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Sample records for landgard pyrolysis system

  1. Pyrolysis system evaluation study

    NASA Technical Reports Server (NTRS)

    1974-01-01

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

  2. Mass balance and exergy analysis of a fast pyrolysis system

    USDA-ARS?s Scientific Manuscript database

    Mass balance closure and exergetic efficiency is evaluated for a bench scale fast pyrolysis system. The USDA Agricultural Research Service (ARS) has developed this system for processing energy crops and agricultural residues for bio-oil (pyrolysis oil or pyrolysis liquids) production. Mass balance c...

  3. Mineral nutrient recovery from pyrolysis systems

    USDA-ARS?s Scientific Manuscript database

    Bioenergy crops such as high-energy sorghum (HES), bioenergy rice, corn stover, and switchgrass can be thermo-chemically converted by pyrolysis to produce bio-oil, synthesis gas from non-condensable gases, and biochar. The biochar fraction can be recycled back to the production field to improve soil...

  4. INTEGRATED PYROLYSIS COMBINED CYCLE BIOMASS POWER SYSTEM CONCEPT DEFINITION

    SciTech Connect

    Eric Sandvig; Gary Walling; Robert C. Brown; Ryan Pletka; Desmond Radlein; Warren Johnson

    2003-03-01

    Advanced power systems based on integrated gasification/combined cycles (IGCC) are often presented as a solution to the present shortcomings of biomass as fuel. Although IGCC has been technically demonstrated at full scale, it has not been adopted for commercial power generation. Part of the reason for this situation is the continuing low price for coal. However, another significant barrier to IGCC is the high level of integration of this technology: the gas output from the gasifier must be perfectly matched to the energy demand of the gas turbine cycle. We are developing an alternative to IGCC for biomass power: the integrated (fast) pyrolysis/ combined cycle (IPCC). In this system solid biomass is converted into liquid rather than gaseous fuel. This liquid fuel, called bio-oil, is a mixture of oxygenated organic compounds and water that serves as fuel for a gas turbine topping cycle. Waste heat from the gas turbine provides thermal energy to the steam turbine bottoming cycle. Advantages of the biomass-fueled IPCC system include: combined cycle efficiency exceeding 37 percent efficiency for a system as small as 7.6 MW{sub e}; absence of high pressure thermal reactors; decoupling of fuel processing and power generation; and opportunities for recovering value-added products from the bio-oil. This report provides a technical overview of the system including pyrolyzer design, fuel clean-up strategies, pyrolysate condenser design, opportunities for recovering pyrolysis byproducts, gas turbine cycle design, and Rankine steam cycle. The report also reviews the potential biomass fuel supply in Iowa, provide and economic analysis, and present a summery of benefits from the proposed system.

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

    USGS Publications Warehouse

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

    2002-01-01

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

  6. Investigating the potential for a self-sustaining slow pyrolysis system under varying operating conditions.

    PubMed

    Crombie, Kyle; Mašek, Ondřej

    2014-06-01

    This work aimed to investigate the impact of highest treatment temperature (HTT), heating rate, carrier gas flow rate and feedstock on the composition and energy content of pyrolysis gas to assess whether a self-sustained system could be achieved through the combustion of the gas fraction alone, leaving other co-products available for alternative high-value uses. Calculations based on gas composition showed that the pyrolysis process could be sustained by the energy contained within the pyrolysis gases alone. The lower energy limit (6% biomass higher heating value (HHV)) was surpassed by pyrolysis at ⩾450°C while only a HTT of 650°C consistently met the upper energy limit (15% biomass HHV). These findings fill an important gap in literature related to the energy balance of the pyrolysis systems for biochar production, and show that, at least from an energy balance perspective; self-sustained slow pyrolysis for co-production of biochar and liquid products is feasible.

  7. Pyrolysis biochar systems for recovering biodegradable materials: A life cycle carbon assessment.

    PubMed

    Ibarrola, Rodrigo; Shackley, Simon; Hammond, James

    2012-05-01

    A life cycle assessment (LCA) focused on biochar and bioenergy generation was performed for three thermal treatment configurations (slow pyrolysis, fast pyrolysis and gasification). Ten UK biodegradable wastes or residues were considered as feedstocks in this study. Carbon (equivalent) abatement (CA) and electricity production indicators were calculated. Slow pyrolysis systems offer the best performance in terms of CA, with net results varying from 0.07 to 1.25tonnes of CO(2)eq.t(-1) of feedstock treated. On the other hand, gasification achieves the best electricity generation outputs, with results varying around 0.9MWhet(-1) of feedstock. Moreover, selection of a common waste treatment practice as the reference scenario in an LCA has to be undertaken carefully as this will have a key influence upon the CA performance of pyrolysis or gasification biochar systems (P/GBS). Results suggest that P/GBS could produce important environmental benefits in terms of CA, but several potential pollution issues arising from contaminants in the biochar have to be addressed before biochar and bioenergy production from biodegradable waste can become common practice.

  8. Energy Conversion Loop: A Testbed for Nuclear Hybrid Energy Systems Use in Biomass Pyrolysis

    NASA Astrophysics Data System (ADS)

    Verner, Kelley M.

    Nuclear hybrid energy systems are a possible solution for contemporary energy challenges. Nuclear energy produces electricity without greenhouse gas emissions. However, nuclear power production is not as flexible as electrical grids demand and renewables create highly variable electricity. Nuclear hybrid energy systems are able to address both of these problems. Wasted heat can be used in processes such as desalination, hydrogen production, or biofuel production. This research explores the possible uses of nuclear process heat in bio-oil production via biomass pyrolysis. The energy conversion loop is a testbed designed and built to mimic the heat from a nuclear reactor. Small scale biomass pyrolysis experiments were performed and compared to results from the energy conversion loop tests to determine future pyrolysis experimentation with the energy conversion loop. Further improvements must be made to the energy conversion loop before more complex experiments may be performed. The current conditions produced by the energy conversion loop are not conducive for current biomass pyrolysis experimentation.tion.

  9. Pyrolysis typing of isolates from a recurrence of systemic cryptococcosis.

    PubMed

    Magee, J T; Philpot, C; Yang, J; Hosein, I K

    1994-03-01

    Cryptococcal meningitis was diagnosed in a 71-year-old male diabetic patient with underlying ischaemic heart disease, asthma and bilateral axillo-femoral vascular grafts. After treatment with fluconazole for 2 months, the patient appeared to be cured. Two years later he presented with an aneurysm of the right graft that was resected and replaced with a new graft segment. Cryptococcus neoformans var. neoformans was grown from post-operative blood cultures and samples of the excised graft. The patient was treated with fluconazole and discharged after 6 weeks. Multiple isolates from both episodes had been preserved, and these, together with isolates from other UK patients, were cultured in duplicate, blind coded and characterised by pyrolysis mass spectrometry (PMS). Duplicate culture and re-isolate sets formed tight clusters, with each patient set clearly distinct. Sets of isolates from the two episodes in this patient formed a single tight cluster and were indistinguishable by PMS. These results support the contention that C. neoformans infection can be reactivated after being dormant for a prolonged period.

  10. Fundamental Pyrolysis Studies

    SciTech Connect

    Milne, T. A.; Evans, R. J.; Soltys, M. N.

    1983-03-01

    Progress on the direct mass spectrometric sampling of pyrolysis products from wood and its constituents is described for the period from June 1982 to February 1983. A brief summary and references to detailed reports, of the qualitative demonstration of our approach to the study of the separated processes of primary and secondary pyrolysis is presented. Improvements and additions to the pyrolysis and data acquisition systems are discussed and typical results shown. Chief of these are a heated-grid pyrolysis system for controlled primary pyrolysis and a sheathed flame arrangement for secondary cracking studies. Qualitative results of the secondary cracking of cellulose, lignin, and wood are shown as are comparisons with the literature for the pyrolysis spectra of cellulose, lignin, and levoglucosan. 'Fingerprints' for a number of materials are shown, with spectra taken under carefully controlled conditions so that sensitivity calibrations for different compounds, now being determined, can be applied.

  11. Investigating the use of phenolic rich fraction of pyrolysis bio-oils as an adhesive system

    NASA Astrophysics Data System (ADS)

    Sahaf, Amir

    Fast pyrolysis allows converting of up to 75 % of biomass into a crude bio-oil, which can be separated into a phenolic rich fraction (PRF) via ethyl acetate extraction while a sugar rich fraction preferentially concentrates in the aqueous phase. Rheological and thermal characterization of heat treated PRF from pyrolysis of Douglas Fir is performed using cone and plate rheology set up, dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). The results show that this material demonstrates a unique thermoplastic behavior with low Tg and softening point that can be systematically manipulated through changes in thermal history. As these materials are good candidates for development of hot melt adhesives, lap shear tests were also performed using wood stripes to evaluate their mechanical properties as an adhesive. Optimization of properties of the PRF is sought in this study through polymer blending with other bio-degradable thermoplastic poly(epsilon-caprolactone) (PCL) and poly(lactic acid) (PLA). Blends of PRF/PCL and PRF/PLA of different ratios are prepared by solvent casting and melt blending and thermally and thermomechanically characterized for their miscibility and phase behavior. Presence of molecular interactions are furthur investigated using Fourier transform infrared spectoscopy (FTIR). The blends show complete miscibility based on their Tg and melting points and significant improvement in shear strength is observed. Mechanisms leading to changes in properties are described and a physical model is proposed. The blend systems have good potential to be used as a thermoplastic bio degradable adhesives with satisfactoty properies.

  12. Rock samples analysis with the pyrolysis system of the Mars Organic Molecule Analyzer (MOMA)

    NASA Astrophysics Data System (ADS)

    Steininger, H.; Goetz, W.; Goesmann, F.

    2012-12-01

    The Mars Organic Molecule Analyzer (MOMA) is a combined pyrolysis gas chromatograph mass spectrometer (GC-MS) and laser desorption mass spectrometer (LD-MS). It will be the key instrument of the ESA/Roscosmos ExoMars 2018 mission to search for extinct and extant life. Additionally the instrument will be able to detect the organic background which has possibly been delivered to Mars by meteorites. Several samples containing a wide range of organic molecules have been tested with a flight analog injection system. The results of the tests were compared to results obtained by a commercial pyrolysis system, the Pyrola pyrolysis unit. The first experimental setup (Pyrola unit) consists of a small quartz tube with an electrically heated platinum filament. A constant helium flow transports the volatilized compounds through an injection needle directly into the injector of the GC. The whole system is heated to 175°C. The second experimental setup (flight analog injection system) consists of a 6 mm diameter platinum oven connected to a microvalve plate to route the gas from the oven to the GC. The microvalves can be switched electrically. The volatiles are subsequently trapped in a cold trap consisting of a Tenax filed tube. Heating this tube releases the volatiles and injects them through an injection needle into the GC. A Varian 4000 GC-MS with RTX-5 column was used to separate and analyze the volatiles generated from both experimental setups. During the experiments several natural rock samples with a broad content of organic material have been analyzed. The sample material was crushed and ground. To obtain comparable results the same amount of sample was used in both setups. Lower temperatures were used in the flight analog injection system due to restrictions of the reusable oven. Lower temperatures normally lead to only a slight decrease in the very heavy and non-volatile compounds but do not change the overall appearance of the chromatogram. Significant differences in

  13. Comparison of in-situ and ex-situ catalytic pyrolysis in a micro-reactor system.

    PubMed

    Wang, Kaige; Johnston, Patrick A; Brown, Robert C

    2014-12-01

    In this study, we compared ex-situ catalytic pyrolysis (CP) and in-situ CP of hybrid poplar in a micro-reactor system. When both pyrolysis and catalysis were performed at 700 °C, the carbon yield of olefins was greater for ex-situ CP than for in-situ CP (17.4% vs. 5.4%). On the other hand, in-situ CP produced more aromatic hydrocarbons than ex-situ CP (26.1% vs. 18.9%). The remarkably high yield of olefins from ex-situ CP indicates the potential of exploiting the process to preferentially produce olefins as a primary product from biomass, with aromatics being the secondary products. The carbon yield of carbonaceous residues from ex-situ CP was 18.6% compared to 31.3% for in-situ CP. Substantial carbon was deposited as char during ex-situ CP, which could be easily recovered as by-product, simplifying catalyst regeneration. The effects of catalyst loading, pyrolysis temperature and catalysis temperature on product distributions for ex-situ CP were also investigated. Our results showed that catalyst temperature strongly affected product distribution. While high catalyst temperature enhanced both olefin and aromatic production, yield of olefin increased to a greater extent than did aromatics. Neither pyrolysis temperature nor catalyst loadings had significant effect on product distribution for ex-situ CP.

  14. On methane pyrolysis special applications

    NASA Astrophysics Data System (ADS)

    Toncu, D. C.; Toncu, G.; Soleimani, S.

    2015-11-01

    Methane pyrolysis represents one of the most important processes in industrial use, with applications rising from the chemical and petrochemical industry, combustion, materials and protective coatings. Despite the intense research, experimental data lack kinetic aspects, and the thermodynamics involved often leads to inaccurate results when applied to various systems. Carrying out a comparative analysis of several available data on methane pyrolysis, the paper aims to study the phenomenon of methane pyrolysis under different environments (combustion and plasma), concluding on the most possible reaction pathways involved in many of its applications. Computer simulation using different database underlines the conclusion, helping to the understanding of methane pyrolysis importance in future technologies.

  15. Energy and costs scoping study for plasma pyrolysis thermal processing system

    SciTech Connect

    Sherick, K.E.; Findley, J.E.

    1992-01-01

    The purpose of this study was to provide information in support of an investigation of thermal technologies as possible treatment process for buried wastes at the INEL. Material and energy balances and a cost estimate were generated for a representative plasma torch-based thermal waste treatment system operating in a pyrolysis mode. Two waste streams were selected which are representative of INEL buried wastes, large in volume, and difficult to treat by other technologies. These streams were a solidified nitrate sludge waste stream and a waste/soil mix of other buried waste components. The treatment scheme selected includes a main plasma chamber operating under pyrolyzing conditions; a plasma afterburner to provide additional residence time at high temperature to ensure complete destruction of hazardous organics; an off-gas treatment system; and a incinerator and stack to oxidize carbon monoxide to carbon dioxide and vent the clean, oxidized gases to atmosphere. The material balances generated provide materials flow and equipment duty information of sufficient accuracy to generate initial rough-order-of-magnitude (ROM) system capital and operating cost estimates for a representative plasma thermal processing system.

  16. Liquid–Liquid Equilibrium Measurements for Model Systems Related to Catalytic Fast Pyrolysis of Biomass

    DOE PAGES

    Jasperson, Louis V.; McDougal, Rubin J.; Diky, Vladimir; ...

    2017-01-12

    We report liquid-liquid mutual solubilities for binary aqueous mixtures involving 2-, 3-, and 4-ethylphenol, 2-, 3-, and 4-methoxyphenol, benzofuran, and 1H-indene for the temperature range (300 < T/K < 360). Measurements in the water-rich phase for (2-ethylphenol + water) were extended to T = 440 K to facilitate comparison with literature values. Liquid-liquid equilibrium tie-line determinations were made for four ternary systems involving (water + toluene) mixed with a third component; phenol, 3-ethylphenol, 4-methoxyphenol, or 2,4-dimethylphenol. Literature values at higher temperatures are available for the three (ethylphenol + water) systems, and, in general, good agreement is seen. The ternary systemmore » (water + toluene + phenol) has been studied previously with inconsistent results reported in the literature, and one report is shown to be anomalous. All systems are modeled with the predictive methods NIST-Modified-UNIFAC and NIST-COSMO-SAC, with generally good success in the temperature range of interest (300 < T/K < 360). This work is part of a larger project on the testing and development of predictive phase equilibrium models for compound types occurring in catalytic fast pyrolysis of biomass, and background information for the larger project is provided.« less

  17. Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

    NASA Technical Reports Server (NTRS)

    McCoy, LaShelle E.

    2012-01-01

    The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified .. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and cbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes. Issues such as carbon sequestration and subsequent carbon balance of the closed system and identifying ideal process methods to achieve the highest quality products, whilst being energy friendly, will also be addressed.

  18. In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

    DOE PAGES

    Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; ...

    2016-02-03

    In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 degrees C, and the weight hourly space velocity was 1.1 h-1. Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun. Themore » in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16-18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one- to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). Lastly, high fractions of oxygen were rejected as water, CO, and CO2, which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.« less

  19. In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

    SciTech Connect

    Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; Yung, Matthew M.; Johnson, David K.; ten Dam, Jeroen; Watson, Michael J.; Nimlos, Mark R.

    2016-02-03

    In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 degrees C, and the weight hourly space velocity was 1.1 h-1. Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun. The in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16-18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one- to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). Lastly, high fractions of oxygen were rejected as water, CO, and CO2, which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.

  20. In Situ and ex Situ Catalytic Pyrolysis of Pine in a Bench-Scale Fluidized Bed Reactor System

    SciTech Connect

    Iisa, Kristiina; French, Richard J.; Orton, Kellene A.; Yung, Matthew M.; Johnson, David K.; ten Dam, Jeroen; Watson, Michael J.; Nimlos, Mark R.

    2016-03-17

    In situ and ex situ catalytic pyrolysis were compared in a system with two 2-in. bubbling fluidized bed reactors. Pine was pyrolyzed in the system with a catalyst, HZSM-5 with a silica-to-alumina ratio of 30, placed either in the first (pyrolysis) reactor or the second (upgrading) reactor. Both the pyrolysis and upgrading temperatures were 500 degrees C, and the weight hourly space velocity was 1.1 h-1. Five catalytic cycles were completed in each experiment. The catalytic cycles were continued until oxygenates in the vapors became dominant. The catalyst was then oxidized, after which a new catalytic cycle was begun. The in situ configuration gave slightly higher oil yield but also higher oxygen content than the ex situ configuration, which indicates that the catalyst deactivated faster in the in situ configuration than the ex situ configuration. Analysis of the spent catalysts confirmed higher accumulation of metals in the in situ experiment. In all experiments, the organic oil mass yields varied between 14 and 17% and the carbon efficiencies between 20 and 25%. The organic oxygen concentrations in the oils were 16-18%, which represented a 45% reduction compared to corresponding noncatalytic pyrolysis oils prepared in the same fluidized bed reactor system. GC/MS analysis showed the oils to contain one- to four-ring aromatic hydrocarbons and a variety of oxygenates (phenols, furans, benzofurans, methoxyphenols, naphthalenols, indenols). High fractions of oxygen were rejected as water, CO, and CO2, which indicates the importance of dehydration, decarbonylation, and decarboxylation reactions. Light gases were the major sources of carbon losses, followed by char and coke.

  1. Increased Oxygen Recovery from Sabatier Systems Using Plasma Pyrolysis Technology and Metal Hydride Separation

    NASA Technical Reports Server (NTRS)

    Greenwood, Zachary W.; Abney, Morgan B.; Perry, Jay L.; Miller, Lee A.; Dahl, Roger W.; Hadley, Neal M.; Wambolt, Spencer R.; Wheeler, Richard R.

    2015-01-01

    State-of-the-art life support carbon dioxide (CO2) reduction technology is based on the Sabatier reaction where less than 50% of the oxygen required for the crew is recovered from metabolic CO2. The reaction produces water as the primary product and methane as a byproduct. Oxygen recovery is constrained by the limited availability of reactant hydrogen. This is further exacerbated when Sabatier methane (CH4) is vented as a waste product resulting in a continuous loss of reactant hydrogen. Post-processing methane with the Plasma Pyrolysis Assembly (PPA) to recover hydrogen has the potential to dramatically increase oxygen recovery and thus drastically reduce the logistical challenges associated with oxygen resupply. The PPA decomposes methane into predominantly hydrogen and acetylene. Due to the highly unstable nature of acetylene, a separation system is necessary to purify hydrogen before it is recycled back to the Sabatier reactor. Testing and evaluation of a full-scale Third Generation PPA is reported and investigations into metal hydride hydrogen separation technology is discussed.

  2. Synthesis of CuInS2 thin films by spray pyrolysis deposition system

    NASA Astrophysics Data System (ADS)

    Hussain, K. M. A.; Podder, J.; Saha, D. K.

    2013-02-01

    Copper indium disulfide (CuInS2) thin films were deposited on the glass substrate by the locally made spray pyrolysis deposition system. The films were characterized by using energy dispersive analytical X-ray (EDAX) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) and UV-VIS-NIR spectrophotometry. The XRD pattern indicated that the prepared CuInS2 thin films are chalcopyrite structure. Lattice parameters and FWHM values were verified by the standard values of JCPDS 270159 file. The EDAX analysis indicated the stoichiometric ratio of 1.14:1:1.88 (CIS-2) thin films. The SEM analysis showed that the average grain size of the film was 100-800 nm and that of XRD data indicate the values of 30-50 nm. The high absorption co-efficient and 1.48 eV band gap of the films indicate that the films are useful as an absorber for photovoltaic application in the solar cell.

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

    PubMed

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

    2017-07-08

    In this study, an integrated two-stage system, including the in-situ catalytic microwave pyrolysis (ICMP) and subsequent catalytic wet oxidation (CWO) processes, was proposed to remove H2S released from microwave-induced pyrolysis of sewage sludge. The emission profile and H2S removal from the pyrolysis of raw sewage sludge (SS) and sewage sludge spiked with conditioner CaO (SS-CaO) were investigated. The results showed that CaO played a positive role on sulfur fixation during the pyrolysis process. It was found that SS-CaO (10 wt.%) contributed to about 35% of H2S removal at the first stage (ICMP process). Additionally, the CWO process was demonstrated to have promising potential for posttreatment of remaining H2S gas. At the Fe(3+) concentration of 30 g/L, the maximum H2S removal efficiency of 94.8% was obtained for a single Fe(3+)/Cu(2+) solution. Finally, at the pyrolysis temperature of 800 °C, 99.7% of H2S was eliminated by the integrated two-stage system meeting the discharge standard of China. Therefore, the integrated two-stage system of ICMP + CWO may provide a promising strategy to remove H2S dramatically for the biomass pyrolysis industry.

  4. The Power-Supply Control System in the Device of Acetylene Production by H-Plasma Pyrolysis Coal

    NASA Astrophysics Data System (ADS)

    Chen, Feiyun; Zhang, Ming; Fu, Peng; Weng, Peide

    2006-09-01

    The device of acetylene production by hydrogen (H-) plasma pyrolysis coal is examined and developed not only for studying the application of low temperature plasma but also for studying the clean use of coal. The power-supply control system is used to ensure supplying a steady energy to generate and maintain the plasma electric arc of the device. The hardware configuration and the software design of the system are described in this paper. Verified by experiments, this system can meet the requirements of real-time performance, reliability and extensibility for the device.

  5. ENGINEERING BULLETIN: PYROLYSIS TREATMENT

    EPA Science Inventory

    Pyrolysis is formally defined as chemical decomposition induced in organic materials by heat in the absence of oxygen. In practice, it is not possible to achieve a completely oxygen-free atmosphere; actual pyrolytic systems are operated with less than stoichiometric quantities of...

  6. ENGINEERING BULLETIN: PYROLYSIS TREATMENT

    EPA Science Inventory

    Pyrolysis is formally defined as chemical decomposition induced in organic materials by heat in the absence of oxygen. In practice, it is not possible to achieve a completely oxygen-free atmosphere; actual pyrolytic systems are operated with less than stoichiometric quantities of...

  7. Fundamental pyrolysis studies. Annual report FY 1982

    SciTech Connect

    Milne, T.A.; Soltys, M.N.

    1983-04-01

    Progress on the direct mass spectrometric sampling of pyrolysis products from wood and its constituents is described for FY 83. A brief summary, and references to detailed reports, of the qualitative demonstration of our approach to the study of the separated processes of primary and secondary pyrolysis is presented. Improvements and additions to the pyrolysis and data acquisition systems are discussed and typical results shown. Chief of these are a heated-grid pyrolysis system for controlled primary pyrolysis and a sheathed-flame arrangement for secondary cracking studies. Qualitative results of the secondary cracking of cellulose, lignin, and wood are shown as are comparisons with the literature for the pyrolysis spectra of cellulose, lignin, and levoglucosan.

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

    PubMed

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

    2016-08-15

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

  9. Coal pyrolysis to acetylene using dc hydrogen plasma torch: effects of system variables on acetylene concentration

    NASA Astrophysics Data System (ADS)

    Chen, Longwei; Meng, Yuedong; Shen, Jie; Shu, Xingsheng; Fang, Shidong; Xiong, Xinyang

    2009-03-01

    In order to unveil the inner mechanisms that determine acetylene concentration, experimental studies on the effect of several parameters such as plasma torch power, hydrogen flux and coal flux were carried out from coal pyrolysis in a dc plasma torch. Xinjiang long flame coals including volatile constituents at a level of about 42% were used in the experiment. Under the following experimental conditions, namely plasma torch power, hydrogen flow rate and pulverized coal feed speed of 2.12 MW, 32 kg h-1 and 900 kg h-1, respectively, acetylene volume concentration of about 9.4% was achieved. The experimental results indicate that parameters such as plasma torch power and coal flux play important roles in the formation of acetylene. Acetylene concentration increases inconspicuously with hydrogen flux. A chemical thermodynamic equilibrium model using the free energy method is introduced in this paper to numerically simulate each experimental condition. The numerical results are qualitatively consistent with the experimental results. Two parameters, i.e. the gas temperature and the ratio of hydrogen/carbon, are considered to be the dominant and independent factors that determine acetylene concentration.

  10. Method and system including a double rotary kiln pyrolysis or gasification of waste material

    DOEpatents

    McIntosh, Michael J.; Arzoumanidis, Gregory G.

    1997-01-01

    A method of destructively distilling an organic material in particulate form wherein the particulates are introduced through an inlet into one end of an inner rotating kiln ganged to and coaxial with an outer rotating kiln. The inner and outer kilns define a cylindrical annular space with the inlet being positioned in registry with the axis of rotation of the ganged kilns. During operation, the temperature of the wall of the inner rotary kiln at the inlet is not less than about 500.degree. C. to heat the particulate material to a temperature in the range of from about 200.degree. C. to about 900.degree. C. in a pyrolyzing atmosphere to reduce the particulate material as it moves from the one end toward the other end. The reduced particulates including char are transferred to the annular space between the inner and the outer rotating kilns near the other end of the inner rotating kiln and moved longitudinally in the annular space from near the other end toward the one end in the presence of oxygen to combust the char at an elevated temperature to produce a waste material including ash. Also, heat is provided which is transferred to the inner kiln. The waste material including ash leaves the outer rotating kiln near the one end and the pyrolysis vapor leaves through the particulate material inlet.

  11. Method and system including a double rotary kiln pyrolysis or gasification of waste material

    DOEpatents

    McIntosh, M.J.; Arzoumanidis, G.G.

    1997-09-02

    A method is described for destructively distilling an organic material in particulate form wherein the particulates are introduced through an inlet into one end of an inner rotating kiln ganged to and coaxial with an outer rotating kiln. The inner and outer kilns define a cylindrical annular space with the inlet being positioned in registry with the axis of rotation of the ganged kilns. During operation, the temperature of the wall of the inner rotary kiln at the inlet is not less than about 500 C to heat the particulate material to a temperature in the range of from about 200 C to about 900 C in a pyrolyzing atmosphere to reduce the particulate material as it moves from the one end toward the other end. The reduced particulates including char are transferred to the annular space between the inner and the outer rotating kilns near the other end of the inner rotating kiln and moved longitudinally in the annular space from near the other end toward the one end in the presence of oxygen to combust the char at an elevated temperature to produce a waste material including ash. Also, heat is provided which is transferred to the inner kiln. The waste material including ash leaves the outer rotating kiln near the one end and the pyrolysis vapor leaves through the particulate material inlet. 5 figs.

  12. A method and system including a double rotary kiln pyrolysis or gasification of waste material

    SciTech Connect

    McIntosh, M.J.; Arzoumanidis, G.G.

    1995-12-31

    A method is described for destructively distilling an organic material in particulate form wherein the particulates are introduced through an inlet into one end of an inner rotating kiln ganged to and coaxial with an outer rotating kiln. The inner and outer kilns define a cylindrical annular space with the inlet being positioned in registry with the axis of rotation of the ganged kilns. During operation, the temperature of the wall of the inner rotary kiln at the inlet is not less than about 500 C to heat the particulate material to a temperature in the range of from about 200 C to about 900 C in a pyrolyzing atmosphere to reduce the particulate material as it moves from the one end toward the other end. The reduced particulates including char are transferred to the annular space between the inner and the outer rotating kilns near the other end of the inner rotating kiln and moved longitudinally in the annular space from near the other end toward the one end in the presence of oxygen to combust the char at an elevated temperature to produce a waste material including ash. Also, heat is provided which is transferred to the inner kiln. The waste material including ash leaves the outer rotating kiln near the one end and the pyrolysis vapor leaves through the particulate material inlet.

  13. Method and system including a double rotary kiln pyrolysis or gasification of waste material

    SciTech Connect

    McIntosh, M.J.; Arzoumanidis, G.G.

    1997-09-02

    A method is described for destructively distilling an organic material in particulate form wherein the particulates are introduced through an inlet into one end of an inner rotating kiln ganged to and coaxial with an outer rotating kiln. The inner and outer kilns define a cylindrical annular space with the inlet being positioned in registry with the axis of rotation of the ganged kilns. During operation, the temperature of the wall of the inner rotary kiln at the inlet is not less than about 500 C to heat the particulate material to a temperature in the range of from about 200 C to about 900 C in a pyrolyzing atmosphere to reduce the particulate material as it moves from the one end toward the other end. The reduced particulates including char are transferred to the annular space between the inner and the outer rotating kilns near the other end of the inner rotating kiln and moved longitudinally in the annular space from near the other end toward the one end in the presence of oxygen to combust the char at an elevated temperature to produce a waste material including ash. Also, heat is provided which is transferred to the inner kiln. The waste material including ash leaves the outer rotating kiln near the one end and the pyrolysis vapor leaves through the particulate material inlet. 5 figs.

  14. Vapor phase pyrolysis

    NASA Technical Reports Server (NTRS)

    Steurer, Wolfgang

    1992-01-01

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

  15. Macro controlling of copper oxide deposition processes and spray mode by using home-made fully computerized spray pyrolysis system

    NASA Astrophysics Data System (ADS)

    Essa, Mohammed Sh.; Chiad, Bahaa T.; Shafeeq, Omer Sh.

    2017-09-01

    Thin Films of Copper Oxide (CuO) absorption layer have been deposited using home-made Fully Computerized Spray Pyrolysis Deposition system FCSPD on glass substrates, at the nozzle to substrate distance equal to 20,35 cm, and computerized spray mode (continues spray, macro-control spray). The substrate temperature has been kept at 450 °c with the optional user can enter temperature tolerance values ± 5 °C. Also that fixed molar concentration of 0.1 M, and 2D platform speed or deposition platform speed of 4mm/s. more than 1000 instruction program code, and specific design of graphical user interface GUI to fully control the deposition process and real-time monitoring and controlling the deposition temperature at every 200 ms. The changing in the temperature has been recorded during deposition processes, in addition to all deposition parameters. The films have been characterized to evaluate the thermal distribution over the X, Y movable hot plate, the structure and optical energy gap, thermal and temperature distribution exhibited a good and uniform distribution over 20 cm2 hot plate area, X-ray diffraction (XRD) measurement revealed that the films are polycrystalline in nature and can be assigned to monoclinic CuO structure. Optical band gap varies from 1.5-1.66 eV depending on deposition parameter.

  16. A Review: Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

    NASA Technical Reports Server (NTRS)

    McCoy, LaShelle E.

    2013-01-01

    The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing. and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and carbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes.

  17. Supercritical Fuel Pyrolysis

    DTIC Science & Technology

    2010-05-30

    experiments are conducted in the isothermal , isobaric reactor designed expressly for such purposes by Davis [22] and used by Stewart [11,12] in the AFOSR... isothermal , isobaric reactor specially designed for such purposes, we have conducted supercritical pyrolysis experiments with three model fuels: 1...prevalent understanding of how these different component groups behave under pyrolysis conditions. Clearly we need to know more about the pyrolysis

  18. Characteristics and potential values of bio-oil, syngas and biochar derived from Salsola collina Pall. in a fixed bed slow pyrolysis system.

