, N{sub 2}O and HCl, and is shown to occur in the solid phase within the AP particles. 200{micro} diameter AP particles undergo 25% decomposition in the solid phase, whereas 20{micro} diameter AP particles undergo only 13% decomposition. The second process is dissociative sublimation of AP to NH{sub 3} + HClO{sub 4} followed by the decomposition of, and reaction between, these two products in the gas phase. The dissociative sublimation process occurs over the entire temperature range of AP decomposition, but only becomes dominant at temperatures above those for the solid-phase decomposition. AP-based composite propellants are used extensively in both small tactical rocket motors and large strategic rocket systems.
Date: March 24, 1998
Creator: Behrens, R. & Minier, L.
Partner: UNT Libraries Government Documents Department

Pyrolysis Capillary Chromatography of Refuse-Derived Fuel and Aquatic Fulvic Acids

Description: Pyrolysis-capillary gas chromatography combined with FID, ECD and MS detection were used to characterize refuse-derived fuel and aquatic fulvic acids. Different pyrolysis methods and programs were evaluated. Pyrolysis temperatures of 700-800°C produced the strongest signal for organics present in RDF and fulvic acid. Cellulose and fatty acids pyrolyzates were identifiable by GC-MS following preparative pyrolysis fractionation. At organic chloride content of 0.023%, only three halogenated compounds were detected in the GC-MS of the fractions. None of the priority pollutants were detected at lower detection limit of 0.72 to 24 mg/ kg RDF. Selective solvent extraction improves the reproduciblities of the technique and allows the detection of polymeric structures. Pyrograms of polyvinyl chloride and regular typing paper showed some common peaks that are present in the RDF pyrogram. About 65% of the peaks in the RDF pyrogram might be of paper origin. The organic chloride content of the RDF was evaluated by ion chromatography of the trapped pyrolyzates in 2% NaOH trap and it was found to be 221 mg Cl/ kg dry RDF. Pyrolysis conditions and temperature programs for FA were systematically evaluated. Samples included purified FA, methylated FA and HPLC separated fractions. Characteristic pyrograms were developed. Profiles of benzene, toluene, phenol, m-cresol and biphenyl from FA were evaluated. The production of phenol was the largest at 800°C, at concentration of 1.61 mg per gram of FA pyrolyzed. The profiles of benzene and toluene followed the same pathways. Both pyrolyzates had at least two precursors. HPLC fractions of FA showed some regular retention patterns characteristic of polymeric material. DL-proline, seriene and vanillic acid pyrograms showed some peaks with the same retention times as those in FA pyrogram under the same conditions. A reproducibility of 6% relative standard deviation was achieved in the pyrolysis of RDF and 0.91% in the case ...
Date: December 1989
Creator: Haj-Mahmoud, Qasem M. (Qasem Mohammed)
Partner: UNT Libraries

Analysis of photographic records of coal pyrolysis. Final report

Description: Bituminous coals upon heating undergo melting and pyrolytic decomposition with significant parts of the coal forming an unstable liquid that can escape from the coal by evaporation. The transient liquid within the pyrolyzing coal causes softening or plastic behavior that can influence the chemistry and physics of the process. Bubbles of volatiles can swell the softened coal mass in turn affecting the combustion behavior of the coal particles. The swelling behavior of individual coal particles has to be taken into account both as the layout as well as for the operation of pyrolysis, coking and performance of coal-fired boilers. Increased heating rates generally increase the amount of swelling although it is also known that in some cases, even highly swelling coals can be transformed into char with no swelling if they are heated slowly enough. The swelling characteristics of individual coal particles have been investigated by a number of workers employing various heating systems ranging from drop tube and shock tube furnaces, flow rate reactors and electrical heating coils. Different methods have also been employed to determine the swelling factors. The following sections summarize some of the published literature on the subject and outline the direction in which the method of analysis will be further extended in the study of the swelling characteristics of hvA bituminous coal particles that have been pyrolyzed with a laser beam.
Date: October 1, 1991
Creator: Dodoo, J. N. D.
Partner: UNT Libraries Government Documents Department

Flash Vacuum Pyrolysis of Lignin Model Compounds: Reaction Pathways of Aromatic Methoxy Groups

Description: Currently, there is interest in utilizing lignin, a major constituent of biomass, as a renewable source of chemicals and fuels. High yields of liquid products can be obtained from the flash or fast pyrolysis of biomass, but the reaction pathways that lead to product formation are not understood. To provide insight into the primary reaction pathways under process relevant conditions, we are investigating the flash vacuum pyrolysis (FVP) of lignin model compounds at 500 C. This presentation will focus on the FVP of {beta}-ether linkages containing aromatic methoxy groups and the reaction pathways of methoxy-substituted phenoxy radicals.
Date: March 21, 1999
Creator: Britt, P. F.; Buchanan, A. C., III & Martineau, D. R.
Partner: UNT Libraries Government Documents Department

Potential Hazards Relating to Pyrolysis of c-C{sub 4}F{sub 8} in Selected Gaseous Diffusion Plant Operations