    PubMed

    Yue, Yan; Lin, Qimei; Irfan, Muhammad; Chen, Qun; Zhao, Xiaorong

    2016-11-01

    Salsola collina Pall. as a typical euhalophyte was slowly pyrolyzed at 300°C, 500°C and 700°C in a fixed-bed system. The physiochemical properties of syngas, bio-oil and biochar were assayed to understand the impact of pyrolysis temperature on these parameters and then to evaluate their potential values. The results showed that syngas yield (26.07-46.37%) increased with pyrolysis temperature, while biochar yield (47.54-26.83%) decreased. Bio-oil yield (26-30%) was hardly affected by pyrolysis temperature. Both syngas and bio-oil had poor values as direct fuel. The euhalophyte-derived biochar had higher aromaticity (H/C 0.16-0.85, O/C 0.06-0.26), higher cation exchange capacity (198.82-435.74cmolkg(-1)), and higher K(+) (59.35-80.42gkg(-1)) and Na(+) (37.56-53.26gkg(-1)) compared with glycophyte-derived biochars. Our findings imply that halophyte biochar may be more suitable to use as a soil conditioner, which is worthy of further study.

  19. Sabatier Reactor System Integration with Microwave Plasma Methane Pyrolysis Post-Processor for Closed-Loop Hydrogen Recovery

    NASA Technical Reports Server (NTRS)

    Abney, Morgan B.; Miller, Lee A.; Williams, Tom

    2010-01-01

    The Carbon Dioxide Reduction Assembly (CRA) designed and developed for the International Space Station (ISS) represents the state-of-the-art in carbon dioxide reduction (CDRe) technology. The CRA produces water and methane by reducing carbon dioxide with hydrogen via the Sabatier reaction. The water is recycled to the Oxygen Generation Assembly (OGA) and the methane is vented overboard resulting in a net loss of hydrogen. The proximity to earth and the relative ease of logistics resupply from earth allow for a semi-closed system on ISS. However, long-term manned space flight beyond low earth orbit (LEO) dictates a more thoroughly closed-loop system involving significantly higher recovery of hydrogen, and subsequent recovery of oxygen, to minimize costs associated with logistics resupply beyond LEO. The open-loop ISS system for CDRe can be made closed-loop for follow-on missions by further processing methane to recover hydrogen. For this purpose, a process technology has been developed that employs a microwave-generated plasma to reduce methane to hydrogen and acetylene resulting in 75% theoretical recovery of hydrogen. In 2009, a 1-man equivalent Plasma Pyrolysis Assembly (PPA) was delivered to the National Aeronautics and Space Administration (NASA) for technical evaluation. The PPA has been integrated with a Sabatier Development Unit (SDU). The integrated process configuration incorporates a sorbent bed to eliminate residual carbon dioxide and water vapor in the Sabatier methane product stream before it enters the PPA. This paper provides detailed information on the stand-alone and integrated performance of both the PPA and SDU. Additionally, the integrated test stand design and anticipated future work are discussed.

  20. An in-line micro-pyrolysis system to remove contaminating organic species for precise and accurate water isotope analysis by spectroscopic techniques

    NASA Astrophysics Data System (ADS)

    Panetta, R. J.; Hsiao, G.

    2011-12-01

    Trace levels of organic contaminants such as short alcohols and terpenoids have been shown to cause spectral interference in water isotope analysis by spectroscopic techniques. The result is degraded precision and accuracy in both δD and δ18O for samples such as beverages, plant extracts or slightly contaminated waters. An initial approach offered by manufacturers is post-processing software that analyzes spectral features to identify and flag contaminated samples. However, it is impossible for this software to accurately reconstruct the water isotope signature, thus it is primarily a metric for data quality. Here, we describe a novel in-line pyrolysis system (Micro-Pyrolysis Technology, MPT) placed just prior to the inlet of a cavity ring-down spectroscopy (CRDS) analyzer that effectively removes interfering organic molecules without altering the isotope values of the water. Following injection of the water sample, N2 carrier gas passes the sample through a micro-pyrolysis tube heated with multiple high temperature elements in an oxygen-free environment. The temperature is maintained above the thermal decomposition threshold of most organic compounds (≤ 900 oC), but well below that of water (~2000 oC). The main products of the pyrolysis reaction are non-interfering species such as elemental carbon and H2 gas. To test the efficacy and applicability of the system, waters of known isotopic composition were spiked with varying amounts of common interfering alcohols (methanol, ethanol, propanol, hexanol, trans-2-hexenol, cis-3-hexanol up to 5 % v/v) and common soluble plant terpenoids (carveol, linalool, geraniol, prenol). Spiked samples with no treatment to remove the organics show strong interfering absorption peaks that adversely affect the δD and δ18O values. However, with the MPT in place, all interfering absorption peaks are removed and the water absorption spectrum is fully restored. As a consequence, the δD and δ18O values also return to their original

  1. Comparison for the compositions of fast and slow pyrolysis oils by NMR characterization.

    PubMed

    Ben, Haoxi; Ragauskas, Arthur J

    2013-11-01

    The pyrolysis of softwood (SW) kraft lignin and pine wood in different pyrolysis systems were examined at 400, 500 and 600 °C. NMR including quantitative (13)C and Heteronuclear Single-Quantum Correlation (HSQC)-NMR, and Gel Permeation Chromatography (GPC) were used to characterize various pyrolysis oils. The content of methoxyl groups decreased by 76% for pine wood and 70% for lignin when using fast pyrolysis system. The carbonyl groups also decreased by 76% and nearly completely eliminated in 600 °C pine wood fast pyrolysis oil. Compared to the slow pyrolysis process, fast pyrolysis process was found to improve the cleavage of methoxyl groups, aliphatic CC bonds and carbonyl groups and produce more polyaromatic hydrocarbons (PAH) from lignin and aliphatic CO bonds from carbohydrates. Another remarkable difference between fast and slow pyrolysis oils was the molecular weight of fast pyrolysis oils increased by 85-112% for pine wood and 104-112% for lignin.

  2. Disposal of municipal refuse and RDF in Japan by a two-bed pyrolysis system

    SciTech Connect

    Ishii, N.; Ishi, Y.; Ito, K. Hirayama, Y.

    1985-01-01

    This system efficiently and effectively produces high-quality, high-heating-value fuel gas from municipal refuse and RDF. In 1978, the commercial demonstration plant was constructed in Yokohama and since 1979 it has operated with municipal solid waste, RDF, and industrial refuse. The technology is now ready for commercialization.

  3. Financial performance of a mobile pyrolysis system used to produce biochar from sawmill residues

    Treesearch

    Dongyeob Kim; Nathaniel McLean Anderson; Woodam Chung

    2015-01-01

    Primary wood products manufacturers generate significant amounts of woody biomass residues that can be used as feedstocks for distributed-scale thermochemical conversion systems that produce valuable bioenergy and bioproducts. However, private investment in these technologies is driven primarily by financial performance, which is often unknown for new technologies with...

  4. Direct Preparation of Fine Powders of the 80 K Superconducting Phase in the Bi-Ca-Sr-Cu-O System by Spray Pyrolysis

    NASA Astrophysics Data System (ADS)

    Tohge, Noboru; Tatsumisago, Masahiro; Minami, Tsutomu; Okuyama, Kikuo; Arai, Kouji; Kousaka, Yasuo

    1989-07-01

    Submicron powders of the 80 K superconducting phase in the Bi-Ca-Sr-Cu-O system have been directly prepared by the spray pyrolysis of aqueous solutions of corresponding metal nitrates, Bi:Ca:Sr:Cu=1:1:1:2. The powders obtained were spheres with uniformly distributed diameters below 1 μm. The crystalline phase of these powders was found to greatly depend on the oxygen partial pressure in the carrier gas as well as the decomposition temperature. The preparation conditions for the 80 K superconducting phase were examined.

  5. Pyrolysis of waste tyres: A review

    SciTech Connect

    Williams, Paul T.

    2013-08-15

    Graphical abstract: - Highlights: • Pyrolysis of waste tyres produces oil, gas and char, and recovered steel. • Batch, screw kiln, rotary kiln, vacuum and fluidised-bed are main reactor types. • Product yields are influenced by reactor type, temperature and heating rate. • Pyrolysis oils are complex and can be used as chemical feedstock or fuel. • Research into higher value products from the tyre pyrolysis process is reviewed. - Abstract: Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest 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{sub 2}, C{sub 1}–C{sub 4} hydrocarbons, CO{sub 2}, CO and H{sub 2}S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.

  6. Pyrolysis with cyclone burner

    DOEpatents

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

    1978-07-25

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

  7. Pyrolysis with staged recovery

    DOEpatents

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

    1979-03-20

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

  8. The Construction of a Simple Pyrolysis Gas Chromatograph.

    ERIC Educational Resources Information Center

    Hedrick, Jack L.

    1982-01-01

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

  9. The Construction of a Simple Pyrolysis Gas Chromatograph.

    ERIC Educational Resources Information Center

    Hedrick, Jack L.

    1982-01-01

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

  10. Pyrolysis mechanisms. Quarterly report, April-June 1981

    SciTech Connect

    Milne, T.A.; Soltys, M.N.

    1981-12-01

    The data acquisition system for fast pyrolysis studies is summarized and discussed, based on preliminary applications to fast scans and peak switching of the quadrupole mass spectrometer. The free-jet expansion phenomena of internal-state cooling and clustering are discussed in terms of their relevance to pyrolysis product sampling interpretation. Primary pyrolysis spectra are shown for cotton, wood, and steam-exploded extracted lignin. Both pulsed and steady-state pyrolysis were used to observe the secondary cracking of cotton, wood, levoglucosan, glycerol, and methanol in steam-argon at a nominal 900/sup 0/C. The general plan of future studies is presented.

  11. Formate-assisted pyrolysis

    DOEpatents

    DeSisto, William Joseph; Wheeler, Marshall Clayton; van Heiningen, Adriaan R. P.

    2015-03-17

    The present invention provides, among other thing, methods for creating significantly deoxygenated bio-oils form biomass including the steps of providing a feedstock, associating the feedstock with an alkali formate to form a treated feedstock, dewatering the treated feedstock, heating the dewatered treated feedstock to form a vapor product, and condensing the vapor product to form a pyrolysis oil, wherein the pyrolysis oil contains less than 30% oxygen by weight.

  12. Relationship between hydrous and ordinary pyrolysis

    SciTech Connect

    Burnham, A.K.

    1993-06-01

    Pyrolysis results are reviewed briefly with the intent of drawing comparisons between open, high pressure, and hydrous pyrolysis. Empirically, the degree of pyrolysis severity to form volatile products in open pyrolysis is similar to that required to form an expelled oil phase in hydrous pyrolysis. The yields of hydrocarbons from open pyrolysis are close to those from hydrous pyrolysis, but hydrous pyrolysis tends to assist the separation of hydrocarbons from polar materials. Pressure has a small but measurable affect on the generation kinetics.

  13. [Investigation of a gas chromatographic column system for the on-line analysis of gaseous components in de-propane tower of pyrolysis equipment].

    PubMed

    Cai, H; Liu, L J; Yan, J; Lu, X; Ye, F; Xu, G W

    2000-03-01

    Multi-dimensional gas chromatograph has become an important process analyzer due to the advantages of high resolution and fast speed. According to the production requirement, a gas chromatographic column switching system has been investigated for the on-line analysis of gaseous components from high-pressure and lower-pressure de-propane towers of pyrolysis equipment. By using two different injection times on three injectors, and fore-flush and back-flush techniques, C2-hydrocarbons, propane, propene, methylacetylene, propadiene and C4-hydrocarbons can be separated on 7 columns in 7 minutes. The practical application showed the developed column system is suitable for the on-line monitoring of the production process.

  14. Solar heated oil shale pyrolysis process

    NASA Technical Reports Server (NTRS)

    Qader, S. A. (Inventor)

    1985-01-01

    An improved system for recovery of a liquid hydrocarbon fuel from oil shale is presented. The oil shale pyrolysis system is composed of a retort reactor for receiving a bed of oil shale particules which are heated to pyrolyis temperature by means of a recycled solar heated gas stream. The gas stream is separated from the recovered shale oil and a portion of the gas stream is rapidly heated to pyrolysis temperature by passing it through an efficient solar heater. Steam, oxygen, air or other oxidizing gases can be injected into the recycle gas before or after the recycle gas is heated to pyrolysis temperature and thus raise the temperature before it enters the retort reactor. The use of solar thermal heat to preheat the recycle gas and optionally the steam before introducing it into the bed of shale, increases the yield of shale oil.

  15. Fundamental pyrolysis studies. Annual report for Fiscal Year 1981

    SciTech Connect

    Milne, T.A.; Soltys, M.N.

    1982-03-01

    The direct mass spectrometric studies of fast pyrolysis completed in FY 1981 are summarized, with detailed results of fourth-quarter activities. The latest version of the flame gas pyrolysis/molecular-beam sampling system is schematized with discussion of fast data acquisition capabilities and instrument tuning. Temperature effects in the pyrolysis plume are presented. Background-corrected mass spectra are shown for the pyrolysis in 900/sup 0/C steam-argon of small samples (approx. 10 to 20 mg) of levoglucosan, glucose, cellulose, lignin, and wood. A very preliminary identification of major products and comparison with the literature is presented. The effects of physical dimensions and alkali catalysts on primary pyrolysis products are shown. A grid-heating apparatus is described, and plans for FY 1982 are outlined.

  16. A gas chromatography/pyrolysis/isotope ratio mass spectrometry system for high-precision deltaD measurements of atmospheric methane extracted from ice cores.

    PubMed

    Bock, Michael; Schmitt, Jochen; Behrens, Melanie; Möller, Lars; Schneider, Robert; Sapart, Celia; Fischer, Hubertus

    2010-03-15

    Air enclosures in polar ice cores represent the only direct paleoatmospheric archive. Analysis of the entrapped air provides clues to the climate system of the past in decadal to centennial resolution. A wealth of information has been gained from measurements of concentrations of greenhouse gases; however, little is known about their isotopic composition. In particular, stable isotopologues (deltaD and delta(13)C) of methane (CH(4)) record valuable information on its global cycle as the different sources exhibit distinct carbon and hydrogen isotopic composition. However, CH(4) isotope analysis is limited by the large sample size required and the demanding analysis as high precision is required. Here we present a highly automated, high-precision online gas chromatography/pyrolysis/isotope ratio monitoring mass spectrometry (GC/P/irmMS) technique for the analysis of deltaD(CH(4)). It includes gas extraction from ice, preconcentration, gas chromatographic separation and pyrolysis of CH(4) from roughly 500 g of ice with CH(4) concentrations as low as 350 ppbv. Ice samples with approximately 40 mL air and only approximately 1 nmol CH(4) can be measured with a precision of 3.4 per thousand. The precision for 65 mL air samples with recent atmospheric concentration is 1.5 per thousand. The CH(4) concentration can be obtained along with isotope data which is crucial for reporting ice core data on matched time scales and enables us to detect flaws in the measurement procedure. Custom-made script-based processing of MS raw and peak data enhance the system's performance with respect to stability, peak size dependency, hence precision and accuracy and last but not least time requirement. Copyright 2010 John Wiley & Sons, Ltd.

  17. Pyrolysis of the tetra pak

    SciTech Connect

    Korkmaz, Ahmet; Yanik, Jale Brebu, Mihai; Vasile, Cornelia

    2009-11-15

    This study deals with pyrolysis of tetra pak which is widely used as an aseptic beverage packaging material. Pyrolysis experiments were carried out under inert atmosphere in a batch reactor at different temperatures and by different pyrolysis modes (one- and two-step). The yields of char, liquid and gas were quantified. Pyrolysis liquids produced were collected as three separate phases; aqueous phase, tar and polyethylene wax. Characterization of wax and the determination of the total amount of phenols in aqueous phase were performed. Chemical compositions of gas and char products relevant to fuel applications were determined. Pure aluminum can be also recovered by pyrolysis.

  18. Pyrolysis of the tetra pak.

    PubMed

    Korkmaz, Ahmet; Yanik, Jale; Brebu, Mihai; Vasile, Cornelia

    2009-11-01

    This study deals with pyrolysis of tetra pak which is widely used as an aseptic beverage packaging material. Pyrolysis experiments were carried out under inert atmosphere in a batch reactor at different temperatures and by different pyrolysis modes (one- and two-step). The yields of char, liquid and gas were quantified. Pyrolysis liquids produced were collected as three separate phases; aqueous phase, tar and polyethylene wax. Characterization of wax and the determination of the total amount of phenols in aqueous phase were performed. Chemical compositions of gas and char products relevant to fuel applications were determined. Pure aluminum can be also recovered by pyrolysis.

  19. Pyrolysis of Table Sugar

    PubMed Central

    Karagöz, Selhan

    2013-01-01

    Table sugars were pyrolyzed at different temperatures (300, 400, and 500°C) in a fixed-bed reactor. The effect of pyrolysis temperature on yields of liquid, solid, and gaseous products was investigated. As expected the yield of liquid products gradually increased and the yield of solid products gradually decreased when the pyrolysis temperature was raised. The yield of liquid products was greatest (52 wt%) at 500°C. The composition of bio-oils extracted with diethyl ether was identified by means of gas chromatography mass spectrometry (GC-MS), nuclear magnetic resonance (1H-NMR), and Fourier transform infrared spectroscopy (FTIR). The following compounds were observed in bio-oils produced from the pyrolysis of table sugar at 500°C: 1,4:3,6-dianhydro-α-d-glucopyranose, 5-(hydroxymethyl) furfural, 5-acetoxymethyl-2-furaldehyde, and cyclotetradecane liquid product. The relative concentration of 5-(hydroxymethyl) furfural was the highest in bio-oils obtained from pyrolysis of table sugars at 500°C. PMID:24223500

  20. Pyrolysis of table sugar.

    PubMed

    Bulut, Adnan; Karagöz, Selhan

    2013-01-01

    Table sugars were pyrolyzed at different temperatures (300, 400, and 500°C) in a fixed-bed reactor. The effect of pyrolysis temperature on yields of liquid, solid, and gaseous products was investigated. As expected the yield of liquid products gradually increased and the yield of solid products gradually decreased when the pyrolysis temperature was raised. The yield of liquid products was greatest (52 wt%) at 500°C. The composition of bio-oils extracted with diethyl ether was identified by means of gas chromatography mass spectrometry (GC-MS), nuclear magnetic resonance ((1)H-NMR), and Fourier transform infrared spectroscopy (FTIR). The following compounds were observed in bio-oils produced from the pyrolysis of table sugar at 500°C: 1,4:3,6-dianhydro- α -d-glucopyranose, 5-(hydroxymethyl) furfural, 5-acetoxymethyl-2-furaldehyde, and cyclotetradecane liquid product. The relative concentration of 5-(hydroxymethyl) furfural was the highest in bio-oils obtained from pyrolysis of table sugars at 500°C.

  1. Pyrolysis of phenolic impregnated carbon ablator (PICA).

    PubMed

    Bessire, Brody K; Lahankar, Sridhar A; Minton, Timothy K

    2015-01-28

    Molar yields of the pyrolysis products of thermal protection systems (TPSs) are needed in order to improve high fidelity material response models. The volatile chemical species evolved during the pyrolysis of a TPS composite, phenolic impregnated carbon ablator (PICA), have been probed in situ by mass spectrometry in the temperature range 100 to 935 °C. The relative molar yields of the desorbing species as a function of temperature were derived by fitting the mass spectra, and the observed trends are interpreted in light of the results of earlier mechanistic studies on the pyrolysis of phenolic resins. The temperature-dependent product evolution was consistent with earlier descriptions of three stages of pyrolysis, with each stage corresponding to a temperature range. The two main products observed were H2O and CO, with their maximum yields occurring at ∼350 °C and ∼450 °C, respectively. Other significant products were CH4, CO2, and phenol and its methylated derivatives; these products tended to desorb concurrently with H2O and CO, over the range from about 200 to 600 °C. H2 is presumed to be the main product, especially at the highest pyrolysis temperatures used, but the relative molar yield of H2 was not quantified. The observation of a much higher yield of CO than CH4 suggests the presence of significant hydroxyl group substitution on phenol prior to the synthesis of the phenolic resin used in PICA. The detection of CH4 in combination with the methylated derivatives of phenol suggests that the phenol also has some degree of methyl substitution. The methodology developed is suitable for real-time measurements of PICA pyrolysis and should lend itself well to the validation of nonequilibrium models whose aim is to simulate the response of TPS materials during atmospheric entry of spacecraft.

  2. Kinetic investigation of wood pyrolysis

    SciTech Connect

    Thurner, F.; Mann, U.

    1981-07-01

    The kinetics of wood pyrolysis into gas, tar, and char was investigated in the range of 300 to 400 degrees Celcius at atmospheric pressure. An experimental system which facilitates the monitoring of the actual sample temperature, collection of gas and tar, and measurement of the sample weight loss as a function of time was developed. It has been found that, in the range investigated, wood decomposition into gas, tar, and char can be described by three parallel first-order reactions as suggested by Shafizadeh and Chin (1977). The activation energies for these reactions are 88.6, 112.7 and 106.5 kJ/mol, respectively, and their frequency factors defined on a mass basis are 8.61 x 10 to the power of 5, 2.47 x 10 to the power of 8, and 4.43 x 10 to the power of 7 min-1. The composition of the pyrolysis products was also analyzed. It was found that the gas consists mainly of carbon dioxide, carbon monoxide, oxygen, and C3 + compounds with trace amounts of methane, ethylene, and acetylene. The tar consists of seven compounds with levoglucosan accounting for more than half. The char was analyzed by elemental analysis and it was found that its carbon content increases with increasing reactor temperature. (Refs. 12).

  3. Waste tire recycling by pyrolysis

    SciTech Connect

    Not Available

    1992-10-01

    This project examines the City of New Orleans' waste tire problem. Louisiana State law, as of January 1, 1991, prohibits the knowing disposal of whole waste tires in landfills. Presently, the numerous waste tire stockpiles in New Orleans range in size from tens to hundreds of tires. New Orleans' waste tire problem will continue to increase until legal disposal facilities are made accessible and a waste tire tracking and regulatory system with enforcement provisions is in place. Tires purchased outside of the city of New Orleans may be discarded within the city's limits; therefore, as a practical matter this study analyzes the impact stemming from the entire New Orleans metropolitan area. Pyrolysis mass recovery (PMR), a tire reclamation process which produces gas, oil, carbon black and steel, is the primary focus of this report. The technical, legal and environmental aspects of various alternative technologies are examined. The feasibility of locating a hypothetical PMR operation within the city of New Orleans is analyzed based on the current economic, regulatory, and environmental climate in Louisiana. A thorough analysis of active, abandoned, and proposed Pyrolysis operations (both national and international) was conducted as part of this project. Siting a PMR plant in New Orleans at the present time is technically feasible and could solve the city's waste tire problem. Pending state legislation could improve the city's ability to guarantee a long term supply of waste tires to any large scale tire reclamation or recycling operation, but the local market for PMR end products is undefined.

  4. Pyrolysis products of PCBs.

    PubMed Central

    Paasivirta, J; Herzschuh, R; Humppi, T; Kantolahti, E; Knuutinen, J; Lahtiperä, M; Laitinen, R; Salovaara, J; Tarhanen, J; Virkki, L

    1985-01-01

    Model compound studies which were previously done for impurities and environmental residues of chlorophenols and for wastes of chlorination processes were extended to the impurities and pyrolysis products of polychlorinated biphenyls (PCBs). Model compounds were commercial products or synthesized and their structures proven by spectroscopic methods. These models were used as analytical reference substances in GC/ECD and GC/MS studies of the pyrolyzed PCB samples. In addition to previously known neutral components like polychlorinated dibenzofurans (PCDFs), chlorophenolic substances, especially polychlorophenols (PCPs) and polychlorinated biphenylols (PCB-OHs) were observed as major pyrolysis products of PCBs. Capacitor fires are suggested to produce in many cases chlorophenols which are major toxic hazards to people. PMID:3928353

  5. Pyrolysis characteristics of bean dregs and in situ visualization of pyrolysis transformation.

    PubMed

    Zhu, Guangyong; Zhu, Xian; Xiao, Zuobing; Zhou, Rujun; Yi, Fengping

    2012-12-01

    Biomass is an important renewable and sustainable source of energy. Waste products from biomass are considered as attractive feedstocks for the production of fuel. This work deals with the pyrolysis of bean dregs, a biomass waste from soybean processing industry. A technique has been developed to study bean dregs pyrolysis by in situ visualization of bean dregs transformation in a quartz capillary under a microscope using a charge-coupled device (CCD) camera monitoring system. The technique enables us to observe directly the processes and temperatures of bean dregs transformation during pyrolysis. In situ visualization of reaction revealed that how oily liquids are generated and expulsed concurrently from bean dregs during pyrolysis. Pyrolysis characteristics were investigated under a highly purified N(2) atmosphere using a thermogravimetric analyzer from room temperature to 800 °C at different heating rates of 10, 30 and 50 °C/min. The results showed that three stages appeared in this thermal degradation process. The initial decomposition temperature and the peak shifted towards higher temperature with an increase in heating rate. Kinetic parameters in terms of apparent activation energy and pre-exponential factor were determined.

  6. Pyrolysis process and apparatus

    DOEpatents

    Lee, Chang-Kuei

    1983-01-01

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

  7. Effect of temperature on pyrolysis product of empty fruit bunches

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  8. Effect of temperature on pyrolysis product of empty fruit bunches

    SciTech Connect

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

    2015-04-24

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

  9. Feedstock Supply System Design and Economics for Conversion of Lignocellulosic Biomass to Hydrocarbon Fuels Conversion Pathway: Fast Pyrolysis and Hydrotreating Bio-Oil Pathway "The 2017 Design Case"

    SciTech Connect

    Kevin L. Kenney; Kara G. Cafferty; Jacob J. Jacobson; Ian J. Bonner; Garold L. Gresham; J. Richard Hess; William A. Smith; David N. Thompson; Vicki S. Thompson; Jaya Shankar Tumuluru; Neal Yancey

    2014-01-01

    The U.S. Department of Energy promotes the production of liquid fuels from lignocellulosic biomass feedstocks by funding fundamental and applied research that advances the state of technology in biomass sustainable supply, logistics, conversion, and overall system sustainability. As part of its involvement in this program, Idaho National Laboratory (INL) investigates the feedstock logistics economics and sustainability of these fuels. Between 2000 and 2012, INL quantified and the economics and sustainability of moving biomass from the field or stand to the throat of the conversion process using conventional equipment and processes. All previous work to 2012 was designed to improve the efficiency and decrease costs under conventional supply systems. The 2012 programmatic target was to demonstrate a biomass logistics cost of $55/dry Ton for woody biomass delivered to fast pyrolysis conversion facility. The goal was achieved by applying field and process demonstration unit-scale data from harvest, collection, storage, preprocessing, handling, and transportation operations into INL’s biomass logistics model.

  10. Pyrolysis of wastewater biosolids significantly reduces estrogenicity.

    PubMed

    Hoffman, T C; Zitomer, D H; McNamara, P J

    2016-11-05

    Most wastewater treatment processes are not specifically designed to remove micropollutants. Many micropollutants are hydrophobic so they remain in the biosolids and are discharged to the environment through land-application of biosolids. Micropollutants encompass a broad range of organic chemicals, including estrogenic compounds (natural and synthetic) that reside in the environment, a.k.a. environmental estrogens. Public concern over land application of biosolids stemming from the occurrence of micropollutants hampers the value of biosolids which are important to wastewater treatment plants as a valuable by-product. This research evaluated pyrolysis, the partial decomposition of organic material in an oxygen-deprived system under high temperatures, as a biosolids treatment process that could remove estrogenic compounds from solids while producing a less hormonally active biochar for soil amendment. The estrogenicity, measured in estradiol equivalents (EEQ) by the yeast estrogen screen (YES) assay, of pyrolyzed biosolids was compared to primary and anaerobically digested biosolids. The estrogenic responses from primary solids and anaerobically digested solids were not statistically significantly different, but pyrolysis of anaerobically digested solids resulted in a significant reduction in EEQ; increasing pyrolysis temperature from 100°C to 500°C increased the removal of EEQ with greater than 95% removal occurring at or above 400°C. This research demonstrates that biosolids treatment with pyrolysis would substantially decrease (removal>95%) the estrogens associated with this biosolids product. Thus, pyrolysis of biosolids can be used to produce a valuable soil amendment product, biochar, that minimizes discharge of estrogens to the environment.

  11. WEEE recycling: Pyrolysis of fire retardant model polymers.

    PubMed

    Luda, M P; Euringer, N; Moratti, U; Zanetti, M

    2005-01-01

    Pyrolysis treatments of model polymers were made with the aim of studying the recycling of wastes from electronic, electric equipment containing brominated flame retardants. Pyrolysis of flame retarded high impact polystyrene and epoxy resins were made both in flow and closed systems. Products of pyrolysis were analysed with FT-IR spectroscopy and GC-MS and the evolution of bromine was followed with a bromine ion specific electrode. The effect of alkali on pyrolysis was also studied demonstrating, as far epoxy resin is concerned, to be effective on decreasing bromine content in oil and volatile products leading to the recovery of bromine from the residue by washing. The alkali treatment was shown to be less effective in styrenic polymers containing brominated flame retardants.

  12. Corrosivity Of Pyrolysis Oils

    SciTech Connect

    Keiser, James R; Bestor, Michael A; Lewis Sr, Samuel Arthur; Storey, John Morse

    2011-01-01

    Pyrolysis oils from several sources have been analyzed and used in corrosion studies which have consisted of exposing corrosion coupons and stress corrosion cracking U-bend samples. The chemical analyses have identified the carboxylic acid compounds as well as the other organic components which are primarily aromatic hydrocarbons. The corrosion studies have shown that raw pyrolysis oil is very corrosive to carbon steel and other alloys with relatively low chromium content. Stress corrosion cracking samples of carbon steel and several low alloy steels developed through-wall cracks after a few hundred hours of exposure at 50 C. Thermochemical processing of biomass can produce solid, liquid and/or gaseous products depending on the temperature and exposure time used for processing. The liquid product, known as pyrolysis oil or bio-oil, as produced contains a significant amount of oxygen, primarily as components of water, carboxylic acids, phenols, ketones and aldehydes. As a result of these constituents, these oils are generally quite acidic with a Total Acid Number (TAN) that can be around 100. Because of this acidity, bio-oil is reported to be corrosive to many common structural materials. Despite this corrosive nature, these oils have the potential to replace some imported petroleum. If the more acidic components can be removed from this bio-oil, it is expected that the oil could be blended with crude oil and then processed in existing petroleum refineries. The refinery products could be transported using customary routes - pipelines, barges, tanker trucks and rail cars - without a need for modification of existing hardware or construction of new infrastructure components - a feature not shared by ethanol.

  13. Environmental control technology for biomass flash pyrolysis

    SciTech Connect

    Harkness, J.B.L.; Doctor, R.D.; Seward, W.H.

    1980-01-01

    The rapid commercialization of biomass gasification and pyrolysis technologies will raise questions concerning the environmental impacts of these systems and the associated costs for appropriate control technologies. This study concentrates on characterizing the effluent emissions and control technologies for a dual fluid-bed pyrolysis unit run by Arizona State University, Tempe, Arizona. The ASU system produces a raw product gas that is passed through a catalytic liquefaction system to produce a fuel comparable to No. 2 fuel oil. Argonne National Laboratory is conducting a program that will survey several biomass systems to standardize the sampling techniques, prioritize standard analyses and develop a data base so that environmental issues later may be addressed before they limit or impede the commercialization of biomass gasification and pyrolysis technologies. Emissions will be related to both the current and anticipated emissions standards to generate material balances and set design parameters for effluent treatment systems. This will permit an estimate to be made of the capital and operating costs associated with these technologies.

  14. Comparative pyrolysis studies of ethylarsines

    NASA Astrophysics Data System (ADS)

    Li, S. H.; Larsen, C. A.; Stringfellow, G. B.

    1991-01-01

    The pyrolysis of triethylarsine (TEAs), diethylarsine (DEAsH), and monoethylarsine (MEAsH 2) has been studied at atmospheric pressure in a flow tube reactor using mass spectrometry. He and D 2 were selected as the carrier gases to determine ambient effects and to isotopically label the pyrolysis products. For some experiments, supplemental C 2H 5 and CH 3 radicals, produced from pyrolysis of the co-reactants azoethane ((C 2H 5) 2N 2) and azomethane ((CH 3) 2N 2), were added to investigate the roles of C 2H 5 and CH 3 in the reactions. Significant D 2 effects have been observed for pyrolysis of TEAs but not for DEAsH and MEAsH 2. Pyrolysis of the latter could be enhanced by adding C 2H 5 radicals while the TEAs was nearly unaffected. With the presence of supplemental CH 3 radicals, 85% decomposition was induced for each precursor. The products included DEAsD, rather than DEAsH, for TEAs pyrolysis in D 2. However, DEAsH pyrolysis produced TEAs, and MEAsH 2 decomposed to yield DEAsH and arsine, in both ambients. This suggests that a β-elimination reaction is not a major step for any of the ethylarsine precursors. More likely, radical reactions occur. When trimethylgallium (TMGa) was added, the ethylarsine pyrolysis rates were accelerated due to the CH 3 radicals produced from TMGa pyrolysis. In addition, heterogeneous reactions have been observed for pyrolysis of ethylarsines, especially when a GaAs surface was involved.

  15. Char yield on pyrolysis of cellulose

    Treesearch

    A. Broido; Maxine A. Nelson

    1975-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-05-01

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

  17. Waste tire recycling by pyrolysis

    SciTech Connect

    Not Available

    1992-10-01

    This project examines the City of New Orleans` waste tire problem. Louisiana State law, as of January 1, 1991, prohibits the knowing disposal of whole waste tires in landfills. Presently, the numerous waste tire stockpiles in New Orleans range in size from tens to hundreds of tires. New Orleans` waste tire problem will continue to increase until legal disposal facilities are made accessible and a waste tire tracking and regulatory system with enforcement provisions is in place. Tires purchased outside of the city of New Orleans may be discarded within the city`s limits; therefore, as a practical matter this study analyzes the impact stemming from the entire New Orleans metropolitan area. Pyrolysis mass recovery (PMR), a tire reclamation process which produces gas, oil, carbon black and steel, is the primary focus of this report. The technical, legal and environmental aspects of various alternative technologies are examined. The feasibility of locating a hypothetical PMR operation within the city of New Orleans is analyzed based on the current economic, regulatory, and environmental climate in Louisiana. A thorough analysis of active, abandoned, and proposed Pyrolysis operations (both national and international) was conducted as part of this project. Siting a PMR plant in New Orleans at the present time is technically feasible and could solve the city`s waste tire problem. Pending state legislation could improve the city`s ability to guarantee a long term supply of waste tires to any large scale tire reclamation or recycling operation, but the local market for PMR end products is undefined.

  18. Silane-Pyrolysis Reactor With Nonuniform Heating

    NASA Technical Reports Server (NTRS)

    Iya, Sridhar K.

    1991-01-01

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

  19. Pyrolysis Oil Biorefinery.

    PubMed

    Meier, Dietrich

    2017-03-14

    In biorefineries several conversion processes for biomasses may be applied to obtain maximum value from the feed materials. One viable option is the liquefaction of lignocellulosic feedstocks or residues by fast pyrolysis. The conversion technology requires rapid heating of the biomass particles along with rapid cooling of the hot vapors and aerosols. The main product, bio-oil, is obtained in yields of up to 75 wt% on a dry feed basis, together with by-product char and gas which are used within the process to provide the process heat requirements; there are no waste streams other than flue gas and ash. Bio-oils from fast pyrolysis have a great potential to be used as renewable fuel and/or a source for chemical feedstocks. Existing technical reactor designs are presented together with actual examples. Bio-oil characterization and various options for bio-oil upgrading are discussed based on the potential end-use. Existing and potential utilization alternatives for bio-oils are presented with respect to their use for heat and power generation as well as chemical and material use.

  20. Producing Hydrogen by Plasma Pyrolysis of Methane

    NASA Technical Reports Server (NTRS)

    Atwater, James; Akse, James; Wheeler, Richard

    2010-01-01

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

  1. Chapter 8: Biomass Pyrolysis Oils

    SciTech Connect

    McCormick, Robert L.; Baldwin, Robert M.; Arbogast, Stephen; Bellman, Don; Paynter, Dave; Wykowski, Jim

    2016-09-06

    Fast pyrolysis is heating on the order of 1000 degrees C/s in the absence of oxygen to 40-600 degrees C, which causes decomposition of the biomass. Liquid product yield from biomass can be as much as 80% of starting dry weight and contains up to 75% of the biomass energy content. Other products are gases, primarily carbon monoxide, carbon dioxide, and methane, as well as solid char and ash. Residence time in the reactor is only 0.5-2 s so that relatively small, low-capital-cost reactors can be used. The low capital cost combined with greenhouse gas emission reductions relative to petroleum fuels of 50-95% makes pyrolysis an attractive process. The pyrolysis liquids have been investigated as a refinery feedstock and as stand-alone fuels. Utilization of raw pyrolysis oil has proven challenging. The organic fraction is highly corrosive because of its high organic acid content. High water content lowers the net heating value and can increase corrosivity. It can be poorly soluble in petroleum or petroleum products and can readily absorb water. Distillation residues can be as high as 50%, viscosity can be high, oils can exhibit poor stability in storage, and they can contain suspended solids. The ignition quality of raw pyrolysis oils is poor, with cetane number estimates ranging from 0 to 35, but more likely to be in the lower end of that range. While the use of raw pyrolysis oils in certain specific applications with specialized combustion equipment may be possible, raw oils must be significantly upgraded for use in on-highway spark-ignition (SI) and compression-ignition (CI) engines. Upgrading approaches most often involve catalytic hydrodeoxygenation, one of a class of reactions known as hydrotreating or hydroprocessing. This chapter discusses the properties of raw and upgraded pyrolysis oils, as well as the potential for integrating biomass pyrolysis with a petroleum refinery to significantly reduce the hydroprocessing cost.

  2. Extent of pyrolysis impacts on fast pyrolysis biochar properties.

    PubMed

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

    2012-01-01

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

  3. Initiation reactions in acetylene pyrolysis

    DOE PAGES

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

    2017-05-10

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

  4. Pyrolysis kinetics of lignocellulosic materials

    SciTech Connect

    Balci, S.; Dogu, T.; Yuecel, H. . Dept. of Chemical Engineering)

    1993-11-01

    Pyrolysis kinetics of almond and hazelnut shells and beech wood were carried out using a thermogravimetric technique. Experiments were repeated for different final pyrolysis temperatures ranging from 300 to 850 C. Approximately 90% of the pyrolysis reactions were completed up to 450 C. The initial values of the activation energy of pyrolysis reaction were found to be around 22 kcal/mol for shells of almond and hazelnut. On the other hand, initial activation energy of beech wood pyrolysis was found as 29.4 kcal/mol. Results indicated that a first-order decomposition in terms of volatile content of the reactant showed good agreement with the data only at the initial stages of the reaction. The reaction rate constant was found to decrease with reaction extent due to the changes in the chemical and physical structure of the solid. Among several models proposed, a model which predicted an increase of activation energy with reaction extent gave the best agreement with the experimental data.

  5. Vacuum Pyrolysis and Related ISRU Techniques

    NASA Technical Reports Server (NTRS)

    Cardiff, Eric H.; Pomeroy, Brian R.; Banks, Ian S.; Benz, Alexis

    2007-01-01

    A number of ISRU-related techniques have been developed at NASA Goddard Space Flight Center. The focus of the team has been on development of the vacuum pyrolysis technique for the production of oxygen from the lunar regolith. However, a number of related techniques have also been developed, including solar concentration, solar heating of regolith, resistive heating of regolith, sintering, regolith boiling, process modeling, parts manufacturing, and instrumentation development. An initial prototype system was developed to vaporize regolith simulants using a approx. l square meter Fresnel lens. This system was successfully used to vaporize quantities of approx. lg, and both mass spectroscopy of the gasses produced and Scanning Electron Microscopy (SEM) of the slag were done to show that oxygen was produced. Subsequent tests have demonstrated the use of a larger system With a 3.8m diameter reflective mirror to vaporize the regolith. These results and modeling of the vacuum pyrolysis reaction have indicated that the vaporization of the oxides in the regolith will occur at lower temperature for stronger vacuums. The chemical modeling was validated by testing of a resistive heating system that vaporized quantities of approx. 10g of MLS-1A. This system was also used to demonstrate the sintering of regolith simulants at reduced temperatures in high vacuum. This reduction in the required temperature prompted the development of a small-scale resistive heating system for application as a scientific instrument as well as a proof-of principle experiment for oxygen production.

  6. Volatile Analysis by Pyrolysis of Regolith for Planetary Resource Exploration

    NASA Technical Reports Server (NTRS)

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

    2012-01-01

    The extraction and identification of volatile resources that could be utilized by humans including water, oxygen, noble gases, and hydrocarbons on the Moon, Mars, and small planetary bodies will be critical for future long-term human exploration of these objects. Vacuum pyrolysis at elevated temperatures has been shown to be an efficient way to release volatiles trapped inside solid samples. In order to maximize the extraction of volatiles, including oxygen and noble gases from the breakdown of minerals, a pyrolysis temperature of 1400 C or higher is required, which greatly exceeds the maximum temperatures of current state-of-the-art flight pyrolysis instruments. Here we report on the recent optimization and field testing results of a high temperature pyrolysis oven and sample manipulation system coupled to a mass spectrometer instrument called Volatile Analysis by Pyrolysis of Regolith (VAPoR). VAPoR is capable of heating solid samples under vacuum to temperatures above 1300 C and determining the composition of volatiles released as a function of temperature.

  7. Novel technique for coal pyrolysis and hydrogenation product analysis

    SciTech Connect

    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.

  8. Pyrolysis and gasification of coal at high temperatures

    SciTech Connect

    Zygourakis, K.

    1990-01-01

    We made considerable progress towards developing a thermogravimetric reactor with in-situ video imaging capability (TGA/IVIM). Such a reactor will allow us to observe macroscopic changes in the morphology of pyrolyzing particles and thermal ignitions while monitoring at the time the weight of pyrolyzing or reacting samples. The systematic investigation on the effects of pyrolysis conditions and char macropore structure on char reactivity continued. Pyrolysis and gasification experiments were performed consecutively in our TGA reactor and the char reactivity patterns were measured for a wide range of temperatures (400 to 600[degrees]C). These conditions cover both the kinetic and the diffusion limited regimes. Our results show conclusively that chars produced at high pyrolysis heating rates (and, therefore, having a more open cellular macropore structure) are more reactive and ignite more easily than chars pyrolyzed at low heating rates. These results have been explained using available predictions from theoretical models. We also investigated for the first time the effect of coal particle size and external mass transfer limitations on the reactivity patterns and ignition behavior of char particles combusted in air. Finally, we used our hot stage reactor to monitor the structural transformations occurring during pyrolysis via a video microscopy system. Pyrolysis experiments were videotaped and particle swelling and the particle ignitions were determined and analyzed using digitized images from these experiments.

  9. Development of advanced technologies for biomass pyrolysis

    NASA Astrophysics Data System (ADS)

    Xu, Ran

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

  10. An Optically Accessible Pyrolysis Microreactor

    NASA Astrophysics Data System (ADS)

    Baraban, Joshua H.; David, Donald E.; Ellison, Barney; Daily, John W.

    2016-06-01

    We report an optically accessible pyrolysis micro-reactor suitable for in situ laser spectroscopic measurements. A radiative heating design allows for completely unobstructed views of the micro-reactor along two axes. The maximum temperature demonstrated here is only 1300 K (as opposed to 1700 K for the usual SiC micro-reactor) because of the melting point of fused silica, but alternative transparent materials will allow for higher temperatures. Laser induced fluorescence measurements on nitric oxide are presented as a proof of principle for spectroscopic characterization of pyrolysis conditions. (This work has been published in J. H. Baraban, D. E. David, G. B. Ellison, and J. W. Daily. An Optically Accessible Pyrolysis Micro-Reactor. Review of Scientific Instruments, 87(1):014101, 2016.)

  11. Kinetic investigation of wood pyrolysis

    SciTech Connect

    Thurner, F.; Mann, U.; Beck, S. R.

    1980-06-01

    The objective of this investigation was to determine the kinetics of the primary reactions of wood pyrolysis. A new experimental method was developed which enabled us to measure the rate of gas, tar, and char production while taking into account the temperature variations during the wood heating up. The experimental method developed did not require any sophisticated instruments. It facilitated the collection of gas, tar and residue (unreacted wood and char) as well as accurate measurement of the temperature inside the wood sample. Expressions relating the kinetic parameters to the measured variables were derived. The pyrolysis kinetics was investigated in the range of 300 to 400/sup 0/C at atmospheric pressure and under nitrogen atmosphere. Reaction temperature and mass fractions of gas, tar, and residue were measured as a function of time. Assuming first-order reactions, the kinetic parameters were determined using differential method. The measured activation energies of wood pyrolysis to gas, tar, and char were 88.6, 112.7, and 106.5 kJ/mole, respectively. These kinetic data were then used to predict the yield of the various pyrolysis products. It was found that the best prediction was obtained when an integral-mean temperature obtained from the temperature-time curve was used as reaction temperature. The pyrolysis products were analyzed to investigate the influence of the pyrolysis conditions on the composition. The gas consisted mainly of carbon dioxide, carbon monoxide, oxygen, and C/sub 3//sup +/-compounds. The gas composition depended on reaction time as well as reactor temperature. The tar analysis indicated that the tar consisted of about seven compounds. Its major compound was believed to be levoglucosan. Elemental analysis for the char showed that the carbon content increased with increasing temperature.

  12. An optically accessible pyrolysis microreactor

    SciTech Connect

    Baraban, J. H.; Ellison, G. Barney; David, D. E.; Daily, J. W.

    2016-01-15

    We report an optically accessible pyrolysis micro-reactor suitable for in situ laser spectroscopic measurements. A radiative heating design allows for completely unobstructed views of the micro-reactor along two axes. The maximum temperature demonstrated here is only 1300 K (as opposed to 1700 K for the usual SiC micro-reactor) because of the melting point of fused silica, but alternative transparent materials will allow for higher temperatures. Laser induced fluorescence measurements on nitric oxide are presented as a proof of principle for spectroscopic characterization of pyrolysis conditions.

  13. Impact of thermal pretreatment on the fast pyrolysis conversion of Southern Pine

    SciTech Connect

    Tyler L. Westover; Manunya Phanphanich; Micael L. Clark; Sharna R. Rowe; Steven E. Egan; Christopher T Wright; Richard D. Boardman; Alan H. Zacher

    2013-01-01

    Background: Thermal pretreatment of biomass ranges from simple (nondestructive) drying to more severe treatments that cause devolatization, depolymerization and carbonization. These pretreatments have demonstrated promise for transforming raw biomass into feedstock material that has improved milling, handling, storage and conversion properties. In this work, southern pine material was pretreated at 120, 180, 230 and 270 degrees C, and then subjected to pyrolysis tests in a continuous-feed bubbling-fluid bed pyrolysis system. Results: High pretreatment temperatures were associated with lower specific grinding energies, higher grinding rates and lower hydrogen and oxygen contents. Higher pretreatment temperatures were also correlated with increased char production, decreased total acid number and slight decrease in the oxygen content of the pyrolysis liquid fraction. Conclusion: Thermal pretreatment has both beneficial and detrimental impacts on fast pyrolysis conversion of pine material to bio-oil, and the effect of thermal pretreatment on upgrading of pyrolysis bio-oil requires further attention.

  14. Upgrading of Intermediate Bio-Oil Produced by Catalytic Pyrolysis

    SciTech Connect

    Abdullah, Zia; Chadwell, Brad; Taha, Rachid; Hindin, Barry; Ralston, Kevin

    2015-06-30

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

  15. Kinetics study on biomass pyrolysis for fuel gas production.

    PubMed

    Chen, Guan-Yi; Fang, Meng-Xiang; Andries, J; Luo, Zhong-Yang; Spliethoff, H; Cen, Ke-Fa

    2003-01-01

    Kinetic knowledge is of great importance in achieving good control of the pyrolysis and gasification process and optimising system design. An overall kinetic pyrolysis scheme is therefore addressed here. The kinetic modelling incorporates the following basic steps: the degradation of the virgin biomass materials into primary products (tar, gas and semi-char), the decomposition of primary tar into secondary products and the continuous interaction between primary gas and char. The last step is disregarded completely by models in the literature. Analysis and comparison of predicted results from different kinetic schemes and experimental data on our fixed bed pyrolyser yielded very positive evidence to support our kinetic scheme.

  16. Methods and apparatuses for preparing upgraded pyrolysis oil

    DOEpatents

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

    2013-10-01

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

  17. Experimental toxicology of pyrolysis and combustion hazards.

    PubMed Central

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

    1975-01-01

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

  18. Autothermal pyrolysis of waste tires

    SciTech Connect

    Wey, M.Y.; Liou, B.H.; Wu, S.Y.; Zhang, C.H.

    1995-11-01

    The main objective of this research was to study the operating parameters of autothermal pyrolysis of scrap tires in a laboratory-scale fluidized bed reactor with a 100-cm bed height (10 cm I.D.) and a 100-cm freeboard (25 cm I.D.). Scrap tires were pyrolyzed in a limited oxygen supply, so that the heat for pyrolysis of the scrap tires was provided by combustion of some portion of the scrap tires. The operating parameters evaluated included the effect on the pyrolysis oil products and their relative proportions of (1) the air factor (0.07-0.035); (2) the pyrolysis temperature (370-570{degree}C); and (3) the catalyst added (zeolite and calcium carbonate). The results show that: (1) the composition of the liquid hydrocarbon obtained is affected significantly by the air factor; (2) the higher operating temperature caused a higher yield of gasoline and diesel; (3) the yield of gasoline increased due to the catalyst zeolite added, and the yield of diesel increased due to the addition of the catalyst calcium carbonate; (4) the principal constituents of gasoline included dipentene and diprene. 30 refs., 10 figs., 5 tabs.

  19. Pyrolysis kinetics of waste PVC pipe.

    PubMed

    Kim, S

    2001-01-01

    The pyrolysis kinetics of waste PVC pipe was investigated with a thermal gravimetric analysis system at heating rates of 5, 10, and 30 degrees C/min in a nitrogen atmosphere. Freeman-Carroll method was employed to evaluate kinetic parameters. Two dominant peaks were observed on derivative gravimetric curves, hypothetically suggesting a two-stage apparent reaction model. The first-stage reaction was likely to be represented by stoichiometric reaction to yield volatiles (mainly HCl) and intermediates. The second-stage reaction might be described by thermal degradation of intermediates competitively into gas, liquid, and solid by-products. Quasi-isothermal operations were introduced to verify the reaction types of the first and second reaction. The generation reaction of intermediates achieved at lower temperatures was carried out independently with their decomposition reaction at higher temperatures. The effects of additives on the pyrolysis kinetics of waste PVC pipe seem to be significant, especially on the first-stage reaction. The first-stage reaction was retarded. A merged peak at low temperatures was observed on the derivative thermogravimetry (DTG) curve instead of two peaks usually observed for that of pure PVC resin. The first peak on the DTG curve of pure PVC resin may shift more, resulting in the complete overlap of two peaks. The quantity of evolved HCl was likely to decrease because of interaction of metal components of stabilizers with either HCl or active chlorine atom or both. The final residual fraction increased as a result of pyrolysis of organic forms of additives to yield extra char. On the other hand, the second-stage reaction kinetics demonstrates a similar pattern to that of pure PVC resin, implying that the effects of additives may be less significant in comparison with that at the first-stage reaction.

  20. Dual fluidized bed design for the fast pyrolysis of biomass

    USDA-ARS?s Scientific Manuscript database

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

  1. A summary of the report on prospects for pyrolysis technologies in managing municipal, industrial, and Department of Energy cleanup wastes

    SciTech Connect

    Reaven, S.J.

    1994-08-01

    Pyrolysis converts portions of municipal solid wastes, hazardous wastes and special wastes such as tires, medical wastes and even old landfills into solid carbon and a liquid or gaseous hydrocarbon stream. In the past twenty years, advances in the engineering of pyrolysis systems and in sorting and feeding technologies for solid waste industries have ensured consistent feedstocks and system performance. Some vendors now offer complete pyrolysis systems with performance warranties. This report analyzes the potential applications of pyrolysis in the Long Island region and evaluates the four most promising pyrolytic systems for their readiness, applicability to regional waste management needs and conformity with DOE environmental restoration and waste management requirements. This summary characterizes the engineering performance, environmental effects, costs, product applications and markets for these pyrolysis systems.

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

    PubMed

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

    2015-11-17

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

  3. Dissolved phosphorus speciation of flash carbonization, slow pyrolysis, and fast pyrolysis biochars

    USDA-ARS?s Scientific Manuscript database

    Pyrolysis of waste biomass is a promising technology to produce sterile and renewable organic phosphorus fertilizers. Systematic studies are necessary to understand how different pyrolysis platforms influence the chemical speciation of dissolved (bioavailable) phosphorus. This study employed solut...

  4. Valorization of Rhizoclonium sp. algae via pyrolysis and catalytic pyrolysis.

    PubMed

    Casoni, Andrés I; Zunino, Josefina; Piccolo, María C; Volpe, María A

    2016-09-01

    The valorization of Rhizoclonium sp. algae through pyrolysis for obtaining bio-oils is studied in this work. The reaction is carried out at 400°C, at high contact time. The bio-oil has a practical yield of 35% and is rich in phytol. Besides, it is simpler than the corresponding to lignocellulosic biomass due to the absence of phenolic compounds. This property leads to a bio-oil relatively stable to storage. In addition, heterogeneous catalysts (Al-Fe/MCM-41, SBA-15 and Cu/SBA-15), in contact with algae during pyrolysis, are analyzed. The general trend is that the catalysts decrease the concentration of fatty alcohols and other high molecular weight products, since their mild acidity sites promote degradation reactions. Thus, the amount of light products increases upon the use of the catalysts. Particularly, acetol concentration in the bio-oils obtained from the catalytic pyrolysis with SBA-15 and Cu/SBA-15 is notably high. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Fast pyrolysis of oil palm shell (OPS)

    NASA Astrophysics Data System (ADS)

    Abdullah, Nurhayati; Sulaiman, Fauziah; Aliasak, Zalila

    2015-04-01

    Biomass is an important renewable source of energy. Residues that are obtained from harvesting and agricultural products can be utilised as fuel for energy generation by conducting any thermal energy conversion technology. The conversion of biomass to bio oil is one of the prospective alternative energy resources. Therefore, in this study fast pyrolysis of oil palm shell was conducted. The main objective of this study was to find the optimum condition for high yield bio-oil production. The experiment was conducted using fixed-bed fluidizing pyrolysis system. The biomass sample was pyrolysed at variation temperature of 450°C - 650°C and at variation residence time of 0.9s - 1.35s. The results obtained were further discussed in this paper. The basic characteristic of the biomass sample was also presented here. The experiment shows that the optimum bio-oil yield was obtained at temperature of 500°C at residence time 1.15s.

  6. Desulfurized gas production from vertical kiln pyrolysis

    DOEpatents

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

    1978-05-30

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

  7. Apparatus for entrained coal pyrolysis

    DOEpatents

    Durai-Swamy, Kandaswamy

    1982-11-16

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

  8. Fast Pyrolysis of Wood for Biofuels: Spatiotemporally Resolved Diffuse Reflectance In situ Spectroscopy of Particles.

    PubMed

    Paulsen, Alex D; Hough, Blake R; Williams, C Luke; Teixeira, Andrew R; Schwartz, Daniel T; Pfaendtner, Jim; Dauenhauer, Paul J

    2014-02-20

    Fast pyrolysis of woody biomass is a promising process capable of producing renewable transportation fuels to replace gasoline, diesel, and chemicals currently derived from nonrenewable sources. However, biomass pyrolysis is not yet economically viable and requires significant optimization before it can contribute to the existing oil-based transportation system. One method of optimization uses detailed kinetic models for predicting the products of biomass fast pyrolysis, which serve as the basis for the design of pyrolysis reactors capable of producing the highest value products. The goal of this work is to improve upon current pyrolysis models, usually derived from experiments with low heating rates and temperatures, by developing models that account for both transport and pyrolysis decomposition kinetics at high heating rates and high temperatures (>400 °C). A new experimental technique is proposed herein: spatiotemporally resolved diffuse reflectance in situ spectroscopy of particles (STR-DRiSP), which is capable of measuring biomass composition during fast pyrolysis with high spatial (10 μm) and temporal (1 ms) resolution. Compositional data were compared with a comprehensive 2D single-particle model, which incorporated a multistep, semiglobal reaction mechanism, prescribed particle shrinkage, and thermophysical properties that varied with temperature, composition, and orientation. The STR-DRiSP technique can be used to determine the transport-limited kinetic parameters of biomass decomposition for a wide variety of biomass feedstocks.

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

    USDA-ARS?s Scientific Manuscript database

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

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

    USDA-ARS?s Scientific Manuscript database

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

  11. Pyrolysis processing for solid waste resource recovery

    NASA Technical Reports Server (NTRS)

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

    2007-01-01

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

  12. Pyrolysis process for producing fuel gas

    NASA Technical Reports Server (NTRS)

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

    2007-01-01

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

  13. Pyrolysis mechanisms of thiophene and methylthiophene in asphaltenes.

    PubMed

    Song, Xinli; Parish, Carol A

    2011-04-07

    The pyrolysis mechanisms of thiophene in asphaltenes have been investigated theoretically using density functional and ab initio quantum chemical techniques. All of the possible reaction pathways were explored using B3LYP, MP2, and CBS-QB3 models. A comparison of the calculated heats of reaction with the available experimental values indicates that the CBS-QB3 level of theory is quantitatively reliable for calculating the energetic reaction paths of the title reactions. The pyrolysis process is initiated via four different types of hydrogen migrations. According to the reaction barrier heights, the dominant 1,2-H shift mechanism involves two competitive product channels, namely, C(2)H(2) + CH(2)CS and CS + CH(3)CCH. The minor channels include the formation of CS + CH(2)CCH(2), H(2)S + C(4)H(2), HCS + CH(2)CCH, CS + CH(2)CHCH, H + C(4)H(3)S, and HS + C(4)H(3). The methyl substitution effect was investigated with the pyrolysis of 2-methylthiophene and 3-methylthiophene. The energetics of such systems were very similar to that for unsubstituted thiophene, suggesting that thiophene alkylation may not play a significant role in the pyrolysis of asphaltene compounds.

  14. Rapid identification of bacteria with miniaturized pyrolysis/GC analysis

    NASA Astrophysics Data System (ADS)

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

    2001-02-01

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

  15. Co-pyrolysis of coal with organic solids

    SciTech Connect

    Straka, P.; Buchtele, J.

    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.

  16. Zinc oxide films prepared by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Maciąg, Andrzej; Sagan, Piotr; Kuźma, Marian; Popovych, Volodymyr

    2016-12-01

    In this work we developed and tested spray pyrolysis system for layers deposition. In the system we have used ultrasonic apparatus (nebulizator) as a sprayer. A zinc nitrate aqueous solution has been used as a precursor solution. The idea of the method is the decomposition of nitrate on a hot substrate according to the reaction Zn(NO3)2 → ZnO +2 NO2 +1/2O2. The layers were grown on glass, (001)Si and KCl substrates at the temperatures 300 - 500°C. The thickness of the obtained layers was in the range 50 - 500 nm, depending on the growth time and rate. The influence of substrate temperature on the morphology of the layers has been studied by SEM method. The energy gap of the layers was found to be the range of 3.26-3.3 eV from their absorption spectra.

  17. Zinc oxide films prepared by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Maciąg, Andrzej; Sagan, Piotr; Kuźma, Marian; Popovych, Volodymyr

    2017-01-01

    In this work we developed and tested spray pyrolysis system for layers deposition. In the system we have used ultrasonic apparatus (nebulizator) as a sprayer. A zinc nitrate aqueous solution has been used as a precursor solution. The idea of the method is the decomposition of nitrate on a hot substrate according to the reaction Zn(NO3)2 → ZnO +2 NO2 +1/2O2. The layers were grown on glass, (001)Si and KCl substrates at the temperatures 300 - 500°C. The thickness of the obtained layers was in the range 50 - 500 nm, depending on the growth time and rate. The influence of substrate temperature on the morphology of the layers has been studied by SEM method. The energy gap of the layers was found to be the range of 3.26-3.3 eV from their absorption spectra.

  18. Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

    SciTech Connect

    Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.; Biddy, Mary J.; Knott, Brandon C.; Jarvis, Mark W.; Olstad, Jessica; Mante, Ofei D.; Dayton, David C.; Beckham, Gregg T.

    2016-09-05

    Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, here we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg-1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg-1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent

  19. Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

    DOE PAGES

    Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.; ...

    2016-09-05

    Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, heremore » we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg-1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg-1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent development of selective

  20. Aqueous stream characterization from biomass fast pyrolysis and catalytic fast pyrolysis

    SciTech Connect

    Black, Brenna A.; Michener, William E.; Ramirez, Kelsey J.; Biddy, Mary J.; Knott, Brandon C.; Jarvis, Mark W.; Olstad, Jessica; Mante, Ofei D.; Dayton, David C.; Beckham, Gregg T.

    2016-09-05

    Here, biomass pyrolysis offers a promising means to rapidly depolymerize lignocellulosic biomass for subsequent catalytic upgrading to renewable fuels. Substantial efforts are currently ongoing to optimize pyrolysis processes including various fast pyrolysis and catalytic fast pyrolysis schemes. In all cases, complex aqueous streams are generated containing solubilized organic compounds that are not converted to target fuels or chemicals and are often slated for wastewater treatment, in turn creating an economic burden on the biorefinery. Valorization of the species in these aqueous streams, however, offers significant potential for substantially improving the economics and sustainability of thermochemical biorefineries. To that end, here we provide a thorough characterization of the aqueous streams from four pilot-scale pyrolysis processes: namely, from fast pyrolysis, fast pyrolysis with downstream fractionation, in situ catalytic fast pyrolysis, and ex situ catalytic fast pyrolysis. These configurations and processes represent characteristic pyrolysis processes undergoing intense development currently. Using a comprehensive suite of aqueous-compatible analytical techniques, we quantitatively characterize between 12 g kg-1 of organic carbon of a highly aqueous catalytic fast pyrolysis stream and up to 315 g kg-1 of organic carbon present in the fast pyrolysis aqueous streams. In all cases, the analysis ranges between 75 and 100% of mass closure. The composition and stream properties closely match the nature of pyrolysis processes, with high contents of carbohydrate-derived compounds in the fast pyrolysis aqueous phase, high acid content in nearly all streams, and mostly recalcitrant phenolics in the heavily deoxygenated ex situ catalytic fast pyrolysis stream. Overall, this work provides a detailed compositional analysis of aqueous streams from leading thermochemical processes -- analyses that are critical for subsequent

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

    SciTech Connect

    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.

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

    PubMed

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

    2010-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    Ramped pyrolysis methodology, such as that used in the programmed-temperature pyrolysis/combustion system (PTP/CS), improves radiocarbon analysis of geologic materials devoid of authigenic carbonate compounds and with low concentrations of extractable authochthonous organic molecules. The approach has improved sediment chronology in organic-rich sediments proximal to Antarctic ice shelves (Rosenheim et al., 2008) and constrained the carbon sequestration potential of suspended sediments in the lower Mississippi River (Roe et al., in review). Although ramped pyrolysis allows for separation of sedimentary organic material based upon relative reactivity, chemical information (i.e. chemical composition of pyrolysis products) is lost during the in-line combustion of pyrolysis products. A first order approximation of ramped pyrolysis/combustion system CO2 evolution, employing a simple Gaussian decomposition routine, has been useful (Rosenheim et al., 2008), but improvements may be possible. First, without prior compound-specific extractions, the molecular composition of sedimentary organic matter is unknown and/or unidentifiable. Second, even if determined as constituents of sedimentary organic material, many organic compounds have unknown or variable decomposition temperatures. Third, mixtures of organic compounds may result in significant chemistry within the pyrolysis reactor, prior to introduction of oxygen along the flow path. Gaussian decomposition of the reaction rate may be too simple to fully explain the combination of these factors. To relate both the radiocarbon age over different temperature intervals and the pyrolysis reaction thermograph (temperature (°C) vs. CO2 evolved (μmol)) obtained from PTP/CS to chemical composition of sedimentary organic material, we present a modeling framework developed based upon the ramped pyrolysis decomposition of simple mixtures of organic compounds (i.e. cellulose, lignin, plant fatty acids, etc.) often found in sedimentary

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

    SciTech Connect

    Diebold, J. P.; Scahill, J. W.; Evans, R. J.

    1986-07-01

    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.