Description: As part of a program intended to replace the present evaporative coolant at the gaseous diffusion plants (GDPs) with a non-ozone-depleting alternate, a series of investigations of the suitability of candidate substitutes in under way. One issue concerning a primary candidate, c-C4F8, is the possibility that it might produce the highly toxic perfluoroisobutylene (PFIB) in high temperature environments. This study was commissioned to determine the likelihood and severity of decomposition under two specific high temperature thermal environments, namely the use of a flame test for the presence of coolant vapors and welding in the presence of coolant vapors. The purpose of the study was to develop and evaluate available data to provide information that will allow the technical and industrial hygiene staff at the GDPs to perform appropriate safety evaluations and to determine the need for field testing or experimental work. The scope of this study included a literature search and an evaluation of the information developed therefrom. Part of that evaluation consists of chemical kinetics modeling of coolant decomposition in the two operational environments. The general conclusions are that PFIB formation is unlikely in either situation but that it cannot be ruled out completely under extreme conditions. The presence of oxygen, moisture, and combustion products will tend to lead to formation of oxidation products (COF2, CO, CO2, and HF) rather than PFIB.
Date: March 1, 1999
Creator: Trowbridge, L.D.
Partner: UNT Libraries Government Documents Department

Novel technique for coal pyrolysis and hydrogenation product analysis. Quarterly report, March 1, 1992

Description: This report covers the second to the last quarter of the last year of the three-year grant period. In the final project year, we are focusing on the pyrolysis and oxidative pyrolysis of benzene and benzene acetylene mixtures (along with the pyrolysis of other C5-C12 compounds) in order to develop the VUV-MS technique for compounds more representative of those in coal pyrolysis applications. In the first quarters of the current project year, we have carried out the pyrolysis of mixtures of these compounds without oxygen in a microflow reactor. 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 confirms 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. Two different temperature regimes are considered: below 1000 K, where reactivity is dominated by molecular processes, and above 1000 K, where radical chain mechanisms become the dominant pathway. These experiments were carried out at a large range of total pressures and with different diluents.
Date: December 31, 1992
Creator: Pfefferle, L. D.
Partner: UNT Libraries Government Documents Department

Novel technique for coal pyrolysis and hydrogenation product analysis. Quarterly report, January 1991--March 1991

Description: In the second project year, we are concentrating on the pyrolysis of C{sub 6} and C{sub 7} compounds starting with cyclohexane benzene and toluene in order to develop the VUV-MS technique for compounds more representative of those in coal pyrolysis applications. In the first two quarters of the current project year, we have carried out the pyrolysis and oxidative pyrolysis of cyclohexane and toluene and mixtures of these compounds in a microflow reactor. Figures 1 and 2 show mass spectra for cyclohexane pyrolysis and cyclohexane/toluene pyrolysis at 1400 K and 2 ms residence time. The first step in cyclohexane pyrolysis is ring rupture to hexane. The hexane goes through rapid decomposition or, in the case of the hexane/toluene mixture, is also depleted by methyl addition to ultimately form mass 100. The methyl and methane radicals are formed through toluene pyrolysis to phenyl and methyl radicals. Thus mixture data yields insight into pyrolysis of pure compounds because you can titrate species that either are the same mass as the parent fuel or that are important mechanistically but never reach high steady-state concentrations. Mixture data also provides cross checks on species calibrations through reaction rate analysis. Figures 3 and 4 show mass spectra taken during the oxidative pyrolysis of cyclohexane and cyclohexane/toluene for the same conditions as Figures 1 and 2. Note that for these oxidative pyrolysis conditions an important pathway for toluene loss is a reaction with oxygen to form benzaldehyde.
Date: December 31, 1991
Creator: Pfefferle, L. D.
Partner: UNT Libraries Government Documents Department

Production of Gasoline and Diesel from Biomass via Fast Pyrolysis, Hydrotreating and Hydrocracking: A Design Case

Description: The purpose of this study is to evaluate a processing pathway for converting biomass into infrastructure-compatible hydrocarbon biofuels. This design case investigates production of fast pyrolysis oil from biomass and the upgrading of that bio-oil as a means for generating infrastructure-ready renewable gasoline and diesel fuels. This study has been conducted using similar methodology and underlying basis assumptions as the previous design cases for ethanol. The overall concept and specific processing steps were selected because significant data on this approach exists in the public literature. The analysis evaluates technology that has been demonstrated at the laboratory scale or is in early stages of commercialization. The fast pyrolysis of biomass is already at an early stage of commercialization, while upgrading bio-oil to transportation fuels has only been demonstrated in the laboratory and at small engineering development scale. Advanced methods of pyrolysis, which are under development, are not evaluated in this study. These may be the subject of subsequent analysis by OBP. The plant is designed to use 2000 dry metric tons/day of hybrid poplar wood chips to produce 76 million gallons/year of gasoline and diesel. The processing steps include: 1.Feed drying and size reduction 2.Fast pyrolysis to a highly oxygenated liquid product 3.Hydrotreating of the fast pyrolysis oil to a stable hydrocarbon oil with less than 2% oxygen 4.Hydrocracking of the heavy portion of the stable hydrocarbon oil 5.Distillation of the hydrotreated and hydrocracked oil into gasoline and diesel fuel blendstocks 6. Hydrogen production to support the hydrotreater reactors. The "as received" feedstock to the pyrolysis plant will be "reactor ready". This development will likely further decrease the cost of producing the fuel. An important sensitivity is the possibility of co-locating the plant with an existing refinery. In this case, the plant consists only of the first three steps: feed prep, ...
Date: February 25, 2009
Creator: Jones, Susanne B.; Valkenburt, Corinne; Walton, Christie W.; Elliott, Douglas C.; Holladay, Johnathan E.; Stevens, Don J. et al.
Partner: UNT Libraries Government Documents Department