  5. Fractional condensation of pyrolysis vapors produced from Nordic feedstocks in cyclone pyrolysis

    DOE PAGES

    Johansson, Ann-Christine; Lisa, Kristiina; Sandström, Linda; ...

    2016-12-06

    Pyrolysis oil is a complex mixture of different chemical compounds with a wide range of molecular weights and boiling points. Due to its complexity, an efficient fractionation of the oil may be a more promising approach of producing liquid fuels and chemicals than treating the whole oil. In this work a sampling system based on fractional condensation was attached to a cyclone pyrolysis pilot plant to enable separation of the produced pyrolysis vapors into five oil fractions. The sampling system was composed of cyclonic condensers and coalescing filters arranged in series. Our objective was to characterize the oil fractions producedmore » from three different Nordic feedstocks and suggest possible applications. The oil fractions were thoroughly characterized using several analytical techniques including water content; elemental composition; heating value, and chemical compound group analysis using solvent fractionation, quantitative 13C NMR and 1H NMR and GC x GC - TOFMS. The results show that the oil fractions significantly differ from each other both in chemical and physical properties. The first fractions and the fraction composed of aerosols were highly viscous and contained larger energy-rich compounds of mainly lignin-derived material. The middle fraction contained medium-size compounds with relatively high concentration of water, sugars, alcohols, hydrocarbonyls and acids and finally the last fraction contained smaller molecules such as water, aldehydes, ketones and acids. But, the properties of the respective fractions seem independent on the studied feedstock types, i.e. the respective fractions produced from different feedstock are rather similar. Furthermore, this promotes the possibility to vary the feedstock depending on availability while retaining the oil properties. Possible applications of the five fractions vary from oil for combustion and extraction of the pyrolytic lignin in the early fractions to extraction of sugars from the early and middle

  6. Fractional condensation of pyrolysis vapors produced from Nordic feedstocks in cyclone pyrolysis

    SciTech Connect

    Johansson, Ann-Christine; Lisa, Kristiina; Sandström, Linda; Ben, Haoxi; Pilath, Heidi; Deutch, Steve; Wiinikka, Henrik; Öhrman, Olov G. W.

    2016-12-06

    Pyrolysis oil is a complex mixture of different chemical compounds with a wide range of molecular weights and boiling points. Due to its complexity, an efficient fractionation of the oil may be a more promising approach of producing liquid fuels and chemicals than treating the whole oil. In this work a sampling system based on fractional condensation was attached to a cyclone pyrolysis pilot plant to enable separation of the produced pyrolysis vapors into five oil fractions. The sampling system was composed of cyclonic condensers and coalescing filters arranged in series. Our objective was to characterize the oil fractions produced from three different Nordic feedstocks and suggest possible applications. The oil fractions were thoroughly characterized using several analytical techniques including water content; elemental composition; heating value, and chemical compound group analysis using solvent fractionation, quantitative 13C NMR and 1H NMR and GC x GC - TOFMS. The results show that the oil fractions significantly differ from each other both in chemical and physical properties. The first fractions and the fraction composed of aerosols were highly viscous and contained larger energy-rich compounds of mainly lignin-derived material. The middle fraction contained medium-size compounds with relatively high concentration of water, sugars, alcohols, hydrocarbonyls and acids and finally the last fraction contained smaller molecules such as water, aldehydes, ketones and acids. But, the properties of the respective fractions seem independent on the studied feedstock types, i.e. the respective fractions produced from different feedstock are rather similar. Furthermore, this promotes the possibility to vary the feedstock depending on availability while retaining the oil properties. Possible applications of the five fractions vary from oil for combustion and extraction of the pyrolytic lignin in the early fractions to extraction of sugars from the

  7. Re-Os geochronology and Os isotope fingerprinting of petroleum sourced from a Type I lacustrine kerogen: insights from the natural Green River petroleum system in the Uinta Basin and hydrous pyrolysis experiments

    USGS Publications Warehouse

    Cumming, Vivien M.; Selby, David; Lillis, Paul G.; Lewan, Michael D.

    2014-01-01

    Rhenium–osmium (Re–Os) geochronology of marine petroleum systems has allowed the determination of the depositional age of source rocks as well as the timing of petroleum generation. In addition, Os isotopes have been applied as a fingerprinting tool to correlate oil to its source unit. To date, only classic marine petroleum systems have been studied. Here we present Re–Os geochronology and Os isotope fingerprinting of different petroleum phases (oils, tar sands and gilsonite) derived from the lacustrine Green River petroleum system in the Uinta Basin, USA. In addition we use an experimental approach, hydrous pyrolysis experiments, to compare to the Re–Os data of naturally generated petroleum in order to further understand the mechanisms of Re and Os transfer to petroleum. The Re–Os geochronology of petroleum from the lacustrine Green River petroleum system (19 ± 14 Ma – all petroleum phases) broadly agrees with previous petroleum generation basin models (∼25 Ma) suggesting that Re–Os geochronology of variable petroleum phases derived from lacustrine Type I kerogen has similar systematics to Type II kerogen (e.g., Selby and Creaser, 2005a, Selby and Creaser, 2005b and Finlay et al., 2010). However, the large uncertainties (over 100% in some cases) produced for the petroleum Re–Os geochronology are a result of multiple generation events occurring through a ∼3000-m thick source unit that creates a mixture of initial Os isotope compositions in the produced petroleum phases. The 187Os/188Os values for the petroleum and source rocks at the time of oil generation vary from 1.4 to 1.9, with the mode at ∼1.6. Oil-to-source correlation using Os isotopes is consistent with previous correlation studies in the Green River petroleum system, and illustrates the potential utility of Os isotopes to characterize the spatial variations within a petroleum system. Hydrous pyrolysis experiments on the Green River Formation source rocks show that Re and Os transfer

  8. Re-Os geochronology and Os isotope fingerprinting of petroleum sourced from a Type I lacustrine kerogen: Insights from the natural Green River petroleum system in the Uinta Basin and hydrous pyrolysis experiments

    NASA Astrophysics Data System (ADS)

    Cumming, Vivien M.; Selby, David; Lillis, Paul G.; Lewan, Michael D.

    2014-08-01

    Rhenium-osmium (Re-Os) geochronology of marine petroleum systems has allowed the determination of the depositional age of source rocks as well as the timing of petroleum generation. In addition, Os isotopes have been applied as a fingerprinting tool to correlate oil to its source unit. To date, only classic marine petroleum systems have been studied. Here we present Re-Os geochronology and Os isotope fingerprinting of different petroleum phases (oils, tar sands and gilsonite) derived from the lacustrine Green River petroleum system in the Uinta Basin, USA. In addition we use an experimental approach, hydrous pyrolysis experiments, to compare to the Re-Os data of naturally generated petroleum in order to further understand the mechanisms of Re and Os transfer to petroleum. The Re-Os geochronology of petroleum from the lacustrine Green River petroleum system (19 ± 14 Ma - all petroleum phases) broadly agrees with previous petroleum generation basin models (∼25 Ma) suggesting that Re-Os geochronology of variable petroleum phases derived from lacustrine Type I kerogen has similar systematics to Type II kerogen (e.g., Selby and Creaser, 2005a,b; Finlay et al., 2010). However, the large uncertainties (over 100% in some cases) produced for the petroleum Re-Os geochronology are a result of multiple generation events occurring through a ∼3000-m thick source unit that creates a mixture of initial Os isotope compositions in the produced petroleum phases. The 187Os/188Os values for the petroleum and source rocks at the time of oil generation vary from 1.4 to 1.9, with the mode at ∼1.6. Oil-to-source correlation using Os isotopes is consistent with previous correlation studies in the Green River petroleum system, and illustrates the potential utility of Os isotopes to characterize the spatial variations within a petroleum system. Hydrous pyrolysis experiments on the Green River Formation source rocks show that Re and Os transfer are mimicking the natural system. This

  9. Fast Pyrolysis Conversion Tests of Forest Concepts' Crumbles™. Final Report

    SciTech Connect

    Santosa, Daniel M.; Zacher, Alan H.; Eakin, David E.

    2012-04-02

    The report describes the work done by PNNL on assessing Forest Concept's engineered feedstock using the bench-scale continuous fast pyrolysis system to produce liquid bio-oil, char and gas. Specifically, bio-oil from the following process were evaluated for its yield and quality to determine impact of varying feed size parameters. Furthermore, the report also describes the handling process of the biomass and the challenges of operating the system with above average particle size.

  10. Electrochemical and/or microbiological treatment of pyrolysis wastewater.

    PubMed

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

    2017-10-01

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

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

    PubMed Central

    Honma, Sensho; Hata, Toshimitsu; Watanabe, Takashi

    2014-01-01

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

  12. Biofuel from fast pyrolysis and catalytic hydrodeoxygenation.

    SciTech Connect

    Elliott, Douglas C.

    2015-09-04

    This review addresses recent developments in biomass fast pyrolysis bio-oil upgrading by catalytic hydrotreating. The research in the field has expanded dramatically in the past few years with numerous new research groups entering the field while existing efforts from others expand. The issues revolve around the catalyst formulation and operating conditions. Much work in batch reactor tests with precious metal catalysts needs further validation to verify long-term operability in continuous flow systems. The effect of the low level of sulfur in bio-oil needs more study to be better understood. Utilization of the upgraded bio-oil for feedstock to finished fuels is still in an early stage of understanding.

  13. Solar heated vacuum pyrolysis of lunar soil

    NASA Astrophysics Data System (ADS)

    Sauerborn, M.; Neumann, A.; Seboldt, W.; Diekmann, B.

    The goal of the project is the thermal reduction of samples of lunar regolith simulant as a possible technique for producing oxygen by pyrolysis on a lunar base. The extraterrestrial production of oxygen is a key technology for a lunar base or manned missions to near-Earth asteroids or Mars. The solar heated vacuum pyrolysis has some important advantages, because it is based upon the realities of the lunar environment. As a tool for investigating the basic reactions and the technology the DLR High Flux Solar Furnace was used. This facility is operated since 1994 in Cologne. It delivers concentrated solar radiation up to a peak flux of 5 MW/m2. This power can be used to cause thermal or photochemical effects in irradiated materials. For the astrophysical and mineralogical applications discussed here, a vacuum chamber with a solar-adapted design and new instrumentation was developed. The pyrolysis experiments were conducted under high vacuum. Using the concentrated beam of the solar furnace as heat source, the lunar soil simulant samples achieved liquid phase in 10 - 20 seconds and reached temperatures between 1500 to 1900 K, were the relevant processes took place. The heating phase was followed by a controlled cooling. The partial pressure of oxygen and several other constituents in the vapour phase was measured with a differentially pumped quadrupole mass spectrometer. The temperatures of the samples were measured by an IR camera with a special optical system. Baseline experiments with different reference metal oxides like SiO2, CaO, and ZnO were made to verify the apparatus and investigate background contamination. The data of the five experiments with regolith showed typical features and a similar behaviour of gas partial pressure depending on temperature level, with an increase of oxygen during the strongest irradiation. The detected oxygen originates from thermal decomposition of the mineral sample and caused a large numbers of gas bubbles inside the melt

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

    SciTech Connect

    George, Anthe; Geier, Manfred; Dedrick, Daniel E.

    2014-10-01

    The viability of thermochemically-derived biofuels can be greatly enhanced by reducing the process parasitic energy loads. Integrating renewable power into biofuels production is one method by which these efficiency drains can be eliminated. There are a variety of such potentially viable "hybrid-renewable" approaches; one is to integrate concentrated solar power (CSP) to power biomass-to-liquid fuels (BTL) processes. Barriers to CSP integration into BTL processes are predominantly the lack of fundamental kinetic and mass transport data to enable appropriate systems analysis and reactor design. A novel design for the reactor has been created that can allow biomass particles to be 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.

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

    PubMed

    Islam, M R; Joardder, M U H; Hasan, S M; Takai, K; Haniu, H

    2011-01-01

    In this study on the basis of lab data and available resources in Bangladesh, feasibility study has been carried out for pyrolysis process converting solid tire wastes into pyrolysis oils, solid char and gases. The process considered for detailed analysis was fixed-bed fire-tube heating pyrolysis reactor system. The comparative techno-economic assessment was carried out in US$ for three different sizes plants: medium commercial scale (144 tons/day), small commercial scale (36 tons/day), pilot scale (3.6 tons/day). The assessment showed that medium commercial scale plant was economically feasible, with the lowest unit production cost than small commercial and pilot scale plants for the production of crude pyrolysis oil that could be used as boiler fuel oil and for the production of upgraded liquid-products. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

    SciTech Connect

    Islam, M.R.; Joardder, M.U.H.; Hasan, S.M.; Takai, K.; Haniu, H.

    2011-09-15

    In this study on the basis of lab data and available resources in Bangladesh, feasibility study has been carried out for pyrolysis process converting solid tire wastes into pyrolysis oils, solid char and gases. The process considered for detailed analysis was fixed-bed fire-tube heating pyrolysis reactor system. The comparative techno-economic assessment was carried out in US$ for three different sizes plants: medium commercial scale (144 tons/day), small commercial scale (36 tons/day), pilot scale (3.6 tons/day). The assessment showed that medium commercial scale plant was economically feasible, with the lowest unit production cost than small commercial and pilot scale plants for the production of crude pyrolysis oil that could be used as boiler fuel oil and for the production of upgraded liquid-products.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

  18. Microwave-assisted pyrolysis of methyl ricinoleate for continuous production of undecylenic acid methyl ester (UAME).

    PubMed

    Nie, Yong; Duan, Ying; Gong, Ruchao; Yu, Shangzhi; Lu, Meizhen; Yu, Fengwen; Ji, Jianbing

    2015-06-01

    Undecylenic acid methyl ester (UAME) was continuously produced from methyl ricinoleate using a microwave-assisted pyrolysis system with atomization feeding. The UAME yield of 77 wt.% was obtained at 500°C using SiC as the microwave absorbent and heating medium. The methyl ricinoleate conversion and UAME yield from microwave-assisted pyrolysis process were higher than those from conventional pyrolysis. The effect of temperature on the pyrolysis process was also investigated. The methyl ricinoleate conversion increased but the cracking liquid yield decreased when the temperature increased from 460°C to 560°C. The maximum UAME yield was obtained at the temperature of 500°C.

  19. Preliminary results in the fast pyrolysis of biomass to lower olefins

    SciTech Connect

    Diebold, J.P.

    1980-08-01

    The pyrolysis of pure cellulose and -80-mesh birch wood flour in a low-residence-time, entrained-flow tubular reactor yielded primarily gaseous products, with virtually no char formation. There were some condensible by-products which were almost entirely water soluble. The gases contained significant amounts of olefinic hydrocarbons such as ethylene. Although the yields of the olefinic hydrocarbons were not as high as previous yields from trash-derived organics, this study demonstrated that cellulose and biomass can be used to produce ethylene and other olefins in better yields than attained in conventional gasifiers. Very little of the char from birch wood pyrolysis had a charcoal appearance in scanning electron microscope photographs; instead, it had a sintered or agglomerated appearance. This implies that the char was formed by a different mechanism than charcoal and involves a liquification step. The attempts to feed lignin powder into the reactor, which resulted in the material sintering, bubbling, and charring at the reactor entrance, suggest that the agglomerated birch char particles may have been agglomerated birch lignin char particles; in fact, the heat of combustion of the char was close to that of lignin on an ash-free basis. A feed system for continuous pyrolysis research should be more reproducible and resistant to mass flow fluctuations than the China Lake pyrolysis steam as it was evolved to make pyrolysis gases for the previous gas purification system check out and demonstration. This study consisted of only a preliminary screening of the pyrolysis of pure cellulose, wood flour, and pure lignin. The pyrolysis of these materials needs to be further characterized. The ability to use relatively large feedstock particles in fast pyrolysis to produce olefins would significantly reduce the cost and process energy requirements of feedstock preparation.

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

    NASA Astrophysics Data System (ADS)

    Boon, Jaap J.

    1992-09-01

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

  1. Pyrolysis and mass spectrometry studies of meteoritic organic matter.

    PubMed

    Sephton, M A

    2012-01-01

    Meteorites are fragments of extraterrestrial materials that fall to the Earth's surface. The carbon-rich meteorites are derived from ancient asteroids that have remained relatively unprocessed since the formation of the Solar System 4.56 billion years ago. They contain a variety of extraterrestrial organic molecules that are a record of chemical evolution in the early Solar System and subsequent aqueous and thermal processes on their parent bodies. The major organic component (>70%) is a macromolecular material that resists straightforward solvent extraction. In response to its intractable nature, the most common means of investigating this exotic material involves a combination of thermal decomposition (pyrolysis) and mass spectrometry. Recently the approach has also been used to explore controversial claims of organic matter in meteorites from Mars. This review summarizes the pyrolysis data obtained from meteorites and outlines key interpretations.

  2. Transportation fuels from biomass via fast pyrolysis and hydroprocessing

    SciTech Connect

    Elliott, Douglas C.

    2013-09-21

    Biomass is a renewable source of carbon, which could provide a means to reduce the greenhouse gas impact from fossil fuels in the transportation sector. Biomass is the only renewable source of liquid fuels, which could displace petroleum-derived products. Fast pyrolysis is a method of direct thermochemical conversion (non-bioconversion) of biomass to a liquid product. Although the direct conversion product, called bio-oil, is liquid; it is not compatible with the fuel handling systems currently used for transportation. Upgrading the product via catalytic processing with hydrogen gas, hydroprocessing, is a means that has been demonstrated in the laboratory. By this processing the bio-oil can be deoxygenated to hydrocarbons, which can be useful replacements of the hydrocarbon distillates in petroleum. While the fast pyrolysis of biomass is presently commercial, the upgrading of the liquid product by hydroprocessing remains in development, although it is moving out of the laboratory into scaled-up process demonstration systems.

  3. Kinetics of coal pyrolysis

    SciTech Connect

    Seery, D.J.; Freihaut, J.D.; Proscia, W.M. ); Howard, J.B.; Peters, W.; Hsu, J.; Hajaligol, M.; Sarofim, A. ); Jenkins, R.; Mallin, J.; Espindola-Merin, B. ); Essenhigh, R.; Misra, M.K. )

    1989-07-01

    This report contains results of a coordinated, multi-laboratory investigation of coal devolatilization. Data is reported pertaining to the devolatilization for bituminous coals over three orders of magnitude in apparent heating rate (100 to 100,000 + {degree}C/sec), over two orders of magnitude in particle size (20 to 700 microns), final particle temperatures from 400 to 1600{degree}C, heat transfer modes ranging from convection to radiative, ambient pressure ranging from near vacuum to one atmosphere pressure. The heat transfer characteristics of the reactors are reported in detail. It is assumed the experimental results are to form the basis of a devolatilization data base. Empirical rate expressions are developed for each phase of devolatilization which, when coupled to an awareness of the heat transfer rate potential of a particular devolatilization reactor, indicate the kinetics emphasized by a particular system reactor plus coal sample. The analysis indicates the particular phase of devolatilization that will be emphasized by a particular reactor type and, thereby, the kinetic expressions appropriate to that devolatilization system. Engineering rate expressions are developed from the empirical rate expressions in the context of a fundamental understanding of coal devolatilization developed in the course of the investigation. 164 refs., 223 figs., 44 tabs.

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

    PubMed

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

    2004-01-01

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

  5. Electrochemically assisted pyrolysis of hardwoods

    SciTech Connect

    Koch, V.R.

    1986-08-01

    This project explored the low-temperature, electrochemically assisted pyrolysis of lignocellulosic material to low-molecular-weight organic chemicals. Through the agency of low temperature AlCl{sub 3}-based molten salts, aspen hardwood flour was reacted in AlCl{sub 3}:NaCl, AlCl{sub 3}:NaCl:KCl, and AlCl{sub 3}:BPC (n-butylpyridinium chloride) media at temperatures from 30-220 C. A wide variety of water soluble products were formed comprising CO, CO{sub 2}, keto-alcohols and low molecular weight phenolic compounds as determined by GC and FTIR spectroscopy. The compounds represented about 32% by weight of the aspen wood flour. Owing to the narrow (2 volt) electrochemical window versus an Al reference electrode, neither the wood flour nor the reaction products manifested any electro-activity. Authentic samples of cellulose, hemicellulose, and Klason lignin were also subjected to low temperature pyrolysis. Only the hemicellulose reacted to give CO{sub 2} and keto-alcohols.

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

    SciTech Connect

    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

  7. Flash Vacuum Pyrolysis - Techniques and Reactions.

    PubMed

    Wentrup, Curt

    2017-07-04

    While pyrolysis reactions have been performed since ancient times and been crucial for the invention of several technologies, the methodology now commonly known as flash vacuum pyrolysis, FVP (or flash vacuum thermolysis, FVT) had its early beginnings in the 1940s and1950s, mainly through mass spectrometric detection of pyrolytically formed free radicals. In the 1960s many organic chemists started performing FVP experiments with the purpose of isolating new and interesting compounds and understanding pyrolysis processes. Meanwhile, many different types of apparatus and techniques have been developed, and it is the purpose of this review to present the most important methods as well as a survey of typical reactions and observations that can be achieved with the various techniques. This includes preparative FVP, chemical trapping reactions, matrix isolation and low temperature spectroscopy of reactive intermediates and unstable molecules, the use of online mass, photoelectron, microwave and millimeterwave spectroscopies, gas-phase laser pyrolysis, pulsed pyrolysis with supersonic jet expansion, very low pressure pyrolysis for kinetic investigations, solution-spray and falling-solid FVP for involatile compounds, and pyrolysis over solid supports and reagents. Moreover, the combination of FVP with matrix isolation and photochemistry is a powerful tool for investigations of reaction mechanism. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Mild pyrolysis of selectively oxidized coals

    SciTech Connect

    Hippo, E.J.

    1991-01-01

    The primary objective of this study is to investigate the removal organic sulfur from selectively oxidized Illinois coals using mild thermal/chemical processes. Work completed this quarter includes the investigation of the mild pyrolysis of unoxidized coals plus a selection of selectively oxidized coals. In addition the effect of particle size and extent of oxidation on pyrolysis was investigated. Some preliminary data concerning pyrolysis under vacuum and ambient pressure was also obtained. Work completed this quarter supports the following conclusions: (1) Desulfurization of unoxidized coals increases with increasing pyrolysis temperature and correlates with the loss of volatile matter. (2) Particle size did not influence the extent of desulfurization significantly. (3) Removing pyrite prior to pyrolysis helps to achieve a lower sulfur product beyond that expected from the removal of pyrite alone. (4) The extent of selective oxidation in teh pretreatment step did not effect the level of desulfurization obtained by pyrolysis alone. However this factor was important in the desulfurization obtained with supercritical methanol (SCM)/base. (5) Up to 84% of the sulfur has been removed from the IBC 101 coal by combining selective oxidation and SCM/base reactions. (6) Evidence for regressive reactions between volatilized sulfur compounds and partially desulfurized products was obtained by studying how changes in pyrolysis pressure effected the product sulfur content.

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

    SciTech Connect

    Diebold, J P

    1997-04-01

    The scaleup of biomass fast pyrolysis systems to large pilot and commercial scales will expose an increasingly large number of personnel to potential health hazards, especially during the evaluation of the commercial use of the pyrolysis condensates. Although the concept of fast pyrolysis to optimize liquid products is relatively new, low-temperature pyrolysis processes have been used over the aeons to produce charcoal and liquid by-products, e.g., smoky food flavors, food preservatives, and aerosols containing narcotics, e.g., nicotine. There are a number of studies in the historical literature that concern the hazards of acute and long-term exposure to smoke and 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.

  10. Resources recovery of oil sludge by pyrolysis: Kinetics study

    SciTech Connect

    Shie, J.L.; Chang, C.Y.; Lin, J.P.; Wu, C.H.; Lee, D.J.

    1999-07-01

    Oil sludge, if unused, is one of the major industrial wastes needed to be treated for the petroleum refinery plant or petrochemical industry. It contains a large amount of combustibles with high heating values. The treatment of waste oil sludge by burning has certain benefit; however, it cannot provide the useful resource efficiently. On the other hand, the conversion of oil sludge to lower molecule weight organic compounds by pyrolysis not only solves the disposal problem but also matches the appeal of resource utilization. The major sources of oil sludge include the oil storage tank sludge, the biological sludge, the dissolve air flotation (DAF) scum, the American Petroleum Institute (API) separator sludge and the chemical sludge. In this study, the oil sludge from the oil storage tank of a typical petroleum refinery plant located in the northern Taiwan is used as the raw material of pyrolysis. Its heating value of dry basis and low heating value of wet basis are about 10,681 k cal/kg and 5,870 k cal/kg, respectively. The removal of the moisture of oil sludge significantly increases its heating value. The pyrolysis of oil sludge is conducted by the use of nitrogen as the carrier gas in the temperature range of 380 {approximately} 1,073 K and at various constant heating rates of 5.2, 12.8 and 21.8 K/min. The pyrolytic reaction is significant in 450 {approximately} 800 K and complex. For the sake of simplicity and engineering use, a one-reaction kinetic model is proposed for the pyrolysis of oil sludge, and is found to satisfactorily fit the experimental data. The activation energy, reaction order and frequency factor of the corresponding pyrolysis reaction in nitrogen for oil sludge are 78.22 kJ/mol, 2.92 and 9.48 105 l/min, respectively. These results are very useful for the proper design of the pyrolysis system of the oil sludge under investigation.

  11. The pyrolysis of toluene and ethyl benzene

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

  12. Carbon nanoscrolls by pyrolysis of a polymer

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  13. Coal liquefaction with subsequent bottoms pyrolysis

    DOEpatents

    Walchuk, George P.

    1978-01-01

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

  14. The pyrolysis of toluene and ethyl benzene

    NASA Technical Reports Server (NTRS)

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

    1987-01-01

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

  15. Pyrolysis decomposition of tamarind seed for alternative fuel.

    PubMed

    Kader, M A; Islam, M R; Parveen, M; Haniu, H; Takai, K

    2013-12-01

    The conversion of tamarind seed into bio-oil by pyrolysis has been taken into consideration in the present work. The major components of the system were fixed bed fire-tube heating reactor, liquid condenser and collector. The crushed tamarind seed in particle form was pyrolyzed in an electrically heated fixed bed reactor. The products were liquid, char and gasses. The parameters varied were reactor temperature, running time, gas flow rate and feed particle size. The maximum liquid yield was 45 wt% at 400°C for a feed size of 3200 μm diameter at a gas flow rate of 6l/min with a running time of 30 min. The obtained pyrolysis liquid at these optimum process conditions were analyzed for physical and chemical properties to be used as an alternative fuel. The results show the potential of tamarind seed as an important source of alternative fuel and chemicals as well.

  16. Method of producing pyrolysis gases from carbon-containing materials

    DOEpatents

    Mudge, Lyle K.; Brown, Michael D.; Wilcox, Wayne A.; Baker, Eddie G.

    1989-01-01

    A gasification process of improved efficiency is disclosed. A dual bed reactor system is used in which carbon-containing feedstock materials are first treated in a gasification reactor to form pyrolysis gases. The pyrolysis gases are then directed into a catalytic reactor for the destruction of residual tars/oils in the gases. Temperatures are maintained within the catalytic reactor at a level sufficient to crack the tars/oils in the gases, while avoiding thermal breakdown of the catalysts. In order to minimize problems associated with the deposition of carbon-containing materials on the catalysts during cracking, a gaseous oxidizing agent preferably consisting of air, oxygen, steam, and/or mixtures thereof is introduced into the catalytic reactor at a high flow rate in a direction perpendicular to the longitudinal axis of the reactor. This oxidizes any carbon deposits on the catalysts, which would normally cause catalyst deactivation.

  17. Pyrolysis of fast-growing aquatic biomass -Lemna minor (duckweed): Characterization of pyrolysis products.

    PubMed

    Muradov, Nazim; Fidalgo, Beatriz; Gujar, Amit C; T-Raissi, Ali

    2010-11-01

    The aim of this work was to conduct the experimental study of pyrolysis of fast-growing aquatic biomass -Lemna minor (commonly known as duckweed) with the emphasis on the characterization of main products of pyrolysis. The yields of pyrolysis gas, pyrolytic oil (bio-oil) and char were determined as a function of pyrolysis temperature and the sweep gas (Ar) flow rate. Thermogravimetric/differential thermogravimetric (TG/DTG) analyses of duckweed samples in inert (helium gas) and oxidative (air) atmosphere revealed differences in the TG/DTG patterns obtained for duckweed and typical plant biomass. The bio-oil samples produced by duckweed pyrolysis at different reaction conditions were analyzed using GC-MS technique. It was found that pyrolysis temperature had minor effect on the bio-oil product slate, but exerted major influence on the relative quantities of the individual pyrolysis products obtained. While, the residence time of the pyrolysis vapors had negligible effect on the yield and composition of the duckweed pyrolysis products. Copyright 2010 Elsevier Ltd. All rights reserved.

  18. Analysis of drugs by pyrolysis. I. Selected ion monitoring combined with a pyrolysis method for the determination of carpronium chloride in biological samples.

    PubMed

    Ohya, K; Sano, M

    1977-08-01

    In order to establish an analytical method for carpronium chloride, a parasympathomimetic agent, the pyrolysis reaction of carpronium chloride was examined in a g.c.m.s. system, which revealed that gamma-butyrolactone was produced directly from the drug as the main pyrolysis product. In the case of conversion of [2,2,3,3-2H4]carpronium chloride into the deuterated gamma-butyrolactone, 2H/1H scrambling was observed and confirmed to occur during the pyrolysis process of the deuterated compound. The proportion of gamma-[2H4]butyrolactone among the pyrolysis products was almost independent of the operating conditions, so [2,2,3,3-2H4]carpronium chloride was of practical use as an internal standard for selected ion monitoring. By incorporation of the pyrolysis reaction of carpronium chloride with selected ion monitoring and the use of [2,2,3,3-2H4]carpronium chloride as an internal standard, a rapid, sensitive and selective method was devised for the determination of the drug in biological samples. The method was utilized successfully for the biopharmaceutical studies of carpronium chloride in ma.

  19. Review of NMR characterization of pyrolysis oils

    DOE PAGES

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

    2016-08-24

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

  20. Review of NMR characterization of pyrolysis oils

    SciTech Connect

    Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun; Adhikari, Sushil; Ragauskas, Arthur J.

    2016-08-24

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

  1. Review of NMR characterization of pyrolysis oils

    SciTech Connect

    Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun; Adhikari, Sushil; Ragauskas, Arthur J.

    2016-08-24

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

  2. Zone heating for fluidized bed silane pyrolysis

    NASA Technical Reports Server (NTRS)

    Iya, Sridhar K. (Inventor)

    1987-01-01

    An improved heated fluidized bed reactor and method for the production of high purity polycrystalline silicon by silane pyrolysis wherein silicon seed particles are heated in an upper heating zone of the reactor and admixed with particles in a lower reaction zone, in which zone a silane-containing gas stream, having passed through a lower cooled gas distribution zone not conducive to silane pyrolysis, contacts the heated seed particles whereon the silane is heterogeneously reduced to silicon.

  3. Behavior of sulfur during coal pyrolysis

    USGS Publications Warehouse

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

    1994-01-01

    The behavior of sulfur in Illinois coals during pyrolysis was evaluated by thermogravimetry/ Fourier transform-infrared spectroscopy (TG/FT-IR) techniques. SO2, COS, and H2S were major gaseous sulfur-containing products observed during coal pyrolysis. The release rates of the gaseous sulfur species showed several peaks within the temperature ranges, which were due to the emission of different forms of sulfur in coal. ?? 1994.

  4. High quality fuel gas from biomass pyrolysis with calcium oxide.

    PubMed

    Zhao, Baofeng; Zhang, Xiaodong; Chen, Lei; Sun, Laizhi; Si, Hongyu; Chen, Guanyi

    2014-03-01

    The removal of CO2 and tar in fuel gas produced by biomass thermal conversion has aroused more attention due to their adverse effects on the subsequent fuel gas application. High quality fuel gas production from sawdust pyrolysis with CaO was studied in this paper. The results of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) experiments indicate that the mass ratio of CaO to sawdust (Ca/S) remarkably affects the behavior of sawdust pyrolysis. On the basis of Py-GC/MS results, one system of a moving bed pyrolyzer coupled with a fluid bed combustor has been developed to produce high quality fuel gas. The lower heating value (LHV) of the fuel gas was above 16MJ/Nm(3) and the content of tar was under 50mg/Nm(3), which is suitable for gas turbine application to generate electricity and heat. Therefore, this technology may be a promising route to achieve high quality fuel gas for biomass utilization. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Peat pyrolysis and the analytical semi-empirical model

    SciTech Connect

    Feng, J.; Green, A.E.S.

    2007-07-01

    Pyrolysis of peat could convert this material into useful fuels and valuable hydrocarbons. A study of peat pyrolysis can also serve as a useful bridge between studies of coal pyrolysis and biomass pyrolysis. Using an analytical model of pyrolysis that has previously been applied to biomass and to coal, we present here the results of applications of this model to a representative peat. The analysis suggests means of organizing and processing rate and yield data that should be useful in applications of pyrolysis for the production of fuels and chemicals.

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

    SciTech Connect

    Samolada, M.C.; Zabaniotou, A.A.

    2014-02-15

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

  7. Catalytic partial oxidation of pyrolysis oils

    NASA Astrophysics Data System (ADS)

    Rennard, David Carl

    2009-12-01

    This thesis explores the catalytic partial oxidation (CPO) of pyrolysis oils to syngas and chemicals. First, an exploration of model compounds and their chemistries under CPO conditions is considered. Then CPO experiments of raw pyrolysis oils are detailed. Finally, plans for future development in this field are discussed. In Chapter 2, organic acids such as propionic acid and lactic acid are oxidized to syngas over Pt catalysts. Equilibrium production of syngas can be achieved over Rh-Ce catalysts; alternatively mechanistic evidence is derived using Pt catalysts in a fuel rich mixture. These experiments show that organic acids, present in pyrolysis oils up to 25%, can undergo CPO to syngas or for the production of chemicals. As the fossil fuels industry also provides organic chemicals such as monomers for plastics, the possibility of deriving such species from pyrolysis oils allows for a greater application of the CPO of biomass. However, chemical production is highly dependent on the originating molecular species. As bio oil comprises up to 400 chemicals, it is essential to understand how difficult it would be to develop a pure product stream. Chapter 3 continues the experimentation from Chapter 2, exploring the CPO of another organic functionality: the ester group. These experiments demonstrate that equilibrium syngas production is possible for esters as well as acids in autothermal operation with contact times as low as tau = 10 ms over Rh-based catalysts. Conversion for these experiments and those with organic acids is >98%, demonstrating the high reactivity of oxygenated compounds on noble metal catalysts. Under CPO conditions, esters decompose in a predictable manner: over Pt and with high fuel to oxygen, non-equilibrium products show a similarity to those from related acids. A mechanism is proposed in which ethyl esters thermally decompose to ethylene and an acid, which decarbonylates homogeneously, driven by heat produced at the catalyst surface. Chapter 4

  8. Catalytic fast pyrolysis of lignocellulosic biomass.

    PubMed

    Liu, Changjun; Wang, Huamin; Karim, Ayman M; Sun, Junming; Wang, Yong

    2014-11-21

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

  9. Catalytic fast pyrolysis of lignocellulosic biomass

    SciTech Connect

    Liu, Changjun; Wang, Huamin; Karim, Ayman M.; Sun, Junming; Wang, Yong

    2014-11-21

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

  10. Prospects for pyrolysis technologies in managing municipal, industrial, and DOE cleanup wastes

    SciTech Connect

    Reaven, S.J.

    1994-12-01

    Pyrolysis converts portions of municipal solid wastes, hazardous wastes, and special wastes such as tires, medical wastes, and even old landfills into solid carbon and a liquid or gaseous hydrocarbon stream. Pyrolysis heats a carbonaceous waste stream typically to 290--900 C in the absence of oxygen, and reduces the volume of waste by 90% and its weight by 75%. The solid carbon char has existing markets as an ingredient in many manufactured goods, and as an adsorbent or filter to sequester certain hazardous wastes. Pyrolytic gases may be burned as fuel by utilities, or liquefied for use as chemical feedstocks, or low-pollution motor vehicle fuels and fuel additives. This report analyzes the potential applications of pyrolysis in the Long Island region and evaluates for the four most promising pyrolytic systems their technological and commercial readiness, their applicability to regional waste management needs, and their conformity with DOE requirements for environmental restoration and waste management. This summary characterizes their engineering performance, environmental effects, costs, product applications, and markets. Because it can effectively treat those wastes that are inadequately addressed by current systems, pyrolysis can play an important complementing role in the region`s existing waste management strategy. Its role could be even more significant if the region moves away from existing commitments to incineration and MSW composting. Either way, Long Island could become the center for a pyrolysis-based recovery services industry serving global markets in municipal solid waste treatment and hazardous waste cleanup. 162 refs.

  11. The Building and Commissioning of the Batch Pyrolysis Plant in Studsvik, Sweden - 12447

    SciTech Connect

    Lindberg, Maria; Oesterberg, Carl; Vernersson, Thomas

    2012-07-01

    After a sequence of lab scale and bench scale trials the building of a pyrolysis plant could begin at the Studsvik site in Sweden. The facility is primarily aimed at treatment of uranium contaminated organic waste originating at fuel manufacturing plants and other facilities where the main contamination is uranium. The plant is an extension/addition to the already operating incinerator. In order to further widen the waste acceptance criteria the design of the off-gas treatment system does not have the same design as that of the incinerator. The building of the facility began in April 2011, and the first heating of the facility took place in late December, 2011. The site acceptance tests are planned for January, as are the first inactive trials aimed at optimisation of process control. The facility is planned to be operating with radioactive materials from February 2012. The pyrolysis unit is primarily aimed at treatment of uranium contaminated waste, under conditions that facilitate leaching and recovery of the uranium from the ashes. However, a number of other uses are conceivable. The batch fed pyrolysis unit, with its chosen design of the off-gas treatment system, enables treatment of some waste fractions that are difficult to treat in the incinerator. For instance small campaigns, i.e. smaller quantities of waste (typically <5 tonnes), or waste containing high levels of chlorine and sulphur are possible to treat in the pyrolysis unit. The pyrolysis unit is also expected to perform well in the treatment of other 'difficult' waste fractions, for instance waste containing pyrophoric materials, or other types of waste that benefit from the high level of process control, i.e. control of temperature and atmosphere throughout the process, that can be obtained in the pyrolysis unit compared to the incinerator. Furthermore, treatment in the pyrolysis unit minimises the risk of cross contamination between different waste treatment campaigns. This feature is obtained

  12. Biomarker generation from Type II-S kerogens in claystone and limestone during hydrous and anhydrous pyrolysis

    USGS Publications Warehouse

    Koopmans, M.P.; Carson, F.C.; Sinninghe, Damste J.S.; Lewan, M.D.

    1998-01-01

    A claystone and a limestone containing immature Type II-S kerogen were thermally matured in the presence and absence of water, to study the influence of water and clay minerals on the generation of biomarkers. In contrast to hydrous pyrolysis, anhydrous pyrolysis of the claystone did not generate biomarkers, which resulted in the loss of important information. Desulfurization of the polar fraction of the claystone showed that anhydrous pyrolysis is not capable of converting S-bound biomarkers to free biomarkers. For the limestone, the differences between hydrous and anhydrous pyrolysis are less dramatic. Adsorption of the polar fraction of the claystone to smectite interlayers probably leads to cross-linking reactions, preventing the generation of free biomarkers. During hydrous pyrolysis, the smectite interlayers are occupied by water so that generation of biomarkers can take place. In addition, cross-linking reactions during anhydrous pyrolysis of the claystone may be enhanced because of the presence of S-S bonds in the organic matter of the claystone. These results show that water is important in closed system laboratory experiments designed to simulate natural maturation of sedimentary organic matter.A claystone and a limestone containing immature Type II-S kerogen were thermally matured in the presence and absence of water, to study the influence of water and clay minerals on the generation of biomarkers. In contrast to hydrous pyrolysis, anhydrous pyrolysis of the claystone did not generate biomarkers, which resulted in the loss of important information. Desulfurization of the polar fraction of the claystone showed that anhydrous pyrolysis is not capable of converting S-bound biomarkers to free biomarkers. For the limestone, the differences between hydrous and anhydrous pyrolysis are less dramatic. Adsorption of the polar fraction of the claystone to smectite interlayers probably leads to cross-linking reactions, preventing the generation of free biomarkers

  13. Plasma Pyrolysis Assembly Regeneration Evaluation

    NASA Technical Reports Server (NTRS)

    Medlen, Amber; Abney, Morgan B.; Miller, Lee A.

    2011-01-01

    In April 2010 the Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS). This technology requires hydrogen to recover oxygen from carbon dioxide. This results in the production of water and methane. Water is electrolyzed to provide oxygen to the crew. Methane is vented to space resulting in a loss of valuable hydrogen and unreduced carbon dioxide. This is not critical for ISS because of the water resupply from Earth. However, in order to have enough oxygen for long-term missions, it will be necessary to recover the hydrogen to maximize oxygen recovery. Thus, the Plasma Pyrolysis Assembly (PPA) was designed to recover hydrogen from methane. During operation, the PPA produces small amounts of carbon that can ultimately reduce performance by forming on the walls and windows of the reactor chamber. The carbon must be removed, although mechanical methods are highly inefficient, thus chemical methods are of greater interest. The purpose of this effort was to determine the feasibility of chemically removing the carbon from the walls and windows of a PPA reactor using a pure carbon dioxide stream.

  14. Kapton pyrolysis, the space environment and wiring requirements

    NASA Technical Reports Server (NTRS)

    Ferguson, Dale C.

    1994-01-01

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

  15. Ceramic powder synthesis by spray pyrolysis

    SciTech Connect

    Messing, G.L.; Zhang, Shi Chang; Jayanthi, G.V. . Particulate Materials Center)

    1993-11-01

    A variety of spray pyrolysis (SP) techniques have been developed to directly produce ceramic powders from solutions. This paper reviews the current status of these processes in terms of the process parameters that enable the formation of particles with controlled morphology and composition. A model incorporating solute diffusion in the droplet and solvent evaporation from the droplet surface is presented to establish the critical parameters leading to solid particle formation. The model illustrates that solid particles can be obtained if solutes with high solubility and a large difference between the critical supersaturation and equilibrium concentration are used and if the process is designed to avoid solvent boiling. It is demonstrated that mixed metal oxide, non-oxide, and composite particles that are solid, hollow, porous, or fibrous can be produced by modifying the precursor characteristics, solution properties, and process parameters. The physical and chemical flexibility of SP processes offers numerous opportunities for the controlled synthesis of advanced ceramic powders and films. However, production rates are limited by the need to produce <5-[mu]m-diameter droplets and to avoid subsequent droplet coagulation. Developments in process controls, atomization, and system design are required for wider commercialization of SP-type processes.

  16. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-10-07

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

  17. Catalytic pyrolysis using UZM-39 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christpher P; Boldingh, Edwin P

    2013-12-17

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

  18. Pyrolysis Research at the National Renewable Energy Laboratory

    SciTech Connect

    Iisa, Kristiina; Ciesielski, Peter N.; Nimlos, Mark R.

    2014-01-01

    The overwhelming majority of biomass pyrolysis research at NREL is supported by the US Department of Energy's Office of the Biomass Program and is focused on the production of 'drop-in' transportation fuels. This includes studies of fast pyrolysis and vapor phase upgrading of pyrolysis vapors to produce hydrocarbon fuel blendstocks or refinery feedstocks.

  19. Production and analysis of fast pyrolysis oils from proteinaceous biomass

    USDA-ARS?s Scientific Manuscript database

    Fast pyrolysis of lignocellulosic biomass is a facile method for producing high yields of liquid fuel intermediates. However, because most fast pyrolysis oils are highly oxygenated, acidic and unstable identification of feedstocks that produce higher quality pyrolysis liquids is desirable. Therefor...

  20. Effects of Nonequilibrium Chemistry and Darcy-Forchheimer Pyrolysis Flow for Charring Ablator

    NASA Technical Reports Server (NTRS)

    Chen, Yih-Kanq; Milos, Frank S.

    2013-01-01

    The fully implicit ablation and thermal response code simulates pyrolysis and ablation of thermal protection materials and systems. The governing equations, which include energy conservation, a three-component decomposition model, and a surface energy balance, are solved with a moving grid.This work describes new modeling capabilities that are added to a special version of code. These capabilities include a time-dependent pyrolysis gas flow momentum equation with Darcy-Forchheimer terms and pyrolysis gas species conservation equations with finite rate homogeneous chemical reactions. The total energy conservation equation is also enhanced for consistency with these new additions. Two groups of parametric studies of the phenolic impregnated carbon ablator are performed. In the first group, an Orion flight environment for a proposed lunar-return trajectory is considered. In the second group, various test conditions for arcjet models are examined. The central focus of these parametric studies is to understand the effect of pyrolysis gas momentum transfer on material in-depth thermal responses with finite-rate, equilibrium, or frozen homogeneous gas chemistry. Results indicate that the presence of chemical nonequilibrium pyrolysis gas flow does not significantly alter the in-depth thermal response performance predicted using the chemical equilibrium gas model.

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

    SciTech Connect

    Pfefferle, L.D.

    1992-12-31

    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.

  2. Development of a high-performance coal-fired power generating system with pyrolysis gas and char-fired high temperature furnace (HITAF). Volume 1, Final report

    SciTech Connect

    1996-02-01

    A major objective of the coal-fired high performance power systems (HIPPS) program is to achieve significant increases in the thermodynamic efficiency of coal use for electric power generation. Through increased efficiency, all airborne emissions can be decreased, including emissions of carbon dioxide. High Performance power systems as defined for this program are coal-fired, high efficiency systems where the combustion products from coal do not contact the gas turbine. Typically, this type of a system will involve some indirect heating of gas turbine inlet air and then topping combustion with a cleaner fuel. The topping combustion fuel can be natural gas or another relatively clean fuel. Fuel gas derived from coal is an acceptable fuel for the topping combustion. The ultimate goal for HIPPS is to, have a system that has 95 percent of its heat input from coal. Interim systems that have at least 65 percent heat input from coal are acceptable, but these systems are required to have a clear development path to a system that is 95 percent coal-fired. A three phase program has been planned for the development of HIPPS. Phase 1, reported herein, includes the development of a conceptual design for a commercial plant. Technical and economic feasibility have been analysed for this plant. Preliminary R&D on some aspects of the system were also done in Phase 1, and a Research, Development and Test plan was developed for Phase 2. Work in Phase 2 include s the testing and analysis that is required to develop the technology base for a prototype plant. This work includes pilot plant testing at a scale of around 50 MMBtu/hr heat input. The culmination of the Phase 2 effort will be a site-specific design and test plan for a prototype plant. Phase 3 is the construction and testing of this plant.

  3. Specialists' workshop on fast pyrolysis of biomass

    SciTech Connect

    Not Available

    1980-01-01

    This workshop brought together most of those who are currently working in or have published significant findings in the area of fast pyrolysis of biomass or biomass-derived materials, with the goal of attaining a better understanding of the dominant mechanisms which produce olefins, oxygenated liquids, char, and tars. In addition, background papers were given in hydrocarbon pyrolysis, slow pyrolysis of biomass, and techniques for powdered-feedstock preparation in order that the other papers did not need to introduce in depth these concepts in their presentations for continuity. In general, the authors were requested to present summaries of experimental data with 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)

  4. Behavior of chlorine during coal pyrolysis

    USGS Publications Warehouse

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

    1994-01-01

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

  5. Lunar oxygen production by pyrolysis of regolith

    NASA Technical Reports Server (NTRS)

    Senior, Constance L.

    1991-01-01

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

  6. Lunar oxygen production by pyrolysis of regolith

    NASA Technical Reports Server (NTRS)

    Senior, Constance L.

    1991-01-01

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

  7. Pyrolysis Mechanisms of Aromatic Carboxylic Acids

    SciTech Connect

    Britt, P.F.; Eskay, T.P.; Buchanan, A.C. III

    1997-12-31

    Although decarboxylation of carboxylic acids is widely used in organic synthesis, there is limited mechanistic information on the uncatalyzed reaction pathways of aromatic carboxylic acids at 300-400 {degrees} C. The pyrolysis mechanisms of 1,2-(3,3-dicarboxyphenyl)ethane, 1,2-(4,4-dicarboxylphenyl)ethane, 1-(3-carboxyphenyl)-2-(4- biphenyl)ethane, and substituted benzoic acids have been investigated at 325-425 {degrees} C neat and diluted in an inert solvent. Decarboxylation is the dominant pyrolysis path. Arrhenius parameters, substituent effects, and deuterium isotope effects are consistent with decarboxylation by an electrophilic aromatic substitution reaction. Pyrolysis of benzoic acid in naphthalene, as a solvent, produces significant amounts of 1- and 2-phenylnaphthalenes. The mechanistic pathways for decarboxylation and arylation with be presented.

  8. Characterization of the pyrolysis products of methiopropamine.

    PubMed

    Bouso, Emily D; Gardner, Elizabeth A; O'Brien, John E; Talbot, Brian; Kavanagh, Pierce V

    2014-01-01

    1-(Thien-2-yl)-2-methylaminopropane (methiopropamine, MPA), appeared as a 'legal high' in late 2010. It is structurally similar to methamphetamine, with a thiophene ring replacing the benzene moiety. Methiopropamine reportedly retains the pharmacological properties of amphetamine stimulants, but it does not fall under existing drug laws in the USA and Ireland. The objective of this research was to identify the pyrolysis products formed under conditions that mimic those used by recreational drugs users. Thirteen pyrolysis products were identified and ten were confirmed by comparison to synthesized standards. Methods for synthesizing the standards as well as an alternative method for the synthesis of methiopropamine were developed. The MPA pyrolysis products are formed through N-dealkylation, N-alkylation, N-formylation, β-carbon oxidation, β-carbon oxidation/N-alkylation, amine elimination and carbon-carbon bond cleavage. Two pyrazine isomers also formed. Some of these products have the potential to be psychoactive while others are potentially toxic.

  9. Microwave induced pyrolysis of oil palm biomass.

    PubMed

    Salema, Arshad Adam; Ani, Farid Nasir

    2011-02-01

    The purpose of this paper was to carry out microwave induced pyrolysis of oil palm biomass (shell and fibers) with the help of char as microwave absorber (MA). Rapid heating and yield of microwave pyrolysis products such as bio-oil, char, and gas was found to depend on the ratio of biomass to microwave absorber. Temperature profiles revealed the heating characteristics of the biomass materials which can rapidly heat-up to high temperature within seconds in presence of MA. Some characterization of pyrolysis products was also presented. The advantage of this technique includes substantial reduction in consumption of energy, time and cost in order to produce bio-oil from biomass materials. Large biomass particle size can be used directly in microwave heating, thus saving grinding as well as moisture removal cost. A synergistic effect was found in using MA with oil palm biomass.

  10. Pyrolysis of Sawdust, Rice Husk and Sugarcane Bagasse: Kinetic Modeling and Estimation of Kinetic Parameters using Different Optimization Tools

    NASA Astrophysics Data System (ADS)

    Khonde, Ruta Dhanram; Chaurasia, Ashish Subhash

    2015-04-01

    The present study provides the kinetic model to describe the pyrolysis of sawdust, rice-husk and sugarcane bagasse as biomass. The kinetic scheme used for modelling of primary pyrolysis consisting of the two parallel reactions giving gaseous volatiles and solid char. Estimation of kinetic parameters for pyrolysis process has been carried out for temperature range of 773-1,173 K. As there are serious issues regarding non-convergence of some of the methods or solutions converging to local-optima, the proposed kinetic model is optimized to predict the best values of kinetic parameters for the system using three approaches—Two-dimensional surface fitting non-linear regression technique, MS-Excel Solver Tool and COMSOL software. The model predictions are in agreement with experimental data over a wide range of pyrolysis conditions. The estimated value of kinetic parameters are compared with earlier researchers and found to be matching well.

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

    PubMed Central

    Simmonds, Peter G.

    1970-01-01

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

  12. Reaction pathways of propene pyrolysis.

    PubMed

    Qu, Yena; Su, Kehe; Wang, Xin; Liu, Yan; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong

    2010-05-01

    The gas-phase reaction pathways in preparing pyrolytic carbon with propene pyrolysis have been investigated in detail with a total number of 110 transition states and 50 intermediates. The structure of the species was determined with density functional theory at B3PW91/6-311G(d,p) level. The transition states and their linked intermediates were confirmed with frequency and the intrinsic reaction coordinates analyses. The elementary reactions were explored in the pathways of both direct and the radical attacking decompositions. The energy barriers and the reaction energies were determined with accurate model chemistry method at G3(MP2) level after an examination of the nondynamic electronic correlations. The heat capacities and entropies were obtained with statistical thermodynamics. The Gibbs free energies at 298.15 K for all the reaction steps were reported. Those at any temperature can be developed with classical thermodynamics by using the fitted (as a function of temperature) heat capacities. It was found that the most favorable paths are mainly in the radical attacking chain reactions. The chain was proposed with 26 reaction steps including two steps of the initialization of the chain to produce H and CH(3) radicals. For a typical temperature (1200 K) adopted in the experiments, the highest energy barriers were found in the production of C(3) to be 203.4 and 193.7 kJ/mol. The highest energy barriers for the production of C(2) and C were found 174.1 and 181.4 kJ/mol, respectively. These results are comparable with the most recent experimental observation of the apparent activation energy 201.9 +/- 0.6 or 137 +/- 25 kJ/mol. Copyright 2010 Wiley Periodicals, Inc.

  13. Pyrolysis and volatilization of cocaine

    SciTech Connect

    Martin, B.R.; Lue, L.P.; Boni, J.P. )

    1989-05-01

    The increasing popularity of inhaling cocaine vapor prompted the present study, to determine cocaine's fate during this process. The free base of (3H)cocaine (1 microCi/50 mg) was added to a glass pipe, which was then heated in a furnace to simulate freebasing. Negative pressure was used to draw the vapor through a series of glass wool, ethanol, acidic, and basic traps. Air flow rate and temperature were found to have profound effects on the volatilization and pyrolysis of cocaine. At a temperature of 260 degrees C and a flow rate of 400 mL/min, 37% of the radioactivity remained in the pipe, 39% was found in the glass wool trap, and less than 1% in the remainder of the volatilization apparatus after a 10-min volatilization. Reducing the air flow rate to 100 mL/min reduced the amount of radioactivity collected in the glass wool trap to less than 10% of the starting material and increased the amount that remained in the pipe to 58%. GC/MS analysis of the contents of the glass wool trap after volatilization at 260 degrees C and a flow rate of 400 mL/min revealed that 60% of the cocaine remained intact, while approximately 6 and 2% of the starting material was recovered as benzoic acid and methylecgonidine, respectively. As the temperature was increased to 650 degrees C, benzoic acid and methylecgonidine accounted for 83 and 89% of the starting material, respectively, whereas only 2% of the cocaine remained intact. Quantitation of cocaine in the vapor during the course of volatilization revealed high concentrations during the first two min and low concentrations for the remaining time.

  14. Pyrolysis of Organic Compounds Containing Long Unbranched Alkyl Groups.

    DTIC Science & Technology

    1982-09-21

    Reaction,’ NORDS-NBS21, U.S. Government Printing Office, Washington, D.C., 1967. 28. H. J. Perkins, "Aromatic Substitution," in Free RAdicl . Vol. 1U, J. L...Rice [181 In 19IO" posed his now claical free -radical chain mechanism of hydrocarbon pyrolysi. The Unetma decoamposition- of email alkanse (CI...was attiched to a vacuum system, cooled to 195 K, ad subjected to three free -pump-thaw cycles. The deawrated samples were warmed to room temperature and

  15. Consider Upgrading Pyrolysis Oils Into Renewale Fuels

    SciTech Connect

    Holmgren, J.; Marinangeli, R.; Nair, P.; Elliott, D.; Bain, R.

    2008-09-01

    To enable a sustained supply of biomass-based transportation fuels, the capability to process feedstocks outside the food chain must be developed. Significant industry efforts are underway to develop these new technologies, such as converting cellulosic wastes to ethanol. An alternate route being pursued involves using a fast pyrolysis operation to generate pyrolysis oil (pyoil for short). Current efforts are focused on developing a thermochemical platform to convert pyoils to renewable gasoline, diesel and jet fuel. The fuels produced will be indistinguishable from their fossil fuel counterparts and, therefore, will be compatible with existing transport and distribution infrastructure.

  16. [Kinetic study on pyrolysis of psoralen].

    PubMed

    Fan, Haiyan; Liao, Kun; Hu, Wei; Su, Jiakun; Tian, Yaowei; Qi, Fei; Cai, Jibao

    2012-01-01

    In this study, products of psoralen pyrolysis were detected using a solid pyrolysis apparatus and synchrotron radiation vacuum ultraviolet photoionization mass spectrum (SVUV-PIMS). The pyrolytic kinetics of psoralen was also studied by calculating its initial pyrolytic route in quantum chemistry. According to the findings with SVUV-PIMS, three pyrolytic products were observed, CO, C9H6O and C10H6O2. Theoretically, three fragment pathways were calculated for psoralen, in which the major primary decomposition route was de-CO, and the major secondary decomposition reaction was de-CO reaction of de-CO products.

  17. Volatile Analysis by Pyrolysis of Regolith (Vapor) for Planetary Resource Prospecting

    NASA Technical Reports Server (NTRS)

    Glavin, D. P.; Malespin, C. A.; Ten Kate, I. L.; Mcadam, A.; Getty, S. A.; Mumm, E.; Franz, H. B.; Southard, A. E.; Bleacher, J. E.; Mahaffy, P. R.

    2016-01-01

    Measuring the chemical composition of planetary bodies and their atmospheres is key to understanding the formation of the Solar System and the evolution of the planets and their moons. In situ volatile measurements enable a ground-truth assessment of the distribution and abundance of resources such as water-ice and oxygen, important for a sustained human presence on the Moon and beyond. The Volatile Analysis by Pyrolysis of Regolith (VAPoR) instrument is a compact pyrolysis mass spectrometer designed to detect volatiles released from solid samples that are heated to elevated temperatures and is one technique that should be considered for resource prospecting on the Moon, Mars, and asteroids.

  18. Development of a high-performance, coal-fired power generating system with a pyrolysis gas and char-fired high-temperature furnace

    SciTech Connect

    Shenker, J.

    1995-11-01

    A high-performance power system (HIPPS) is being developed. This system is a coal-fired, combined-cycle plant that will have an efficiency of at least 47 percent, based on the higher heating value of the fuel. The original emissions goal of the project was for NOx and SOx to each be below 0.15 lb/MMBtu. In the Phase 2 RFP this emissions goal was reduced to 0.06 lb/MMBtu. The ultimate goal of HIPPS is to have an all-coal-fueled system, but initial versions of the system are allowed up to 35 percent heat input from natural gas. Foster Wheeler Development Corporation is currently leading a team effort with AlliedSignal, Bechtel, Foster Wheeler Energy Corporation, Research-Cottrell, TRW and Westinghouse. Previous work on the project was also done by General Electric. The HIPPS plant will use a high-Temperature Advanced Furnace (HITAF) to achieve combined-cycle operation with coal as the primary fuel. The HITAF is an atmospheric-pressure, pulverized-fuel-fired boiler/air heater. The HITAF is used to heat air for the gas turbine and also to transfer heat to the steam cycle. its design and functions are very similar to conventional PC boilers. Some important differences, however, arise from the requirements of the combined cycle operation.

  19. MBMS of biomass pyrolysis vapors and catalytic upgrading

    SciTech Connect

    French, R.J.; Rejai, B.

    1995-03-01

    Studies of the production of transportation fuels from woody plants and other biomass sources at NREL have included the catalytic upgrading of vapors produced by the pyrolysis of wood and other materials. Molecular beam mass spectrometry is uniquely suited to the screening of this chemistry because of its ability to fingerprint the complete slate of pyrolysis or catalysis products in real time. It can also follow transient behavior at the rate of several spectra per second, which is useful in modeling the behavior of a riser-cracker or similar industrial system. Laboratory work was done on a dual-bed vertical reactor in which the sample (3-80 mg of solid sample) is pyrolyzed in the lower section of the reactor and then passed over 0.2-1.0 g of various catalysts. It is then diluted and introduced into the molecular beam. This system can be used to compare various catalysts and feedstocks. In other experiments, a pilot-scale (15kg/hr) pyrolysis plant with catalytic riser cracker was monitored with the NREL transportable MBMS. Continuous sampling was done via an atmospheric pressure, heated line. Nitrogen dilution was used to suppress condensation and water clusters. Results will be shown comparing products from wood, sunflower seeds, and mixtures of paper and plastics. Over MFI zeolite catalyst, a product slate similar to the methanol-to-gasoline process is observed--a mixture of alkane, alkene and aromatic compounds--with additional CO and CO{sub 2}. Higher yields of alkenes are produced by the oily and plastic-containing samples. The pilot plant gives spectra similar to the laboratory data. The TMBMS correctly identified improved operating conditions.

  20. Processes for converting lignocellulosics to reduced acid pyrolysis oil

    DOEpatents

    Kocal, Joseph Anthony; Brandvold, Timothy A

    2015-01-06

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

  1. Experimental and theoretical studies into the formation of C4-C6 products in partially chlorinated hydrocarbon pyrolysis systems: a probabilistic approach to congener-specific yield predictions.

    PubMed

    McIntosh, Grant J; Russell, Douglas K

    2014-09-25

    This work presents a study of the pyrolytic formation of vinylacetylene and benzene congeners formed from chlorinated hydrocarbon precursors, a complex, multipath polymerization system formed in a monomer-rich environment. (Co-)pyrolyses of dichloro- and trichloroethylene yield a rich array of products, and assuming a single dominant underlying growth mechanism, this (on comparing expected and observed products) allows a number of potentially competing channels to C4 and C6 products to be ruled out. Poor congener/isomer descriptions rule out even-carbon radical routes, and the absence of C3 and C5 products rule out odd-carbon processes. Vinylidenes appear unable to describe the increased reactivity of acetylenes with chlorination noted in our experiments, leaving molecular acetylene dimerization processes and, in C6 systems, the closely related Diels-Alder cyclization as the likely reaction mechanism. The feasibility of these routes is further supported by ab initio calculations. However, some of the most persuasive evidence is provided by congener-specific yield predictions enabled by the construction of a probability tree analogue of kinetic modeling. This approach is relatively quick to construct, provides surprisingly accurate predictions, and may be a very useful tool in screening for important reaction channels in poorly understood congener- or isomer-rich reaction systems.

  2. Radical reactions in pyrolysis of triethylarsine and diethylarsine

    NASA Astrophysics Data System (ADS)

    Li, S. H.; Larsen, C. A.; Stringfellow, G. B.

    1991-06-01

    Pyrolysis of triethylarsine (TEAs) and diethylarsine (DEAsH) has been studied at atmospheric pressure in a flow tube reactor using mass spectrometry. He and D 2 were selected as the carrier gases to determine the ambient effects and to isotopically label the pyrolysis products. For some experiments, supplemental C 2H 5 radicals, produced from pyrolysis of a co-reactant azoethane ((C 2H 5) 2N 2), were added to investigate the role of C 2H 5 in the pyrolysis reactions of the ethylarsines. A significant ambient effect was observed for pyrolysis of TEAs, but not for DEAsH. The pyrolysis of DEAsH was enhanced by adding C 2H 5 radicals while the TEAs pyrolysis was nearly unaffected. DEAsD, rather than DEAsH, was a product for TEAs pyrolysis in D 2; however, the DEAsH pyrolysis produced TEAs in either ambient. This demonstrates that the β-elimination reaction is not a major step. Instead, radical reactions are more likely to dominate the pyrolysis process. Reaction mechanisms for pyrolysis of TEAs and DEAsH in both ambients have been proposed. The rate constants for the reactions involved were determined. In addition, consistency between the proposed reaction pathways and the experimental data has been examined using computer modelling.

  3. Effect of wastewater treatment processes on the pyrolysis properties of the pyrolysis tars from sewage sludges

    NASA Astrophysics Data System (ADS)

    Wu, Xia; Xie, Li-Ping; Li, Xin-Yu; Dai, Xiao-Hong; Fei, Xue-Ning; Jiang, Yuan-Guang

    2011-06-01

    The pyrolysis properties of five different pyrolysis tars, which the tars from 1# to 5# are obtained by pyrolyzing the sewage sludges of anaerobic digestion and indigestion from the A2/O wastewater treatment process, those from the activated sludge process and the indigested sludge from the continuous SBR process respectively, were studied by thermal gravimetric analysis at a heating rate of 10 °C/min in the nitrogen atmosphere. The results show that the pyrolysis processes of the pyrolysis tars of 1#, 2#, 3# and 5# all can be divided into four stages: the stages of light organic compounds releasing, heavy polar organic compounds decomposition, heavy organic compounds decomposition and the residual organic compounds decomposition. However, the process of 4# pyrolysis tar is only divided into three stages: the stages of light organic compounds releasing, decomposition of heavy polar organic compounds and the residual heavy organic compounds respectively. Both the sludge anaerobic digestion and the "anaerobic" process in wastewater treatment processes make the content of light organic compounds in tars decrease, but make that of heavy organic compounds with complex structure increase. Besides, both make the pyrolysis properties of the tars become worse. The pyrolysis reaction mechanisms of the five pyrolysis tars have been studied with Coats-Redfern equation. It shows that there are the same mechanism functions in the first stage for the five tars and in the second and third stage for the tars of 1#, 2#, 3# and 5#, which is different with the function in the second stage for 4# tar. The five tars are easy to volatile.

  4. Kinetics study on conventional and microwave pyrolysis of moso bamboo.

    PubMed

    Dong, Qing; Xiong, Yuanquan

    2014-11-01

    A comparative study on the pyrolysis kinetics of moso bamboo has been conducted in a conventional thermogravimetric analyzer and a microwave thermogravimetric analyzer respectively. The effect of heating rate on the pyrolysis process was also discussed. The results showed that both the maximum and average reaction rates increased with the heating rate increasing. The values of activation energy increased from 58.30 to 84.22 kJ/mol with the heating rate decreasing from 135 to 60 °C/min during conventional pyrolysis. The value of activation energy was 24.5 kJ/mol for microwave pyrolysis, much lower than that for conventional pyrolysis at a similar heating rate of 160 °C/min. The pyrolysis of moso bamboo exhibited a kinetic compensation effect. The low activation energy obtained under microwave irradiation suggests that microwaves heating would be a promising method for biomass pyrolysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Microwave pyrolysis of wheat straw: product distribution and generation mechanism.

    PubMed

    Zhao, Xiqiang; Wang, Wenlong; Liu, Hongzhen; Ma, Chunyuan; Song, Zhanlong

    2014-04-01

    Microwave pyrolysis of wheat straw is studied, combined with analysis of products, the distribution and generation pathway of products are investigated. Only a small amount of volatiles released when microwave pyrolysis of pure straw. Mixtures of adding CuO and Fe3O4 can pyrolyze, and the majority in pyrolysis products is in liquid-phase. Severe pyrolysis occur after adding carbon residue, the CO content in pyrolysis gas products is high, and the maximum volume content of H2 can exceed 35 vol.%. The high-temperature is helpful for increasing the yield of combustible gas in gaseous products, in particular the H2 production, but also helpful for improving the conversion of sample. Pyrolysis is carried out layer by layer from the inside to outside. As the internal material firstly pyrolyze and pyrolysis products released pass through the low temperature zone, the chance of occurrence of secondary reactions is reduced.

  6. Thermal and catalytic slow pyrolysis of Calophyllum inophyllum fruit shell.

    PubMed

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

    2015-10-01

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

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

    SciTech Connect

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

    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.

  8. Producing Quantum Dots by Spray Pyrolysis

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  9. Pyrolysis-crystallinity relationships in cellulose

    Treesearch

    M. Weinstein; A. Broido

    1970-01-01

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

  10. Low temperature isothermal pyrolysis of cellulose

    Treesearch

    A. Broido; M. Weinstein

    1971-01-01

    By providing continuous weight measurement, thermogravimetry, even for isothermal experiments, offers a major advantage over the classical methods of determining weight-change curves in complex pyrolysis reactions. Thus, even minor weight changes, readily detectable on a continuous record, furnish clues concerning the reaction sequences and indicate conditions under...

  11. Speculations on the nature of cellulose pyrolysis

    Treesearch

    F.J. Kilzer; A. Broido

    1965-01-01

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

  12. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2014-04-29

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

  13. Indirect heating pyrolysis of oil shale

    DOEpatents

    Jones, Jr., John B.; Reeves, Adam A.

    1978-09-26

    Hot, non-oxygenous gas at carefully controlled quantities and at predetermined depths in a bed of lump oil shale provides pyrolysis of the contained kerogen of the oil shale, and cool non-oxygenous gas is passed up through the bed to conserve the heat

  14. Catalytic pyrolysis using UZM-44 aluminosilicate zeolite

    DOEpatents

    Nicholas, Christopher P; Boldingh, Edwin P

    2013-12-17

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

  15. Pyrolysis Mass Spectrometry of Complex Organic Materials.

    ERIC Educational Resources Information Center

    Meuzelaar, Henk L. C.; And Others

    1984-01-01

    Illustrates the state of the art in pyrolysis mass spectrometry techniques through applications in: (1) structural determination and quality control of synthetic polymers; (2) quantitative analysis of polymer mixtures; (3) classification and structural characterization of fossil organic matter; and (4) nonsupervised numerical extraction of…

  16. Primary and secondary lignin pyrolysis reaction pathways

    SciTech Connect

    Jegers, H.E.; Klein, M.T.

    1985-01-01

    The reaction pathways involved in the pyrolysis of kraft lignin, kraft lignin plus tetralin, a milled wood lignin, and pine wood were examined. The temporal variations of the quantitative yields of 33 different products, including 12 gases, water, methanol, and 19 phenolics allowed resolution of primary and secondary pathways, description of the influence of reactor design and lignin type on product yields, and formulation of a simple kinetic lumping scheme. Products within separate guaiacol and catechol lumps attained maximal proportions at 7.5 and 15 min, respectively, during kraft lignin pyrolysis at 400/sup 0/C. Within a lump, the secondary reactions of individual species were nearly synchronous. Further, the similarity of the observed rate of the secondary decomposition of guaiacols during kraft lignin pyrolysis with that previously reported for pyrolysis of pure guaiacol suggest that the reactions of lignin's thermally liberated single-ring products are insensitive to the presence of other molecular species or poymer residuum. All of the foregoing indicates that a simple reaction network based on phenol, guaiacol, and catechol lumps could be a useful model of phenolics product evolution.

  17. Pyrolysis of lipids using various catalysts

    USDA-ARS?s Scientific Manuscript database

    A specific pursuit of the thermochemical (combustion, gasification, pyrolysis, and liquefaction) conversion of biomass to energy research effort is the potential of converting lipids to alkanes, petroleum-like fuels and chemicals. Arguments can be made for, and against, the use of agricultural lipi...

  18. Pyrolysis of Rubber in a Screw Reactor

    NASA Astrophysics Data System (ADS)

    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.

  19. Toxicity of pyrolysis gases from polypropylene

    NASA Technical Reports Server (NTRS)

    Hilado, C. J.; Schneider, J. E.; Brauer, D. F.

    1979-01-01

    A sample of polypropylene was evaluated for toxicity of pyrolysis gases, using the toxicity screening test method developed at the University of San Francisco. The gases from this sample appeared to be equivalent or less toxic than the gases from a sample of polyethylene under these particular test conditions. Carbon monoxide appeared to be the principal toxicant.

  20. Pyrolysis Mass Spectrometry of Complex Organic Materials.

    ERIC Educational Resources Information Center

    Meuzelaar, Henk L. C.; And Others

    1984-01-01

    Illustrates the state of the art in pyrolysis mass spectrometry techniques through applications in: (1) structural determination and quality control of synthetic polymers; (2) quantitative analysis of polymer mixtures; (3) classification and structural characterization of fossil organic matter; and (4) nonsupervised numerical extraction of…

  1. Flash vacuum pyrolysis of lignin model compounds

    SciTech Connect

    Cooney, M.J.; Britt, P.F.; Buchanan, A.C. III

    1997-03-01

    Despite the extensive research into the pyrolysis of lignin, the underlying chemical reactions that lead to product formation are poorly understood. Detailed mechanistic studies on the pyrolysis of biomass and lignin under conditions relevant to current process conditions could provide insight into utilizing this renewable resource for the production of chemicals and fuel. Currently, flash or fast pyrolysis is the most promising process to maximize the yields of liquid products (up to 80 wt %) from biomass by rapidly heating the substrate to moderate temperatures, typically 500{degrees}C, for short residence times, typically less than two seconds. To provide mechanistic insight into the primary reaction pathways under process relevant conditions, we are investigating the flash vacuum pyrolysis (FVP) of lignin model compounds that contain a {beta}-ether. linkage and {alpha}- or {gamma}-alcohol, which are key structural elements in lignin. The dominant products from the FVP of PhCH{sub 2}CH{sub 2}OPh (PPE), PhC(OH)HCH{sub 2}OPh, and PhCH{sub 2}CH(CH{sub 2}OH)OPh at 500{degrees}C can be attributed to homolysis of the weakest bond in the molecule (C-O bond) or 1,2-elimination. Surprisingly, the hydroxy-substituent dramatically increases the decomposition of PPE. It is proposed that internal hydrogen bonding is accelerating the reaction.

  2. Catalytic pyrolysis of automobile shredder residue

    SciTech Connect

    Arzoumanidis, G.G.; McIntosh, M.J.; Steffensen, E.J.

    1995-07-01

    In the United States, approximately 10 million automobiles are scrapped and shredded each year. The mixture of plastics and other materials remaining after recovery of the metals is known as Automobile Shredder Residue (ASR). In 1994, about 3.5 million tons of ASR was produced and disposed of in landfills. However, environmental, legislative, and economic considerations are forcing the industry to search for recycling or other alternatives to disposal. Numerous studies have been done relating the ASR disposal problem to possible recycling treatments such as pyrolysis, gasification, co-liquefaction of ASR with coal, chemical recovery of plastics from ASR, catalytic pyrolysis, reclamation in molten salts, and vacuum pyrolysis. These and other possibilities have been studied intensively, and entire symposia have been devoted to the problem. Product mix, yields, toxicology issues, and projected economics of conceptual plant designs based on experimental results are among the key elements of past studies. Because the kinds of recycling methods that may be developed, along with their ultimate economic value, depend on a very large number of variables, these studies have been open-ended. It is hoped that it may be useful to explore some of these previously studied areas from fresh perspectives. One such approach, currently under development at Argonne National Laboratory, is the catalytic pyrolysis of ASR.

  3. The pyrolysis characteristics of moso bamboo

    Treesearch

    Zehui Jiang; Zhijia Liu; Benhua Fei; Zhiyong Cai; Yan Yu; Xing’e. Liu

    2012-01-01

    In the research, thermogravimetry (TG), a combination of thermogravimetry and Fourier transform infrared spectrometer (TG–FTIR) and X-ray diffraction (XRD) were used to investigate pyrolysis characteristics of moso bamboo (Phyllostachys pubescens). The Flynn–Wall–Ozawa and Coats–Redfern (modified) methods were used to determine the apparent activation energy (

  4. Pyrolysis characteristics and kinetics of Arundo donax using thermogravimetric analysis.

    PubMed

    Jeguirim, Mejdi; Trouvé, Gwenaelle

    2009-09-01

    The increase of the price of fossil means, as well as their programmed disappearing, contributed to increase among appliances based on biomass and energy crops. The thermal behavior of Arundo donax by thermogravimetric analysis was studied under inert atmosphere at heating rates ranging from 5 to 20 degrees C min(-1) from room temperature to 750 degrees C. Gaseous emissions as CO(2), CO and volatile organic compounds (VOC) were measured and global kinetic parameters were determined during pyrolysis with the study of the influence of the heating rate. The thermal process describes two main phases. The first phase named active zone, characterizes the degradation of hemicellulose and cellulose polymers. It started at low temperature (200 degrees C) comparatively to wood samples and was finished at 350 degrees C. The pyrolysis of the lignin polymer occurred during the second phase from 350 to 750 degrees C, named passive zone. Carbon oxides are emitted during the active zone whereas VOC are mainly formed during the passive zone. Mass losses, mass loss rates and emission factors were strongly affected by the variation of the heating rate in the active zone. It was found that the global pyrolysis of A. donax can be satisfactorily described using global independent reactions model for hemicellulose and cellulose in the active zone. The activation energy for hemicellulose was not affected by a variation of the heating rate with a value close to 110 kJ mol(-1) and presented a reaction order close to 0.5. An increase of the heating rate decreased the activation energy of the cellulose. However, a first reaction order was observed for cellulose decomposition. The experimental results and kinetic parameters may provide useful data for the design of pyrolytic processing system using A. donax as feedstock.

  5. Mass balance, energy and exergy analysis of bio-oil production by fast pyrolysis

    USDA-ARS?s Scientific Manuscript database

    Mass, energy and exergy balances are analyzed for bio-oil production in a bench scale fast pyrolysis system developed by the USDA’s Agricultural Research Service (ARS) for the processing of commodity crops to fuel intermediates. Because mass balance closure is difficult to achieve due, in part, to ...

  6. Development of a high-performance coal-fired power generating system with pyrolysis gas and char-fired high-temperature furnace (HITAF): Volume 4. Final report

    SciTech Connect

    1996-05-01

    An outgrowth of our studies of the FWDC coal-fired high performance power systems (HIPPS) concept was the development of a concept for the repowering of existing boilers. The initial analysis of this concept indicates that it will be both technically and economically viable. A unique feature of our greenfields HIPPS concept is that it integrates the operation of a pressurized pyrolyzer and a pulverized fuel-fired boiler/air heater. Once this type of operation is achieved, there are a few different applications of this core technology. Two greenfields plant options are the base case plant and a plant where ceramic air heaters are used to extend the limit of air heating in the HITAF. The greenfields designs can be used for repowering in the conventional sense which involves replacing almost everything in the plant except the steam turbine and accessories. Another option is to keep the existing boiler and add a pyrolyzer and gas turbine to the plant. The study was done on an Eastern utility plant. The owner is currently considering replacing two units with atmospheric fluidized bed boilers, but is interested in a comparison with HIPPS technology. After repowering, the emissions levels need to be 0.25 lb SO{sub x}/MMBtu and 0.15 lb NO{sub x}/MMBtu.

  7. Thiophenic Sulfur Compounds Released During Coal Pyrolysis

    PubMed Central

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-01-01

    Abstract Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography–mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis. PMID:23781126

  8. Thiophenic Sulfur Compounds Released During Coal Pyrolysis.

    PubMed

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-06-01

    Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography-mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis.

  9. [TG-FTIR study on pyrolysis of wheat-straw with abundant CaO additives].

    PubMed

    Han, Long; Wang, Qin-Hui; Yang, Yu-Kun; Yu, Chun-Jiang; Fang, Meng-Xiang; Luo, Zhong-Yang

    2011-04-01

    Biomass pyrolysis in presence of abundant CaO additives is a fundamental process prior to CaO sorption enhanced gasification in biomass-based zero emission system. In the present study, thermogravimetric Fourier transform infrared (TG-FTIR) analysis was adopted to examine the effects of CaO additives on the mass loss process and volatiles evolution of wheat-straw pyrolysis. Observations from TG and FTIR analyses simultaneously demonstrated a two-stage process for CaO catalyzed wheat-straw pyrolysis, different from the single stage process for pure wheat-straw pyrolysis. CaO additives could not only absorb the released CO2 but also reduce the yields of tar species such as toluene, phenol, and formic acid in the first stage, resulting in decreased mass loss and maximum mass loss rate in this stage with an increase in CaO addition. The second stage was attributed to the CaCO3 decomposition and the mass loss and maximum mass loss rate increased with increasing amount of CaO additives. The results of the present study demonstrated the great potential of CaO additives to capture CO2 and reduce tars yields in biomass-based zero emission system. The gasification temperature in the system should be lowered down to avoid CaCO3 decomposition.

  10. Fast Pyrolysis Process Development Unit for Validating Bench Scale Data

    SciTech Connect

    Brown, Robert C.; Jones, Samuel T.

    2010-03-31

    The purpose of this project was to prepare and operate a fast pyrolysis process development unit (PDU) that can validate experimental data generated at the bench scale. In order to do this, a biomass preparation system, a modular fast pyrolysis fluidized bed reactor, modular gas clean-up systems, and modular bio-oil recovery systems were designed and constructed. Instrumentation for centralized data collection and process control were integrated. The bio-oil analysis laboratory was upgraded with the addition of analytical equipment needed to measure C, H, O, N, S, P, K, and Cl. To provide a consistent material for processing through the fluidized bed fast pyrolysis reactor, the existing biomass preparation capabilities of the ISU facility needed to be upgraded. A stationary grinder was installed to reduce biomass from bale form to 5-10 cm lengths. A 25 kg/hr rotary kiln drier was installed. It has the ability to lower moisture content to the desired level of less than 20% wt. An existing forage chopper was upgraded with new screens. It is used to reduce biomass to the desired particle size of 2-25 mm fiber length. To complete the material handling between these pieces of equipment, a bucket elevator and two belt conveyors must be installed. The bucket elevator has been installed. The conveyors are being procured using other funding sources. Fast pyrolysis bio-oil, char and non-condensable gases were produced from an 8 kg/hr fluidized bed reactor. The bio-oil was collected in a fractionating bio-oil collection system that produced multiple fractions of bio-oil. This bio-oil was fractionated through two separate, but equally important, mechanisms within the collection system. The aerosols and vapors were selectively collected by utilizing laminar flow conditions to prevent aerosol collection and electrostatic precipitators to collect the aerosols. The vapors were successfully collected through a selective condensation process. The combination of these two mechanisms

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

    SciTech Connect

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

    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.

  12. Pyrolysis technologies for municipal solid waste: A review

    SciTech Connect

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

    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.

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

    PubMed

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

    2013-10-15

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

  14. Recycling of automobile shredder residue with a microwave pyrolysis combined with high temperature steam gasification.

    PubMed

    Donaj, Pawel; Yang, Weihong; Błasiak, Włodzimierz; Forsgren, Christer

    2010-10-15

    Presently, there is a growing need for handling automobile shredder residues--ASR or "car fluff". One of the most promising methods of treatment ASR is pyrolysis. Apart of obvious benefits of pyrolysis: energy and metals recovery, there is serious concern about the residues generated from that process needing to be recycled. Unfortunately, not much work has been reported providing a solution for treatment the wastes after pyrolysis. This work proposes a new system based on a two-staged process. The ASR was primarily treated by microwave pyrolysis and later the liquid and solid products become the feedstock for the high temperature gasification process. The system development is supported within experimental results conducted in a lab-scale, batch-type reactor at the Royal Institute of Technology (KTH). The heating rate, mass loss, gas composition, LHV and gas yield of producer gas vs. residence time are reported for the steam temperature of 1173 K. The sample input was 10 g and the steam flow rate was 0.65 kg/h. The conversion reached 99% for liquids and 45-55% for solids, dependently from the fraction. The H(2):CO mol/mol ratio varied from 1.72 solids and 1.4 for liquid, respectively. The average LHV of generated gas was 15.8 MJ/Nm(3) for liquids and 15 MJ/Nm(3) for solids fuels. 2010 Elsevier B.V. All rights reserved.

  15. Product distribution from pyrolysis of wood and agricultural residues

    SciTech Connect

    Di Blasi, C.; Signorelli, G.; Di Russo, C.; Rea, G.

    1999-06-01

    The pyrolysis characteristics of agricultural residues (wheat straw, olive husks, grape residues, and rice husks) and wood chips have been investigated on a bench scale. The experimental system establishes the conditions encountered by a thin (4 {times} 10{sup {minus}2} m diameter) packed bed of biomass particles suddenly exposed in a high-temperature environment, simulated by a radiant furnace. Product yields (gases, liquids, and char) and gas composition, measured for surface bed temperatures in the range 650--1000 K, reproduce trends already observed for wood. However, differences are quantitatively large. Pyrolysis of agricultural residues is always associated with much higher solid yields (up to a factor of 2) and lower liquid yields. Differences are lower for the total gas, and approximate relationships exist among the ratios of the main gas species yields, indicating comparable activation energies for the corresponding apparent kinetics of formation. However, while the ratios are about the same for wood chips, rice husks, and straw, much lower values are shown by olive and grape residues. Large differences have also been found in the average values of the specific devolatilization rates. The fastest (up to factors of about 1.5 with respect to wood) have been observed for wheat straw and the slowest (up to factors of 2) for grape residues.

  16. Pyrolysis chemistry of polycarbosilane polymer precursors to ceramics

    NASA Astrophysics Data System (ADS)

    Liu, Qi

    , likely facilitated by the Si-OH-induced attack on the Si-CHsb2-Si linkages. In addition, the microstructure of the gels and their pyrolytic products was investigated by Nsb2 adsorption-desorption test (the BET test). The results suggested that the investigated samples are microporous solids with relatively high surface areas even at 1000sp°C, indicating the potential interest of these samples as microporous materials. Finally, a mixture system was synthesized by introducing oxygen into the (SiHsb2CHsb2), polymer purposely to obtain a model (SiHsb2CHsb2rbracksb{n}rbrack Si(O)CHsb2rbracksb{m} system which has a variable and controllable amount of oxygen. This was the intermediate case between the two extremes. In this system, the pyrolysis mechanisms which worked in the two extreme cases also operated here along with a new mechanism resulting the formation of part of the total Hsb2 between Si-OH and Si-H groups.

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

    PubMed

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

    2016-08-01

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

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

    PubMed

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

    2016-10-01

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

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

    PubMed

    Wang, Ruixue; Xu, Zhenming

    2016-01-25

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. Effects of torrefaction and densification on switchgrass pyrolysis products

    SciTech Connect

    Yang, Zixu; Sarkar, Madhura; Kumar, Ajay; Tumuluru, Jaya Shankar; Huhnke, Raymond L.

    2014-12-01

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

  1. Calcium-catalyzed pyrolysis of lignocellulosic biomass components.

    PubMed

    Case, Paige A; Truong, Chi; Wheeler, M Clayton; DeSisto, William J

    2015-09-01

    The present study examines the effect of calcium pretreatment on pyrolysis of individual lignocellulosic compounds. Previous work has demonstrated that the incorporation of calcium compounds with the feedstock prior to pyrolysis has a significant effect on the oxygen content and stability of the resulting oil. The aim of this work was to further explore the chemistry of calcium-catalyzed pyrolysis. Bench-scale pyrolysis of biomass constituents, including lignin, cellulose and xylan is performed and compared to the oils produced from pyrolysis of the same components after calcium pretreatment. The resulting oils were analyzed by quantitative GC-MS and SEC. These analyses, together with data collected from previous work provide evidence which was used to develop proposed reaction pathways for pyrolysis of calcium-pretreatment biomass. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Regulation for Optimal Liquid Products during Biomass Pyrolysis: A Review

    NASA Astrophysics Data System (ADS)

    Wang, F.; Hu, L. J.; Zheng, Y. W.; Huang, Y. B.; Yang, X. Q.; Liu, C.; Kang, J.; Zheng, Z. F.

    2016-08-01

    The liquid product obtained from biomass pyrolysis is very valuable that it could be used for extraction of chemicals as well as for liquid fuel. The desire goal is to obtain the most bio-oil with desired higher heating value (HHV), high physicochemical stability. The yields and chemical composition of products from biomass pyrolysis are closely related to the feedstock, pyrolysis parameters and catalysts. Current researches mainly concentrated on the co-pyrolysis of different biomass and introduce of novel catalysts as well as the combined effect of catalysts and pyrolysis parameters. This review starts with the chemical composition of biomass and the fundamental parameters and focuses on the influence of catalysts on bio-oil. What is more, the pyrolysis facilities at commercial scales were also involved. The classic researches and the current literature about the yield and composition of products (mainly liquid products) are summarized.

  3. Effects of torrefaction and densification on switchgrass pyrolysis products.

    PubMed

    Yang, Zixu; Sarkar, Madhura; Kumar, Ajay; Tumuluru, Jaya Shankar; Huhnke, Raymond L

    2014-12-01

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

  4. Methods and apparatuses for deoxygenating pyrolysis oil

    DOEpatents

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

    2017-09-12

    Methods and apparatuses are provided for deoxygenating pyrolysis oil. A method includes contacting a pyrolysis oil with a deoxygenation catalyst in a first reactor at deoxygenation conditions to produce a first reactor effluent. The first reactor effluent has a first oxygen concentration and a first hydrogen concentration, based on hydrocarbons in the first reactor effluent, and the first reactor effluent includes an aromatic compound. The first reactor effluent is contacted with a dehydrogenation catalyst in a second reactor at conditions that deoxygenate the first reactor effluent while preserving the aromatic compound to produce a second reactor effluent. The second reactor effluent has a second oxygen concentration lower than the first oxygen concentration and a second hydrogen concentration that is equal to or lower than the first hydrogen concentration, where the second oxygen concentration and the second hydrogen concentration are based on the hydrocarbons in the second reactor effluent.

  5. Pyrolysis of Spent Ion Exchange Resins - 12210

    SciTech Connect

    Braehler, Georg; Slametschka, Rainer

    2012-07-01

    Organic ion exchangers (IEX) play a major and increasing role in the reactor coolant and other water purification processes. During their operation time they receive significant amounts of radioactivity, making their disposal, together with their organic nature, as medium active waste challenging. Processes applied so far do not eliminate the organic matter, which is unwanted in disposal facilities, or, if high temperatures are applied, raise problems with volatile radionuclides. NUKEM Technologies offers their well introduces process for the destruction of spent solvent (TBP), the pebble bed pyrolysis, now for the treatment of spent IEX (and other problematic waste), with the following benefits: the pyrolysis product is free of organic matter, and the operation temperature with approx. 500 deg. C keeps Cs radionuclides completely in the solid residue. (authors)

  6. Pyrolysis of Precambrian kerogens: constraints and capabilities.

    PubMed

    Nagy, B

    1982-01-01

    Precambrian kerogens are currently considered to be the primary candidates for the search of biochemical fossils. Degradation of kerogens by relatively "mild" pyrolysis techniques, such as under high vacuum, can liberate indicative structural moieties which were incorporated in, and perhaps shielded by, these solid and highly condensed, basically aromatic substances. It is necessary to observe analytical constraints (sample size and shape, temperature, pressure, time, etc.) in order to prevent an overabundant yield of secondary pyrolyzates (inter- and intramolecular rearrangements) which can prevent kerogen characterization. Potential biochemical fossils have been found in Precambrian kerogens. Demonstratable syngenetic biochemical fossils are expected after kerogen diagenesis and catagenesis is understood in sufficient detail, and when pyrolysis is augmented by multiple, improved analytical techniques.

  7. Pyrolysis of Precambrian kerogens - Constraints and capabilities

    NASA Technical Reports Server (NTRS)

    Nagy, B.

    1982-01-01

    Precambrian kerogens are currently considered to be the primary candidates for the search of biochemical fossils. Degradation of kerogens by relatively 'mild' pyrolysis techniques, such as under high vacuum, can liberate indicative structural moieties which were incorporated in, and perhaps shielded by, these solid and highly condensed, basically aromatic substances. It is necessary to observe analytical constraints (sample size and shape, temperature, pressure, time, etc.) in order to prevent an overabundant yield of secondary pyrolyzates (inter- and intramolecular rearrangements) which can prevent kerogen characterization. Potential biochemical fossils have been found in Precambrian kerogens. Demonstratable syngenetic biochemical fossils are expected after kerogen diagenesis and catagenesis is understood in sufficient detail, and when pyrolysis is augmented by multiple, improved analytical techniques.

  8. Improved Pyrolysis Micro reactor Design via Computational Fluid Dynamics Simulations

    DTIC Science & Technology

    2017-05-23

    NUMBER (Include area code) 23 May 2017 Briefing Charts 25 April 2017 - 23 May 2017 Improved Pyrolysis Micro-reactor Design via Computational Fluid... PYROLYSIS MICRO-REACTOR DESIGN VIA COMPUTATIONAL FLUID DYNAMICS SIMULATIONS Ghanshyam L. Vaghjiani* DISTRIBUTION A: Approved for public release...Approved for public release, distribution unlimited. PA Clearance 17247 Chen-Source (>240 references from SciFinder as of 5/1/17): Flash pyrolysis

  9. Temperature Jump Pyrolysis Studies of RP 2 Fuel

    DTIC Science & Technology

    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...Mixture Distribution A: Approved for public release; distribution unlimited. PA Clearance 17026 4 RP-2 Pyrolysis /Combustion Chemistries? • Recent

  10. Method and apparatus for producing pyrolysis oil having improved stability

    DOEpatents

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

    2016-12-27

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

  11. Methods for deoxygenating biomass-derived pyrolysis oil

    DOEpatents

    Brandvold, Timothy A.

    2015-07-14

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

  12. Novel Precursor Approached for CMC Derived by Polymer Pyrolysis

    DTIC Science & Technology

    1994-02-15

    DERIVED BY POLYMER PYROLYSIS Prepared by W. R. Schmidt FINAL TECHNICAL REPORT3 for period 15 Dec 1990 through 14 December 93 Contract F49620-91-C-0017...NOVEL PRECURSOR APPROACHES FOR CMC DERIVED F49620-91-C-0017 BY POLYMER PYROLYSIS 56. AUTHOR(S) Wayde R. Schmidt 7. PERFORMING ORGANIZATION NAME(S) AND...processing and pyrolysis . The conversion of PMVS to carbon-rich nanocrystalline silicon carbide ceramic was studied using a variety- of analytical

  13. Methane Pyrolysis and Disposing Off Resulting Carbon

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

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

  14. Toxicity of Pyrolysis Gases from Elastomers

    NASA Technical Reports Server (NTRS)

    Hilado, Carlos J.; Kosola, Kay L.; Solis, Alida N.; Kourtides, Demetrius A.; Parker, John A.

    1977-01-01

    The toxicity of the pyrolysis gases from six elastomers was investigated. The elastomers were polyisoprene (natural rubber), styrene-butadiene rubber (SBR), ethylene propylene diene terpolymer (EPDM), acrylonitrile rubber, chlorosulfonated polyethylene rubber, and polychloroprene. The rising temperature and fixed temperature programs produced exactly the same rank order of materials based on time to death. Acryltonitrile rubber exhibited the greatest toxicity under these test conditions; carbon monoxide was not found in sufficient concentrations to be the primary cause of death.

  15. Methane Pyrolysis and Disposing Off Resulting Carbon

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

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

  16. Coal pyrolysis for utility use: Final report

    SciTech Connect

    McKinsey, R.; Luebke, C.P.; Thelen, H.J.; ya Nsakala, N.; Riegel, H.

    1987-07-01

    EPRI undertook an extensive research effort to evaluate the viability of coal pyrolysis products for utility use. The objectives of the studies were to evaluate the combustion and storage characteristics of pyrolysis char and to evaluate the upgrading potential of pyrolysis liquid products (tar). To achieve these objectives, it was necessary to produce sufficient quantities of the char and tar in a process unit large enough to produce commercially representative products. For both technical and availability reasons, EPRI selected the Lurgi-Ruhrgas (L-R) process for the production run (under subcontract to Bechtel Group, Inc. RP2505-2). Several contractors were to do the liquid upgrading. Two contractors were selected to use alternative processes for upgrading the L-R heavy tar: Lummus-Crest, Inc. (RP2505-5), using its LC-fining technology, and Veba Oel (RP2505-6), using its Combi-Cracking process. (The Combi-Cracking process also simultaneously hydrotreats the coal-tar-derived distillates.) Universal Oil Products, Inc. (UOP) was selected to hydrotreat the light and middle oils from the L-R process (RP2505-7), as well as the distillable material produced by Lummus. Unfortunately, none of these contractors received the anticipated products. The light oil was in the form of a light oil-water emulsion and the middle oil had been blended with the solids-laden heavy oil during L-R operation. Combustion Engineering, Inc. carried out a two-phase program to evaluate the combustion characteristics of pyrolysis char (RP2505-4).

  17. 18O/16O ratio measurements of inorganic and organic materials by elemental analysis-pyrolysis-isotope ratio mass spectrometry continuous-flow techniques.

    PubMed

    Fourel, François; Martineau, François; Lécuyer, Christophe; Kupka, Hans-Joachim; Lange, Lutz; Ojeimi, Charles; Seed, Mike

    2011-10-15

    We have used a high-precision, easy, low-cost and rapid method of oxygen isotope analysis applied to various O-bearing matrices, organic and inorganic (sulfates, nitrates and phosphates), whose (18)O/(16)O ratios had already been measured. It was first successfully applied to (18)O analyses of natural and synthetic phosphate samples. The technique uses high-temperature elemental analysis-pyrolysis (EA-pyrolysis) interfaced in continuous-flow mode to an isotope ratio mass spectrometry (IRMS) system. Using the same pyrolysis method we have been able to generate a single calibration curve for all those samples showing pyrolysis efficiencies independent of the type of matrix pyrolysed. We have also investigated this matrix-dependent pyrolysis issue using a newly developed pyrolysis technique involving 'purge-and-trap' chromatography. As previously stated, silver phosphate being a very stable material, weakly hygroscopic and easily synthesized with predictable (18)O/(16)O values, could be considered as a good candidate to become a reference material for the determination of (18)O/(16)O ratios by EA-pyrolysis-IRMS. Copyright © 2011 John Wiley & Sons, Ltd.

  18. Detecting Pyrolysis Products from Bacteria on Mars

    NASA Technical Reports Server (NTRS)

    Glavin, Daniel; Schubert, Michael; Botta, Oliver; Kminek, Gerhard; Bada, Jeffrey L.

    2001-01-01

    A pyrolysis/sublimation technique was developed to isolate volatile amine compounds from a Mars soil analogue inoculated with approx. 10 billion Escherichia coli cells. In this technique, the inoculated soil is heated to 500 C for several seconds at Martian ambient pressure and the sublimate, collected by a cold finger, then analyzed using high performance liquid chromatography. Methylamine and ethylamine, produced from glycine and alanine decarboxylation, were the most abundant amine compounds detected after pyrolysis of the cells. A heating cycle similar to that utilized in our experiment was also used to release organic compounds from the Martian soil in the 1976 Viking gas chromatography/mass spectrometry (GC/MS) pyrolysis experiment. The Viking GC/MS did not detect any organic compounds of Martian origin above a level of a few parts per billion in the Martian surface soil. Although the Viking GC/MS instruments were not specifically designed to search for the presence of living cells on Mars, our experimental results indicate that at the part per billion level, the degradation products generated from several million bacterial cells per gram of Martian soil would not have been detected.

  19. Mass spectrometric studies of trimethylindium pyrolysis

    NASA Technical Reports Server (NTRS)

    Buchan, N. I.; Larsen, C. A.; Stringfellow, G. B.

    1988-01-01

    The kinetics of the pyrolysis of trimethylindium (TMIn) in He, D2, and H2 carriers was investigated using the atmospheric pressure flow-tube apparatus described by Larsen et al. (1987) and a time-of-flight mass spectrometer. The rate constant for the pyrolysis of TMIn in He was found to be comparable to that found by Jacko and Price (1964) for TMIn in toluene carrier (a radical scavenger), indicating that TMIn decomposes in He not by radical attack of methyl groups, but by homolytic fission. The decomposition of TMIn is enhanced in D2 and H2 carriers, where the principal products are CH3D and C2H6, and CH4 and C2H6, respectively, indicating that the reaction pathway in these carriers is different from those in He and toluene. The pyrolysis in H2 and D2 is attributed to a radical attack by H or D on TMIn. A reaction mechanism involving a short-lived hypervalent DTMIn species was proposed and was tested using numerical modeling techniques.

  20. Oxygen production by pyrolysis of lunar regolith

    NASA Technical Reports Server (NTRS)

    Senior, Constance L.

    1991-01-01

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

  1. Detecting Pyrolysis Products from Bacteria on Mars

    NASA Technical Reports Server (NTRS)

    Glavin, Daniel; Schubert, Michael; Botta, Oliver; Kminek, Gerhard; Bada, Jeffrey L.

    2001-01-01

    A pyrolysis/sublimation technique was developed to isolate volatile amine compounds from a Mars soil analogue inoculated with approx. 10 billion Escherichia coli cells. In this technique, the inoculated soil is heated to 500 C for several seconds at Martian ambient pressure and the sublimate, collected by a cold finger, then analyzed using high performance liquid chromatography. Methylamine and ethylamine, produced from glycine and alanine decarboxylation, were the most abundant amine compounds detected after pyrolysis of the cells. A heating cycle similar to that utilized in our experiment was also used to release organic compounds from the Martian soil in the 1976 Viking gas chromatography/mass spectrometry (GC/MS) pyrolysis experiment. The Viking GC/MS did not detect any organic compounds of Martian origin above a level of a few parts per billion in the Martian surface soil. Although the Viking GC/MS instruments were not specifically designed to search for the presence of living cells on Mars, our experimental results indicate that at the part per billion level, the degradation products generated from several million bacterial cells per gram of Martian soil would not have been detected.

  2. Alternative pathways for pyrolysis of cellulose

    SciTech Connect

    Shafizadph, F.

    1983-01-01

    Pyrolysis of biomass involves heterogeneous substrates and complex reactions. The substrate may contain various amounts of cellulose, hemicelluloses, lignin, extractives and inorganics with different thermal properties. The reactions involve alternative pathways and consecutive series, which are affected by pyrolytic conditions including the time and temperature profile, ambient atmosphere and catalysis by inorganic materials. Consequently, composition, yield and rate of formation of the products are highly dependent on the employed substrate and pyrolytic condition. Pyrolysis at temperatures below 300/sup 0/C involves depolymerization, dehydration, rearrangement and formation of carboxyl and carbonyl groups, evolution of CO and CO/sub 2/, development of free radicals and condensation to char. At temperatures above 300/sup 0/C, these reactions are accompanied by the conversion of the glycosyl units to levoglucosan by transglycosylation. This reaction is preceded by the activation of the molecule, presumably through glass transition, which gives the required conformational flexibility. At still higher temperatures (above 500/sup 0/C), the glycosyl structure of the levoglucosan or cellulose rapidly breaks down to provide a variety of low molecular weight fission products, including hydrocarbons and hydrogen as well as CO, CO/sub 2/ and H/sub 2/O obtained at lower temperatures. The pyrolysis products could further react to alter the composition of the pyrolysate.

  3. Oxygen production by pyrolysis of lunar regolith

    NASA Technical Reports Server (NTRS)

    Senior, Constance L.

    1991-01-01

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

  4. Thermogravimetric analysis and fast pyrolysis of Milkweed.

    PubMed

    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.

  5. Supercritical water pyrolysis of sewage sludge.

    PubMed

    Ma, Wenchao; Du, Guiyue; Li, Jian; Fang, Yuanhao; Hou, Li'an; Chen, Guanyi; Ma, Degang

    2017-01-01

    Municipal sewage sludge (SS) from wastewater treatment plant containing high water content (>85wt.%), lead to the difficulty of co-combustion with MSW or coal due to the high cost of drying. This study explores an alternative method by supercritical water (SCW) pyrolysis of sewage sludge (SS) in a high pressure reaction vessel. The effects of temperature and moisture content of SS on yield and composition of the products (bio-oil, bio char and non-condensable gas) were studied. A temperature of 385°C and moisture content of 85wt.% were found to be the optimum conditions for the maximum bio-oil production of 37.23wt.%, with a higher heating value of 31.08MJ/kg. In the optimum condition, the yields of aliphatic hydrocarbon and phenols were about 29.23wt.% and 12.51wt.%, respectively. The physical and chemical properties of bio-char were analyzed by using XRF and BET. Results of GC analyses of NCG showed that it has the maximum HHV of 13.39MJ/m(3) at 445°C and moisture content of 85wt.%. The reaction path from SS to bio-oil through SCW pyrolysis was given. Moreover, carbon balance was calculated for the optimal condition, and finding out that 64.27wt.% of the carbon content was transferred from SS to bio-oil. Finally, this work demonstrates that the SCW pyrolysis is a promising disposal method for SS.

  6. Pyrolysis technologies for municipal solid waste: a review.

    PubMed

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

    2014-12-01

    Pyrolysis has been examined as an attractive alternative to incineration for municipal solid waste (MSW) disposal that allows energy and resource recovery; however, it has seldom been applied independently with the output of pyrolysis products as end products. This review addresses the state-of-the-art of MSW pyrolysis in regards to its technologies and reactors, products and environmental impacts. In this review, first, the influence of important operating parameters such as final temperature, heating rate (HR) and residence time in the reaction zone on the pyrolysis behaviours and products is reviewed; then the pyrolysis technologies and reactors adopted in literatures and scale-up plants are evaluated. Third, the yields and main properties of the pyrolytic products from individual MSW components, refuse-derived fuel (RDF) made from MSW, and MSW are summarised. In the fourth section, in addition to emissions from pyrolysis processes, such as HCl, SO2 and NH3, contaminants in the products, including PCDD/F and heavy metals, are also reviewed, and available measures for improving the environmental impacts of pyrolysis are surveyed. It can be concluded that the single pyrolysis process is an effective waste-to-energy convertor but is not a guaranteed clean solution for MSW disposal. Based on this information, the prospects of applying pyrolysis technologies to dealing with MSW are evaluated and suggested. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Process for minimizing solids contamination of liquids from coal pyrolysis

    DOEpatents

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

    1981-04-21

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

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

    PubMed

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

    2015-03-01

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

  9. Methods for deoxygenating biomass-derived pyrolysis oil

    DOEpatents

    Baird, Lance Awender; Brandvold, Timothy A.

    2015-06-30

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

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

    PubMed

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

    2014-12-01

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

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

    SciTech Connect

    Mukarakate, C.; Robichaud, D.; Donohoe, B.; Jarvis, M.; Mino, K.; Bahng, M. K.; Nimlos, M.

    2012-01-01

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

  12. Confined-Pyrolysis as an Experimental Method for Hydrothermal Organic Synthesis

    NASA Technical Reports Server (NTRS)

    Leif, Roald N.; Simoneit, Bernd R. T.

    1995-01-01

    A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic and the competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.

  13. Predicting properties of gas and solid streams by intrinsic kinetics of fast pyrolysis of wood

    SciTech Connect

    Klinger, Jordan; Bar-Ziv, Ezra; Shonnard, David; Westover, Tyler; Emerson, Rachel

    2015-12-12

    Pyrolysis has the potential to create a biocrude oil from biomass sources that can be used as fuel or as feedstock for subsequent upgrading to hydrocarbon fuels or other chemicals. The product distribution/composition, however, is linked to the biomass source. This work investigates the products formed from pyrolysis of woody biomass with a previously developed chemical kinetics model. Different woody feedstocks reported in prior literature are placed on a common basis (moisture, ash, fixed carbon free) and normalized by initial elemental composition through ultimate analysis. Observed product distributions over the full devolatilization range are explored, reconstructed by the model, and verified with independent experimental data collected with a microwave-assisted pyrolysis system. These trends include production of permanent gas (CO, CO2), char, and condensable (oil, water) species. Elementary compositions of these streams are also investigated. As a result, close agreement between literature data, model predictions, and independent experimental data indicate that the proposed model/method is able to predict the ideal distribution from fast pyrolysis given reaction temperature, residence time, and feedstock composition.

  14. Biofuels from pyrolysis in perspective: trade-offs between energy yields and soil-carbon additions.

    PubMed

    Woolf, Dominic; Lehmann, Johannes; Fisher, Elizabeth M; Angenent, Largus T

    2014-06-03

    Coproduction of biofuels with biochar (the carbon-rich solid formed during biomass pyrolysis) can provide carbon-negative bioenergy if the biochar is sequestered in soil, where it can improve fertility and thus simultaneously address issues of food security, soil degradation, energy production, and climate change. However, increasing biochar production entails a reduction in bioenergy obtainable per unit biomass feedstock. Quantification of this trade-off for specific biochar-biofuel pathways has been hampered by lack of an accurate-yet-simple model for predicting yields, product compositions, and energy balances from biomass slow pyrolysis. An empirical model of biomass slow pyrolysis was developed and applied to several pathways for biochar coproduction with gaseous and liquid biofuels. Here, we show that biochar production reduces liquid biofuel yield by at least 21 GJ Mg(-1) C (biofuel energy sacrificed per unit mass of biochar C), with methanol synthesis giving this lowest energy penalty. For gaseous-biofuel production, the minimum energy penalty for biochar production is 33 GJ Mg(-1) C. These substitution rates correspond to a wide range of Pareto-optimal system configurations, implying considerable latitude to choose pyrolysis conditions to optimize for desired biochar properties or to modulate energy versus biochar yields in response to fluctuating price differentials for the two commodities.

  15. Predicting properties of gas and solid streams by intrinsic kinetics of fast pyrolysis of wood

    DOE PAGES

    Klinger, Jordan; Bar-Ziv, Ezra; Shonnard, David; ...

    2015-12-12

    Pyrolysis has the potential to create a biocrude oil from biomass sources that can be used as fuel or as feedstock for subsequent upgrading to hydrocarbon fuels or other chemicals. The product distribution/composition, however, is linked to the biomass source. This work investigates the products formed from pyrolysis of woody biomass with a previously developed chemical kinetics model. Different woody feedstocks reported in prior literature are placed on a common basis (moisture, ash, fixed carbon free) and normalized by initial elemental composition through ultimate analysis. Observed product distributions over the full devolatilization range are explored, reconstructed by the model, andmore » verified with independent experimental data collected with a microwave-assisted pyrolysis system. These trends include production of permanent gas (CO, CO2), char, and condensable (oil, water) species. Elementary compositions of these streams are also investigated. As a result, close agreement between literature data, model predictions, and independent experimental data indicate that the proposed model/method is able to predict the ideal distribution from fast pyrolysis given reaction temperature, residence time, and feedstock composition.« less

  16. Confined-pyrolysis as an experimental method for hydrothermal organic synthesis

    NASA Astrophysics Data System (ADS)

    Leif, Roald N.; Simoneit, Bernd R. T.

    1995-10-01

    A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic compounds and the competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.

  17. Confined-Pyrolysis as an Experimental Method for Hydrothermal Organic Synthesis

    NASA Technical Reports Server (NTRS)

    Leif, Roald N.; Simoneit, Bernd R. T.

    1995-01-01

    A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic and the competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.

  18. Estimation of risks by chemicals produced during laser pyrolysis of tissues

    NASA Astrophysics Data System (ADS)

    Weber, Lothar W.; Spleiss, Martin

    1995-01-01

    Use of laser systems in minimal invasive surgery results in formation of laser aerosol with volatile organic compounds of possible health risk. By use of currently identified chemical substances an overview on possibly associated risks to human health is given. The class of the different identified alkylnitriles seem to be a laser specific toxicological problem. Other groups of chemicals belong to the Maillard reaction type, the fatty acid pyrolysis type, or even the thermally activated chemolysis. In relation to the available different threshold limit values the possible exposure ranges of identified substances are discussed. A rough estimation results in an exposure range of less than 1/100 for almost all substances with given human threshold limit values without regard of possible interactions. For most identified alkylnitriles, alkenes, and heterocycles no threshold limit values are given for lack of, until now, practical purposes. Pyrolysis of anaesthetized organs with isoflurane gave no hints for additional pyrolysis products by fragment interactions with resulting VOCs. Measurements of pyrolysis gases resulted in detection of small amounts of NO additionally with NO2 formation at plasma status.

  19. Confined-pyrolysis as an experimental method for hydrothermal organic synthesis.

    PubMed

    Leif, R N; Simoneit, B R

    1995-10-01

    A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic compounds and competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.

  20. Rapid characterisation of Candida albicans by pyrolysis mass spectrometry.

    PubMed

    White, G C; Sisson, P R; Freeman, R; Cookson, B D

    1994-08-01

    Clinical isolates (41) of Candida spp. from three possible outbreaks of nosocomially-acquired infection were compared by pyrolysis mass spectrometry (PMS) and by a combined morphotyping and resistotyping (M-R typing) method. Both systems characterised all the isolates and distinguished one isolate of C. tropicalis and another of C. glabrata from the 39 isolates of C. albicans. Results from both systems suggested that cross-infection with a single strain contributed to two of the outbreaks. In several instances, more than one strain of C. albicans was found amongst multiple isolates from the same patient. PMS is a simple, rapid and objective technique capable of characterising C. albicans isolates; discrimination was similar to M-R typing.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Methane Pyrolysis and Disposing Off Resulting Carbon

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

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

  3. Methane Pyrolysis and Disposing Off Resulting Carbon

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  5. Effects of pretreatment in steam on the pyrolysis behavior of Loy Yang brown coal

    SciTech Connect

    Cai Zeng; George Favas; Hongwei Wu; Alan L. Chaffee; Jun-ichiro Hayashi; Chun-Zhu Li

    2006-02-01

    Dewatering/drying of Victorian brown coal will be an integral part of future brown coal utilization processes aimed at the reduction of greenhouse gas emissions. This study aims to investigate the effects of the thermal pretreatment of brown coal in the presence of steam/water on its subsequent pyrolysis behavior. A Victorian (Loy Yang) brown coal was thermally pretreated in pressurized steam and inert atmospheres. The pyrolysis behavior of these pretreated coal samples was investigated in a wire-mesh reactor. While the pretreatment in steam at temperatures higher than 250{sup o}C increased the char yield of the steam-treated coal, it did not affect the overall pyrolysis char yield at 1000{sup o} C s{sup -1} if the weight loss during the pretreatment in steam was also considered. However, the tar yield decreased significantly after the pretreatment in the presence of steam. The UV-fluorescence spectroscopy of tars revealed that the release of large aromatic systems from the steam-treated coal was only affected by the pretreatment in steam if the treatment temperature was very high (e.g. 350{sup o}C). The loss of NaCl and the use of high pressure during the pretreatment of brown coal in steam were not the main reasons for the changes in the observed tar yield. The hydrolysis of O-containing structures such as ethers, esters, and carboxylates during the pretreatment in the presence of steam plays an important role in the fates of these O-containing structures during pretreatment and subsequent pyrolysis, leading to changes in the pyrolysis behavior of the brown coal. 36 refs., 8 figs.

  6. Continuous polyethylene pyrolysis for hybrid flame/CVD synthesis of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Richardson, Nicholas Wilder

    2011-12-01

    A system was designed to integrate the continuous feeding of polyethylene for pyrolysis into the hybrid flame/CVD carbon nanotube (CNT) synthesis process previously developed in this laboratory. Following the completion of the stainless steel design and machining operations, the polyethylene dispenser, screw conveyor, pyrolysis chamber, venturi flame holder, particle filter, synthesis chamber and dual]zone heating system were successfully integrated for full operation. A water cooling unit was incorporated with the screw conveyor to ensure flawless delivery of polyethylene to the pyrolysis chamber, as well as a support system to suspend the CNT catalyst within the synthesis chamber. As with the previously developed process, the intended use of combustion effluent within the apparatus was to synthesize multi]walled CNTs using stainless steel wire mesh. This was facilitated by an extensive study of the effluent produced with this continuous feeding system at varying system settings and in comparison to the previous apparatus, followed by a determination of the system parameters, which result in conditions most favorable to multi walled CNT growth.

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

    PubMed

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

    2013-01-11

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

  8. Pyrolysis of hydrochar from digestate: Effect of hydrothermal carbonization and pyrolysis temperatures on pyrochar formation.

    PubMed

    Garlapalli, Ravinder K; Wirth, Benjamin; Reza, M Toufiq

    2016-11-01

    Digestate from anaerobic digestion of biomass often contains more than 90% of water, which is economically unfavorable for pyrolysis. Hydrothermal carbonization (HTC) has potential to treat very wet biomass, however, the hydrochar may be acidic, contains polycyclic aromatic hydrocarbons (PAH) and toxic organic substances (e.g., phenolic compounds), and has very low Brunauer-Emmett-Teller (BET) surface area. In this study, pyrolysis of digestate derived hydrochar is performed at various pyrolysis and HTC temperatures. Solid chars were characterized for elemental analysis, pH, PAH, BET, pore size and volume, and phenolic substances, while HTC process liquids were characterized for pH, organic acids, furfural derivatives, and phenolic substances. Physicochemical characteristics of pyro-HTC char were compared with corresponding pyrochar and hydrochar. Pyro-HTC chars produced at higher HTC (i.e., 260°C) and pyrolysis temperatures (i.e., 800°C) showed highest BET surface area (63.5m(2)g(-1)), no PAH, relatively mild basic pH (9.34), and no phenolic compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Pyrolysis of sugarcane bagasse and co-pyrolysis with an Argentinean subbituminous coal

    SciTech Connect

    Bonelli, P.R.; Buonomo, E.L.; Cukierman, A.L.

    2007-07-01

    Physicochemical properties of the charcoal arising from pyrolysis of sugarcane bagasse at 600{sup o}C and 800{sup o}C were determined to evaluate potentialities for specific end uses. The charcoals were found fairly adequate as solid bio-fuels. Their quality was comparable to charcoals obtained from some other agro-industrial by-products, reportedly proposed as substitutes of wood-based ones. Surface properties of the charcoal generated at the higher temperature indicated that it is reasonably suited for potential use as low-cost rough adsorbent, soil amender, and/or for further upgrading to activated carbon. Moreover, kinetic measurements for pyrolysis of the sugarcane bagasse individually and mixed with an Argentinean subbituminous coal in equal proportions were conducted by thermogravimetry for the range 25 -900{sup o}C. Data modeling accounting for variations in the activation energy with process evolution provided a proper description of pyrolysis and co-pyrolysis over the entire temperature range.

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

    PubMed

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

    2017-12-01

    Biochar samples produced from rice straw by pyrolysis at different temperatures (400°C and 800°C) and under different atmospheres (N2 and CO2) were applied to lettuce growth in a 'preparation-application' system. The conversion of potassium in the prepared biochar and the effect of the temperature used for pyrolysis on the bioavailability of potassium in the biochar were investigated. Root samples from lettuce plants grown with and without application of biochar were assayed by X-ray photoelectron spectroscopy (XPS). The optimal conditions for preparation of biochar to achieve the maximum bioavailability of potassium (i.e. for returning biochar to soil) were thus determined. Complex-K, a stable speciation of potassium in rice straw, was transformed into potassium sulfate, potassium nitrate, potassium nitrite, and potassium chloride after oxygen-limited pyrolysis. The aforementioned ionic-state potassium species can be directly absorbed and used by plants. Decomposition of the stable speciation of potassium during the pyrolysis process was more effective at higher temperature, whereas the pyrolysis atmosphere (CO2 and N2) had little effect on the quality of the biochar. Based on the potassium speciation in the biochar, the preparation cost, and the plant growth and rigor after the application of returning biochar to soil, 400°C and CO2 atmosphere were the most appropriate conditions for preparation of biochar. Copyright © 2017. Published by Elsevier B.V.

  11. Self-heating co-pyrolysis of excessive activated sludge with waste biomass: energy balance and sludge reduction.

    PubMed

    Ding, Hong-Sheng; Jiang, Hong

    2013-04-01

    In this work, co-pyrolysis of sludge with sawdust or rice husk was investigated. The results showed that the co-pyrolysis technology could be used to dispose of the excessive activated sludge without external energy input. The results also demonstrated that no obvious synergistic effect occurred except for heat transfer in the co-pyrolysis if the co-feeding biomass and sludge had similar thermogravimetric characteristics. The experimental results combined with calculation showed that adding sawdust accounting for 49.6% of the total feedstock or rice husk accounting for 74.7% could produce bio-oil to keep the energy balance of the co-pyrolysis system and self-heat it. The sludge from solar drying bed can be further reduced by 38.6% and 35.1% by weight when co-pyrolyzed with rice husk and sawdust, respectively. This study indicates that sludge reduction without external heat supply through co-pyrolysis of sludge with waste biomass is practically feasible.

  12. Pyrolysis and gasification of coal at high temperatures. Quarterly progress report No. 10, December 15, 1989--March 15, 1990

    SciTech Connect

    Zygourakis, K.

    1990-12-31

    We made considerable progress towards developing a thermogravimetric reactor with in-situ video imaging capability (TGA/IVIM). Such a reactor will allow us to observe macroscopic changes in the morphology of pyrolyzing particles and thermal ignitions while monitoring at the time the weight of pyrolyzing or reacting samples. The systematic investigation on the effects of pyrolysis conditions and char macropore structure on char reactivity continued. Pyrolysis and gasification experiments were performed consecutively in our TGA reactor and the char reactivity patterns were measured for a wide range of temperatures (400 to 600{degrees}C). These conditions cover both the kinetic and the diffusion limited regimes. Our results show conclusively that chars produced at high pyrolysis heating rates (and, therefore, having a more open cellular macropore structure) are more reactive and ignite more easily than chars pyrolyzed at low heating rates. These results have been explained using available predictions from theoretical models. We also investigated for the first time the effect of coal particle size and external mass transfer limitations on the reactivity patterns and ignition behavior of char particles combusted in air. Finally, we used our hot stage reactor to monitor the structural transformations occurring during pyrolysis via a video microscopy system. Pyrolysis experiments were videotaped and particle swelling and the particle ignitions were determined and analyzed using digitized images from these experiments.

  13. Charcoal from the pyrolysis of rapeseed plant straw-stalk

    SciTech Connect

    Karaosmanoglu, F.; Tetik, E.

    1999-07-01

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

  14. Stabilization of Fast Pyrolysis Oil: Post Processing Final Report

    SciTech Connect

    Elliott, Douglas C.; Lee, Suh-Jane; Hart, Todd R.

    2012-03-01

    UOP LLC, a Honeywell Company, assembled a comprehensive team for a two-year project to demonstrate innovative methods for the stabilization of pyrolysis oil in accordance with DOE Funding Opportunity Announcement (FOA) DE-PS36-08GO98018, Biomass Fast Pyrolysis Oil (Bio-oil) Stabilization. In collaboration with NREL, PNNL, the USDA Agricultural Research Service (ARS), Pall Fuels and Chemicals, and Ensyn Corporation, UOP developed solutions to the key technical challenges outlined in the FOA. The UOP team proposed a multi-track technical approach for pyrolysis oil stabilization. Conceptually, methods for pyrolysis oil stabilization can be employed during one or both of two stages: (1) during the pyrolysis process (In Process); or (2) after condensation of the resulting vapor (Post-Process). Stabilization methods fall into two distinct classes: those that modify the chemical composition of the pyrolysis oil, making it less reactive; and those that remove destabilizing components from the pyrolysis oil. During the project, the team investigated methods from both classes that were suitable for application in each stage of the pyrolysis process. The post processing stabilization effort performed at PNNL is described in this report. The effort reported here was performed under a CRADA between PNNL and UOP, which was effective on March 13, 2009, for 2 years and was subsequently modified March 8, 2011, to extend the term to December 31, 2011.

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

    USDA-ARS?s Scientific Manuscript database

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

  16. Evaluation of Pyrolysis Oil as Carbon Source for Fungal Fermentation.

    PubMed

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

    2016-01-01

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

  17. Evaluation of Pyrolysis Oil as Carbon Source for Fungal Fermentation

    PubMed Central

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

    2016-01-01

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

  18. Fuel and fuel blending components from biomass derived pyrolysis oil

    DOEpatents

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

    2012-12-11

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

  19. Microwave-assisted pyrolysis of biomass for liquid biofuels production.

    PubMed

    Yin, Chungen

    2012-09-01

    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 dielectric heating" effects. This paper presents a state-of-the-art review of microwave-assisted pyrolysis of biomass. First, conventional fast pyrolysis and microwave dielectric heating is briefly introduced. Then microwave-assisted pyrolysis process is thoroughly discussed stepwise from biomass pretreatment to bio-oil collection. The existing efforts are summarized in a table, providing a handy overview of the activities (e.g., feedstock and pretreatment, reactor/pyrolysis conditions) and findings (e.g., pyrolysis products) of various investigations.

  20. Adding value to ethanol production byproducts through microwave assisted pyrolysis

    USDA-ARS?s Scientific Manuscript database

    The aim of this project is to increase the value of distillers grain by utilizing it as a feedstock for microwave assisted pyrolysis (MAP). Pyrolysis is the chemical/thermal conversion of biomass without the presence of oxygen into newly formed products: gases, liquids and solids. This conversion pr...

  1. Catalytic pyrolysis-GC/MS of lignin from several sources

    USDA-ARS?s Scientific Manuscript database

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

  2. Advanced Plasma Pyrolysis Assembly (PPA) Reactor and Process Development

    NASA Technical Reports Server (NTRS)

    Wheeler, Richard R., Jr.; Hadley, Neal M.; Dahl, Roger W.; Abney, Morgan B.; Greenwood, Zachary; Miller, Lee; Medlen, Amber

    2012-01-01

    Design and development of a second generation Plasma Pyrolysis Assembly (PPA) reactor is currently underway as part of NASA's Atmosphere Revitalization Resource Recovery effort. By recovering up to 75% of the hydrogen currently lost as methane in the Sabatier reactor effluent, the PPA helps to minimize life support resupply costs for extended duration missions. To date, second generation PPA development has demonstrated significant technology advancements over the first generation device by doubling the methane processing rate while, at the same time, more than halving the required power. One development area of particular interest to NASA system engineers is fouling of the PPA reactor with carbonaceous products. As a mitigation plan, NASA MSFC has explored the feasibility of using an oxidative plasma based upon metabolic CO2 to regenerate the reactor window and gas inlet ports. The results and implications of this testing are addressed along with the advanced PPA reactor development.

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

    NASA Astrophysics Data System (ADS)

    Urban, Brook

    Thermochemical conversion methods such as pyrolysis have the potential for converting diverse biomass feedstocks into liquid fuels. In particular, bio-oil yields can be maximized by implementing flash pyrolysis to facilitate rapid heat transfer to the solids along with short vapor residence times to minimize secondary degradation of bio-oils. This study first focused on the design and construction of a fluidized-bed flash pyrolysis reactor with a high-efficiency bio-oil recovery unit. Subsequently, the reactor was used to perform flash pyrolysis of soybean pellets to assess the thermochemical conversion of oleaginous biomass feedstocks. The fluidized bed reactor design included a novel feed input mechanism through suction created by flow of carrier gas through a venturi which prevented plugging problems that occur with a more conventional screw feeders. In addition, the uniquely designed batch pyrolysis unit comprised of two tubes of dissimilar diameters. The bottom section consisted of a 1" tube and was connected to a larger 3" tube placed vertically above. At the carrier gas flow rates used in these studies, the feed particles remained fluidized in the smaller diameter tube, but a reduction in carrier gas velocity in the larger diameter "disengagement chamber" prevented the escape of particles into the condensers. The outlet of the reactor was connected to two Allihn condensers followed by an innovative packed-bed dry ice condenser. Due to the high carrier gas flow rates in fluidized bed reactors, bio-oil vapors form dilute aerosols upon cooling which that are difficult to coalesce and recover by traditional heat exchange condensers. The dry ice condenser provided high surface area for inertial impaction of these aerosols and also allowed easy recovery of bio-oils after natural evaporation of the dry ice at the end of the experiments. Single step pyrolysis was performed between 250-610°C with a vapor residence time between 0.3-0.6s. At 550°C or higher, 70% of

  4. Molecular configuration and pyrolysis reactions of phenolic-novolaks.

    NASA Technical Reports Server (NTRS)

    Winkler, E. L.; Parker, J. A.

    1971-01-01

    Description of a statistical method for characterizing the structure of an average phenolic-novolak prepolymer molecule in terms of the total number of phenolic nuclei that compose the molecule and the number of these nuclei that are pendent. It is only necessary to resort to experimental pyrolysis to evaluate the thermokinetic parameters for pyrolysis for the ablator. In addition, the fraction of phenolic involved in the major pyrolysis reactions can be estimated in terms of the parameters previously evaluated. It is shown that the overlapping reactions which occur during pyrolysis of a phenolic-novolak can be resolved by pyrolyzing samples with different extents of cure. It is then possible to determine the kinetic parameters for pyrolysis for the major reactions by well-known methods which often fail when reactions are not well resolved.

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

    PubMed

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

    2012-01-01

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

  6. Combustion Properties of Biomass Flash Pyrolysis Oils: Final Project Report

    SciTech Connect

    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.

  7. Pyrolysis of furan in a microreactor

    NASA Astrophysics Data System (ADS)

    Urness, Kimberly N.; Guan, Qi; Golan, Amir; Daily, John W.; Nimlos, Mark R.; Stanton, John F.; Ahmed, Musahid; Ellison, G. Barney

    2013-09-01

    A silicon carbide microtubular reactor has been used to measure branching ratios in the thermal decomposition of furan, C4H4O. The pyrolysis experiments are carried out by passing a dilute mixture of furan (approximately 0.01%) entrained in a stream of helium through the heated reactor. The SiC reactor (0.66 mm i.d., 2 mm o.d., 2.5 cm long) operates with continuous flow. Experiments were performed with a reactor inlet pressure of 100-300 Torr and a wall temperature between 1200 and 1600 K; characteristic residence times in the reactor are 60-150 μs. The unimolecular decomposition pathway of furan is confirmed to be: furan (+ M) rightleftharpoons α-carbene or β-carbene. The α-carbene fragments to CH2=C=O + HC≡CH while the β-carbene isomerizes to CH2=C=CHCHO. The formyl allene can isomerize to CO + CH3C≡CH or it can fragment to H + CO + HCCCH2. Tunable synchrotron radiation photoionization mass spectrometry is used to monitor the products and to measure the branching ratio of the two carbenes as well as the ratio of [HCCCH2]/[CH3C≡CH]. The results of these pyrolysis experiments demonstrate a preference for 80%-90% of furan decomposition to occur via the β-carbene. For reactor temperatures of 1200-1400 K, no propargyl radicals are formed. As the temperature rises to 1500-1600 K, at most 10% of the decomposition of CH2=C=CHCHO produces H + CO + HCCCH2 radicals. Thermodynamic conditions in the reactor have been modeled by computational fluid dynamics and the experimental results are compared to the predictions of three furan pyrolysis mechanisms. Uncertainty in the pressure-dependency of the initiation reaction rates is a possible a source of discrepancy between experimental results and theoretical predictions.

  8. Kinetics of coal pyrolysis and devolatilization

    SciTech Connect

    Seery, D.J.; Freihaut, J.D.; Proscia, W.M.

    1991-01-01

    The objective of these coordinated experimental and modeling studies is to develop an improved understanding of the kinetics of coal devolatilization which are relevant to suspension firing of powdered coal. These fundamental kinetic studies address several topics related to an improved understanding of pulverized coal combustion and includes both homogeneous and hetergeneous reactions. The principal topics include: (a) the pyrolysis and devolatilization of coal; and (b) the formation of char. Research activities include small-scale experimentation, interpretation of experimental results in terms of mechanistic understanding and the development and validation of kinetic models of fundamental processes. 6 refs., 20 figs., 7 tabs.

  9. Analytical pyrolysis of cells and cell fragments

    SciTech Connect

    Faix, O.; Bertelt, E.

    1995-12-01

    Wood of spruce, beech and birch was disintegrated without chemical pretreatment after 10 minutes of steaming at 110{degrees}C in a laboratory defibrator. Fibers, vessels, and fragments of secondary wall were separated by wet screening. A hydrocylon was used for separation of middle lamellae. By using analytical pyrolysis-GC/MS, parenchymatic cells were found to be richer in lignin than the other cells. The lignin content of middle lamellae was 35% (beech, spruce) and 39% (birch). In agreement with the literature, the S/G ratios of the vessels and middle lamellae was lower than those of the other cells and cell fragments.

  10. Pyrolysis reactor and fluidized bed combustion chamber

    DOEpatents

    Green, Norman W.

    1981-01-06

    A solid carbonaceous material is pyrolyzed in a descending flow pyrolysis reactor in the presence of a particulate source of heat to yield a particulate carbon containing solid residue. The particulate source of heat is obtained by educting with a gaseous source of oxygen the particulate carbon containing solid residue from a fluidized bed into a first combustion zone coupled to a second combustion zone. A source of oxygen is introduced into the second combustion zone to oxidize carbon monoxide formed in the first combustion zone to heat the solid residue to the temperature of the particulate source of heat.

  11. Initial Stages of Pyrolysis of Polyethylene

    NASA Astrophysics Data System (ADS)

    Popov, Konstantin V.

    Combustion and flammability of plastics are important topics of practical interest directly related to fire safety and recycling of polymeric materials; pyrolysis of the solid is the initial step of its combustion. One of the main ways to study such complicated processes is through detailed mechanistic modeling, in which the process is represented by a set of many elementary reactions. Mechanistic modeling of combustion of plastics is considerably hindered by the lack of necessary kinetic data. In virtually all existing models of polymer pyrolysis the majority of kinetic data used are derived from the corresponding gas phase values of smaller species. The use of gas phase rate constants is, generally, not justified without an experimental justification. In the first part of the work the influence of condensed phase on the rate of scission of a carbon-carbon bond (the reaction that initiates pyrolysis and combustion) in polyethylene (PE) was studied using the method of Reactive Molecular Dynamics (RMD). A method based on a two-step kinetic mechanism was developed to decouple the cage effect from the kinetics of the reaction under study. It was observed that under the conditions of condensed phase the rate constant of C-C bond scission in PE decreased by an order of magnitude compared to that obtained in vacuum. It was also shown that under the conditions of polymer melt the rate constant does not depend on the length of the polymer chain. In the second part of the work the kinetics of liquid phase and gas phase products of PE pyrolysis were studied experimentally using Gas Chromatography and Nuclear Magnetic Resonance. Based on the assumption of applicability of gas phase kinetic data for C-C scission reaction and beta-scission reaction under the conditions of polymer melt, rate constants of hydrogen transfer, radical addition to double bonds, and radical recombination were determined via kinetic modeling of the experimental results. The obtained values of the rate

  12. Toxicity of pyrolysis gases from wood

    NASA Technical Reports Server (NTRS)

    Hilado, C. J.; Huttlinger, N. V.; Oneill, B. A.; Kourtides, D. A.; Parker, J. A.

    1977-01-01

    The toxicity of the pyrolysis gases from nine wood samples was investigated. The samples of hardwoods were aspen poplar, beech, yellow birch, and red oak. The samples of softwoods were western red cedar, Douglas fir, western hemlock, eastern white pine, and southern yellow pine. There was no significant difference between the wood samples under rising temperature conditions, which are intended to simulate a developing fire, or under fixed temperature conditions, which are intended to simulate a fully developed fire. This test method is used to determine whether a material is significantly more toxic than wood under the preflashover conditions of a developing fire.

  13. Rapid habitability assessment of Mars samples by pyrolysis-FTIR

    NASA Astrophysics Data System (ADS)

    Gordon, Peter R.; Sephton, Mark A.

    2016-02-01

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

  14. Intermediate pyrolysis of biomass energy pellets for producing sustainable liquid, gaseous and solid fuels.

    PubMed

    Yang, Y; Brammer, J G; Mahmood, A S N; Hornung, A

    2014-10-01

    This work describes the use of intermediate pyrolysis system to produce liquid, gaseous and solid fuels from pelletised wood and barley straw feedstock. Experiments were conducted in a pilot-scale system and all products were collected and analysed. The liquid products were separated into an aqueous phase and an organic phase (pyrolysis oil) under gravity. The oil yields were 34.1 wt.% and 12.0 wt.% for wood and barley straw, respectively. Analysis found that both oils were rich in heterocyclic and phenolic compounds and have heating values over 24 MJ/kg. The yields of char for both feedstocks were found to be about 30 wt.%, with heating values similar to that of typical sub-bituminous class coal. Gas yields were calculated to be approximately 20 wt.%. Studies showed that both gases had heating values similar to that of downdraft gasification producer gas. Analysis on product energy yields indicated the process efficiency was about 75%.

  15. Decoupling HZSM-5 catalyst activity from deactivation during upgrading of pyrolysis oil vapors.

    PubMed

    Wan, Shaolong; Waters, Christopher; Stevens, Adam; Gumidyala, Abhishek; Jentoft, Rolf; Lobban, Lance; Resasco, Daniel; Mallinson, Richard; Crossley, Steven

    2015-02-01

    The independent evaluation of catalyst activity and stability during the catalytic pyrolysis of biomass is challenging because of the nature of the reaction system and rapid catalyst deactivation that force the use of excess catalyst. In this contribution we use a modified pyroprobe system in which pulses of pyrolysis vapors are converted over a series of HZSM-5 catalysts in a separate fixed-bed reactor controlled independently. Both the reactor-bed temperature and the Si/Al ratio of the zeolite are varied to evaluate catalyst activity and deactivation rates independently both on a constant surface area and constant acid site basis. Results show that there is an optimum catalyst-bed temperature for the production of aromatics, above which the production of light gases increases and that of aromatics decrease. Zeolites with lower Si/Al ratios give comparable initial rates for aromatics production, but far more rapid catalyst deactivation rates than those with higher Si/Al ratios.

  16. Thermodynamical Study on Production of Acetylene from Coal Pyrolysis in Hydrogen Plasma

    NASA Astrophysics Data System (ADS)

    Wang, Fei; Guo, Wenkang; Yuan, Xingqiu; Zhao, Taize

    2006-05-01

    The chemical thermodynamic equilibrium of acetylene production by coal pyrolysis in hydrogen plasma was studied. The thermodynamic equilibrium is obtained by using the method of free energy. Calculated results show that the hydrogen concentration in the equilibrium system is very important for the acetylene production by coal conversion and the energy consumption for the production of acetylene per-kilogram strongly depends on the hydrogen concentration and the temperature.

  17. Organic emissions from coal pyrolysis: mutagenic effects.

    PubMed Central

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

    1987-01-01

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

  18. Combustion, pyrolysis, gasification, and liquefaction of biomass

    SciTech Connect

    Reed, T.B.

    1980-09-01

    All the products now obtained from oil can be provided by thermal conversion of the solid fuels biomass and coal. As a feedstock, biomass has many advantages over coal and has the potential to supply up to 20% of US energy by the year 2000 and significant amounts of energy for other countries. However, it is imperative that in producing biomass for energy we practice careful land use. Combustion is the simplest method of producing heat from biomass, using either the traditional fixed-bed combustion on a grate or the fluidized-bed and suspended combustion techniques now being developed. Pyrolysis of biomass is a particularly attractive process if all three products - gas, wood tars, and charcoal - can be used. Gasification of biomass with air is perhaps the most flexible and best-developed process for conversion of biomass to fuel today, yielding a low energy gas that can be burned in existing gas/oil boilers or in engines. Oxygen gasification yields a gas with higher energy content that can be used in pipelines or to fire turbines. In addition, this gas can be used for producing methanol, ammonia, or gasoline by indirect liquefaction. Fast pyrolysis of biomass produces a gas rich in ethylene that can be used to make alcohols or gasoline. Finally, treatment of biomass with high pressure hydrogen can yield liquid fuels through direct liquefaction.

  19. Biofuel from jute stick by pyrolysis technology

    NASA Astrophysics Data System (ADS)

    Ferdous, J.; Parveen, M.; Islam, M. R.; Haniu, H.; Takai, K.

    2017-06-01

    In this study the conversion of jute stick into biofuels and chemicals by externally heated fixed-bed pyrolysis reactor have been taken into consideration. The solid jute stick was characterized through proximate and ultimate analysis, gross calorific values and thermo-gravimetric analysis to investigate their suitability as feedstock for this consideration. The solid biomass particles were fed into the reactor by gravity feed type reactor feeder. The products were oil, char and gases. The liquid and char products were collected separately while the gas was flared into the atmosphere. The process conditions were varied by fixed-bed temperature; feed stock particle size, N2 gas flow rate and running time. All parameters were found to influence the product yields significantly. The maximum liquid yields were 50 wt% of solid jute stick at reactor temperature 425°C for N2 gas flow rate 6 l/min, feed particle size 1180-1700 µm and running time 30 min. Liquid products obtained at these conditions were characterized by physical properties, chemical analysis and GC-MS techniques. The results show that it is possible to obtained liquid products that are comparable to petroleum fuels and valuable chemical feedstock from the selected biomass if the pyrolysis conditions are chosen accordingly.

  20. Kinetic studies on the pyrolysis of pinewood.

    PubMed

    Mishra, Garima; Kumar, Jitendra; Bhaskar, Thallada

    2015-04-01

    The kinetic study for pyrolysis of pine wood has been studied by a thermogravimetric analyzer in an inert atmosphere. Non isothermal model free kinetic methods were used to evaluate kinetics at six different heating rates of 5-40°C/min. Three zones can be detected from the iso-conversional plot of pine with average activation energy values of 134.32 kJ/mol, 146.89 kJ/mol and 155.76 kJ/mol in the conversion range of 1-22%, 24-84% and 85-90%, respectively. The activation energy values were used to determine the reaction mechanism using master plots and compensation parameters. The results show that the pyrolysis process of pine wood can be described by two dimensional diffusion reaction mechanism in a wide range of conversion up to 0.7, followed by close to one and half order reaction mechanism. The kinetic results were validated by making isothermal predictions from non-isothermal data.

  1. Combustion, pyrolysis, gasification, and liquefaction of biomas

    NASA Astrophysics Data System (ADS)

    Reed, T. B.

    1980-09-01

    The advantages of biomass as a feedstock are examined and biomass conversion techniques are described. Combustion is the simplest method of producing heat from biomass, using either the traditional fixed bed combustion on a grate or the fluidized bed and suspended combustion techniques now being developed. Pyrolysis of biomass is a particularly attractive process if all three products gas, wood tars, and charcoal can be used. Gasification of biomass with air is perhaps the most flexible and best developed process for conversion of biomass to fuel, yielding a low energy gas that can be burned in existing gas/oil boilers or in engines. Oxygen gasification yields a gas with higher energy content that can be used in pipelines or to fire turbines. In addition, this gas can be used for producing methanol, ammonia, or gasoline by indirect liquefaction. Fast pyrolysis of biomass produces a gas rich in ethylene that can be used to make alcohols or gasoline. Finally, treatment of biomass with high pressure hydrogen can yield liquid fuels through direct liquefaction.

  2. Catalytic pyrolysis of olive mill wastewater sludge

    NASA Astrophysics Data System (ADS)

    Abdellaoui, Hamza

    From 2008 to 2013, an average of 2,821.4 kilotons/year of olive oil were produced around the world. The waste product of the olive mill industry consists of solid residue (pomace) and wastewater (OMW). Annually, around 30 million m3 of OMW are produced in the Mediterranean area, 700,000 m3 year?1 in Tunisia alone. OMW is an aqueous effluent characterized by an offensive smell and high organic matter content, including high molecular weight phenolic compounds and long-chain fatty acids. These compounds are highly toxic to micro-organisms and plants, which makes the OMW a serious threat to the environment if not managed properly. The OMW is disposed of in open air evaporation ponds. After evaporation of most of the water, OMWS is left in the bottom of the ponds. In this thesis, the effort has been made to evaluate the catalytic pyrolysis process as a technology to valorize the OMWS. The first section of this research showed that 41.12 wt. % of the OMWS is mostly lipids, which are a good source of energy. The second section proved that catalytic pyrolysis of the OMWS over red mud and HZSM-5 can produce green diesel, and 450 °C is the optimal reaction temperature to maximize the organic yields. The last section revealed that the HSF was behind the good fuel-like properties of the OMWS catalytic oils, whereas the SR hindered the bio-oil yields and quality.

  3. Pyrolysis of high sulfur Indian coals

    SciTech Connect

    B.P. Baruah; Puja Khare

    2007-12-15

    Pyrolysis experiments under laboratory conditions for five numbers of high sulfur coal samples from the states of Meghalaya and Nagaland, India, were carried out at temperatures of 450, 600, 850, and 1000{sup o}C, respectively. The yield of products and thermal release of sulfur from these coals are investigated. The distribution of sulfur in the pyrolyzed products, i.e., char/coke, gas, and tar, is also reported. Hydrocarbon and sulfurous gases released at different temperatures were analyzed by a gas chromatograph (GC) with an FID (flame ionized detector) and an FPD (flame photometric detector), respectively. H{sub 2}S evolution during coal pyrolysis was found to be a function of temperature up to 850{sup o}C. The low concentration of SO{sub 2} detected for some of the samples is due to decomposition of inorganic sulphates present. Evolution of methane for the coals tested increases with the increase of temperature. Maximum sulfur release was found in the range of 600-850{sup o}C and has a decreasing tendency from 850-1000{sup o}C, which might be due to the incorporation of sulfur released into the coal matrix. Activation energies for sulfur release were found in the range of 38-228 kJ mol{sup -1}, which were higher than the reported activation energies for lignites and bituminous coals mainly due to highly stable organic sulfur functionalities. 52 refs., 9 figs., 6 tabs.

  4. Comparison of direct and indirect pyrolysis of micro-algae Isochrysis.

    PubMed

    Wang, Xin; Zhao, Bingwei; Tang, Xiaohan; Yang, Xiaoyi

    2015-03-01

    Yield and composition of pyrolysis oil in direct and indirect pyrolysis process were investigated which indicated that pyrolysis of defatted microalgae provided a potential way to convert protein and carbohydrate to biofuels. Defatted microalgae pyrolysis with lipid extraction has higher total oil yield than only microalgae direct pyrolysis. There was an increase for N-heterocyclic compounds and phenols and a decrease for hydrocarbons in defatted microalgae pyrolysis oil. There is an apparent decrease from C12 to C16 and nearly no carbon distribution from C17 to C22 for defatted microalgae pyrolysis. Based on composition of pyrolysis feedstock, pyrolysis oil yields were simulated by Compounds Biofuel Model and their accuracy was less than ±4.4%. Considering total oil yield and characteristics, microalgae pyrolysis after lipid extraction process is a promising way for microalgae utilization. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. High-resolution mass spectrometric analysis of biomass pyrolysis vapors

    DOE PAGES

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

    2017-01-19

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

  6. Mass spectrometric studies of fast pyrolysis of cellulose.

    PubMed

    Degenstein, John C; Hurt, Matt; Murria, Priya; Easton, McKay; Choudhari, Harshavardhan; Yang, Linan; Riedeman, James; Carlsen, Mark S; Nash, John J; Agrawal, Rakesh; Delgass, W Nicholas; Ribeiro, Fabio H; Kenttämaa, Hilkka I

    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.

  7. Pyrolysis of Dried Wastewater Biosolids Can Be Energy Positive.

    PubMed

    McNamara, Patrick J; Koch, Jon D; Liu, Zhongzhe; Zitomer, Daniel H

    Pyrolysis is a thermal process that converts biosolids into biochar (a soil amendment), py-oil and py-gas, which can be energy sources. The objectives of this research were to determine the product yield of dried biosolids during pyrolysis and the energy requirements of pyrolysis. Bench-scale experiments revealed that temperature increases up to 500 °C substantially decreased the fraction of biochar and increased the fraction of py-oil. Py-gas yield increased above 500 °C. The energy required for pyrolysis was approximately 5-fold less than the energy required to dry biosolids (depending on biosolids moisture content), indicating that, if a utility already uses energy to dry biosolids, then pyrolysis does not require a substantial amount of energy. However, if a utility produces wet biosolids, then implementing pyrolysis may be costly because of the energy required to dry the biosolids. The energy content of py-gas and py-oil was always greater than the energy required for pyrolysis.

  8. Thermal effects in cellulose pyrolysis: Relationship to char formation processes

    SciTech Connect

    Milosavljevic, I.; Oja, V.; Suuberg, E.M.

    1996-03-01

    The thermochemistry of cellulose pyrolysis has been studied by a combination of differential scanning calorimetry and thermogravimetric analysis. Additionally, the vapor pressure and heat of vaporization of levoglucosan have been determined by an effusion method. The cellulose pyrolysis has been carried out under inert gas at heating rates from 0.1 to 60 K/min. The main cellulose thermal degradation pathway is endothermic, in the absence of mass transfer limitations that promote char formation. The endothermicity is estimated to be about 538 J/g of volatiles evolved. It is concluded that this endothermicity mainly reflects a latent heat requirement for vaporizing the primary tar decomposition products. Pyrolysis can be driven in the exothermic direction by char-forming processes that compete with tar-forming processes. The formation of char is estimated to be exothermic to the extent of about 2 kJ/g of char formed. Low heating rates, in concert with mass transfer limitations, serve to drive the pyrolysis in this direction. The enthalpy of cellulose pyrolysis is thus seen to be a sensitive function of the pyrolysis conditions. Pyrolysis appears to initially follow a common thermal pathway (in terms of enthalpy required per mass of volatile loss), irrespective of heating rate. Only at some finite level of conversion does the thermal trajectory of the process follow a heating rate dependent path, as significant char formation begins to occur.

  9. Mass spectrometric studies of fast pyrolysis of cellulose

    SciTech Connect

    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.

  10. Additives initiate selective production of chemicals from biomass pyrolysis.

    PubMed

    Leng, Shuai; Wang, Xinde; Wang, Lei; Qiu, Huizhe; Zhuang, Guilin; Zhong, Xing; Wang, Jianguo; Ma, Fengyun; Liu, Jingmei; Wang, Qiang

    2014-03-01

    To improve chemicals selectivity under low temperature, a new method that involves the injection of additives into biomass pyrolysis is introduced. This method allows biomass pyrolysis to achieve high selectivity to chemicals under low temperature (300°C), while nothing was obtained in typical pyrolysis under 300°C. However, by using the new method, the first liquid drop emerged at the interval between 140°C and 240°C. Adding methanol to mushroom scrap pyrolysis obtained high selectivity to acetic acid (98.33%), while adding ethyl acetate gained selectivity to methanol (65.77%) in bagasse pyrolysis and to acetone (72.51%) in corncob pyrolysis. Apart from basic chemicals, one high value-added chemical (2,3-dihydrobenzofuran) was also detected, which obtained the highest selectivity (10.33%) in corncob pyrolysis through the addition of ethyl acetate. Comparison of HZSM-5 and CaCO3 catalysis showed that benzene emerged in the liquid because of the larger degree of cracking and hydrodeoxygenation over HZSM-5.

  11. Mechanism and kinetics for the initial steps of pyrolysis and combustion of 1,6-dicyclopropane-2,4-hexyne from ReaxFF reactive dynamics.

    PubMed

    Liu, Lianchi; Bai, Chen; Sun, Huai; Goddard, William A

    2011-05-19

    We report the kinetic analysis and mechanism for the initial steps of pyrolysis and combustion of a new fuel material, 1,6-dicyclopropane-2,4-hexyne, that has enormous heats of pyrolysis and combustion, making it a potential high-energy fuel or fuel additive. These studies employ the ReaxFF force field for reactive dynamics (RD) simulations of both pyrolysis and combustion processes for both unimolecular and multimolecular systems. We find that both pyrolysis and combustion initiate from unimolecular reactions, with entropy-driven reactions being most important in both processes. Pyrolysis initiates with extrusion of an ethylene molecule from the fuel molecule and is followed quickly by isomerization of the fuel molecule, which induces additional radicals that accelerate the pyrolysis process. In the combustion process, we find three distinct mechanisms for the O(2) attack on the fuel molecule: (1) attack on the cyclopropane, ring expanding to form the cyclic peroxide which then decomposes; (2) attack onto the central single bond of the diyne which then fissions to form two C(5)H(5)O radicals; (3) attack on the alkyne-cyclopropane moiety to form a seven-membered ring peroxide which then decomposes. Each of these unimolecular combustion processes releases energy that induces additional radicals to accelerate the combustion process. Here oxygen has major effects both as the radical acceptor and as the radical producer. We extract both the effective activation energy and the effective pre-exponential factor by kinetic analysis of pyrolysis and combustion from these ReaxFF simulations. The low value of the derived effective activation energy (26.18 kcal/mol for pyrolysis and 16.40 kcal/mol for combustion) reveals the high activity of this fuel molecule.

  12. Rapid pyrolysis of agricultural residues at high temperatures

    SciTech Connect

    Zanzi, R.; Sjoestroem, K.; Bjoernbom, E.

    1995-11-01

    Agriculture plays an important role in the economy of many countries especially in Latin America. Gasification of agricultural residues such as bagasse from sugar cane for electricity production is a solution to meet energy demands with a favourable effect on the environment. Pyrolysis (heating solid biomass in absence of air to produce solid, liquid or gaseous fuels) is the first step in gasification and combustion. Depending on the conditions the solid, liquid or gaseous products are maximized. The treatment conditions in the pyrolysis determine the char yield and its reactivity in gasification. Char yield and char reactivity are important for the capacity of the gasifier. The rapid pyrolysis of biomass is performed in a free-fall reactor at 850{degrees}C. The biomass used in the study was wood (birch) and agricultural residues such as bagasse and leaves both from sugar cane and banana. The reactivity of the char obtained in pyrolysis is determined by reaction with steam in a thermobalance. The low amounts of a highly porous char and the high yield of gaseous products obtained in rapid pyrolysis of bagasse at high temperature are similar to those produced in rapid pyrolysis of wood. Bagasse gives more volatiles and less char than sugar cane residues and banana harvest residues. Bagasse produces a less reactive char after devolatilization than wood. The char obtained by rapid pyrolysis contains a fraction that can be further volatilized by slow pyrolysis. The fraction of char removed by slow pyrolysis is lower in chars from bagasse and sugar cane leaves than in chars from wood. The structures of the chars obtained from birch, bagasse, sugar cane and banana leaves were observed by scanning electron microscope. Qualitative X-ray microanalysis of the chars was made using an electron microscope supplied with an energy dispersive spectrometer. Ca, K, S, Si, Al and Mg were visible on the surface of the chars.

  13. Fates of Chemical Elements in Biomass during Its Pyrolysis.

    PubMed

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

    2017-05-10

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

  14. Co-pyrolysis of sewage sludge and manure.

    PubMed

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

    2017-01-01

    The management and valorization of residual organic matter, such as sewage sludge and manure, is gaining interest because of the increasing volume of these residues, their localized generation and the related problems. The anaerobic digestion of mixtures of sewage sludge and manure could be performed due to the similarities between both residues. The purpose of this study is to evaluate the feasibility of the co-pyrolysis of sewage sludge (SS) and digested manure (DM) as a potential management technology for these residues. Pyrolysis of a sewage sludge/manure blend (50:50%) was performed at 525°C in a stirred batch reactor under N2 atmosphere. The product yields and some characteristics of the product were analyzed and compared to the results obtained in the pyrolysis of pure residues. Potential synergetic and antagonist effects during the co-pyrolysis process were evaluated. Although sewage sludge and manure seem similar in nature, there are differences in their pyrolysis product properties and distribution due to their distinct ash and organic matter composition. For the co-pyrolysis of SS and DM, the product yields did not show noticeable synergistic effects with the exception of the yields of organic compounds, being slightly higher than the predicted average, and the H2 yield, being lower than expected. Co-pyrolysis of SS and DM could be a feasible management alternative for these residues in locations where both residues are generated, since the benefits and the drawbacks of the co-pyrolysis are similar to those of the pyrolysis of each residue. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Vacuum pyrolysis of waste tires with basic additives

    SciTech Connect

    Zhang Xinghua; Wang Tiejun Ma Longlong; Chang Jie

    2008-11-15

    Granules of waste tires were pyrolyzed under vacuum (3.5-10 kPa) conditions, and the effects of temperature and basic additives (Na{sub 2}CO{sub 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) {approx}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{sub 2}CO{sub 3} addition. Pyrolysis gas was mainly composed of H{sub 2}, CO, CH{sub 4}, CO{sub 2}, C{sub 2}H{sub 4} and C{sub 2}H{sub 6}. Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5 wt%) was much higher.

  16. Vacuum pyrolysis of waste tires with basic additives.

    PubMed

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

    2008-11-01

    Granules of waste tires were pyrolyzed under vacuum (3.5-10 kPa) conditions, and the effects of temperature and basic additives (Na2CO3, NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48 wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50 wt% was achieved at 480 degrees C by adding 3 wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39 wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na2CO3 addition. Pyrolysis gas was mainly composed of H2, CO, CH4, CO2, C2H4 and C2H6. Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5 wt%) was much higher.

  17. CFD modeling of space-time evolution of fast pyrolysis products in a bench-scale fluidized-bed reactor

    USDA-ARS?s Scientific Manuscript database

    A model for the evolution of pyrolysis products in a fluidized bed has been developed. In this study the unsteady constitutive transport equations for inert gas flow and decomposition kinetics were modeled using the commercial computational fluid dynamics (CFD) software FLUENT-12. The model system d...

  18. Can portable pyrolysis units make biomass utilization affordable while using bio-char to enhance soil productivity and sequester carbon?

    Treesearch

    Mark Coleman; Deborah Page-Dumroese; Jim Archuleta; Phil Badger; Woodum Chung; Tyron Venn; Dan Loeffler; Greg Jones; Kristin McElligott

    2010-01-01

    We describe a portable pyrolysis system for bioenergy production from forest biomass that minimizes long-distance transport costs and provides for nutrient return and long-term soil carbon storage. The cost for transporting biomass to conversion facilities is a major impediment to utilizing forest biomass. If forest biomass could be converted into bio-oil in the field...

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

    PubMed

    Zhao, Bingwei; Wang, Xin; Yang, Xiaoyi

    2015-12-01

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

  20. Recent developments in fast pyrolysis of ligno-cellulosic materials.

    PubMed

    Kersten, Sascha; Garcia-Perez, Manuel

    2013-06-01

    Pyrolysis is a thermochemical process to convert ligno-cellulosic materials into bio-char and pyrolysis oil. This oil can be further upgraded or refined for electricity, transportation fuels and chemicals production. At the time of writing, several demonstration factories are considered worldwide aiming at maturing the technology. Research is focusing on understanding the underlying processes at all relevant scales, ranging from the chemistry of cell wall deconstruction to optimization of pyrolysis factories, in order to produce better quality oils for targeted uses. Among the several bio-oil applications that are currently investigated the production and fermentation of pyrolytic sugars explores the promising interface between thermochemistry and biotechnology.

  1. Pyrolysis of carbonaceous materials with solvent quench recovery

    DOEpatents

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

    1978-04-18

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

  2. Method for preventing plugging in the pyrolysis of agglomerative coals

    DOEpatents

    Green, Norman W.

    1979-01-23

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

  3. Catalytic pyrolysis of plastic wastes - Towards an economically viable process

    SciTech Connect

    McIntosh, M.J.; Arzoumanidis, G.G.; Brockmeier, F.E.

    1996-07-01

    The ultimate goal of our project is an economically viable pyrolysis process to recover useful fuels and/or chemicals from plastics- containing wastes. This paper reports the effects of various promoted and unpromoted binary oxide catalysts on yields and compositions of liquid organic products, as measured in a small laboratory pyrolysis reactor. On the basis of these results, a commercial scale catalytic pyrolysis reactor was simulated by the Aspen software and rough costs were estimated. The results suggest that such a process has potential economic viability.

  4. Pyrolysis of oil palm empty fruit bunch biomass pellets using multimode microwave irradiation.

    PubMed

    Salema, Arshad Adam; Ani, Farid Nasir

    2012-12-01

    Oil palm empty fruit bunch pellets were subjected to pyrolysis in a multimode microwave (MW) system (1 kW and 2.45 GHz frequency) with and without the MW absorber, activated carbon. The ratio of biomass to MW absorber not only affected the temperature profiles of the EFB but also pyrolysis products such as bio-oil, char, and gas. The highest bio-oil yield of about 21 wt.% was obtained with 25% MW absorber. The bio-oil consisted of phenolic compounds of about 60-70 area% as detected by GC-MS and confirmed by FT-IR analysis. Ball lightning (plasma arc) occurred due to residual palm oil in the EFB biomass without using an MW absorber. The bio-char can be utilized as potential alternative fuel because of its heating value (25 MJ/kg). Copyright © 2012 Elsevier Ltd. All rights reserved.

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

    PubMed

    Cao, Hongliang; Xin, Ya; Yuan, Qiaoxia

    2016-02-01

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

  6. Integration of decentralized torrefaction with centralized catalytic pyrolysis to produce green aromatics from coffee grounds.

    PubMed

    Chai, Li; Saffron, Christopher M; Yang, Yi; Zhang, Zhongyu; Munro, Robert W; Kriegel, Robert M

    2016-02-01

    The aim of this work was to integrate decentralized torrefaction with centralized catalytic pyrolysis to convert coffee grounds into the green aromatic precursors of terephthalic acid, namely benzene, toluene, ethylbenzene, and xylenes (BTEX). An economic analysis of this bioproduct system was conducted to examine BTEX yields, biomass costs and their sensitivities. Model predictions were verified experimentally using pyrolysis GC/MS to quantify BTEX yields for raw and torrefied biomass. The production cost was minimized when the torrefier temperature and residence time were 239°C and 34min, respectively. This optimization study found conditions that justify torrefaction as a pretreatment for making BTEX, provided that starting feedstock costs are below $58 per tonne. Copyright © 2015. Published by Elsevier Ltd.

  7. Thermodynamic study on the formation of acetylene during coal pyrolysis in the arc plasma jet

    SciTech Connect

    Bao, W.; Li, F.; Cai, G.; Lu, Y.; Chang, L.

    2009-07-01

    Based on the principle of minimizing the Gibbs free energy, the composition of C-H-O-N-S equilibrium system about acetylene formation during the pyrolysis in arc plasma jet for four kinds of different rank-ordered coals such as Datong, Xianfeng, Yangcheng, and Luan was analyzed and calculated. The results indicated that hydrogen, as the reactive atmosphere, was beneficial to the acetylene formation. The coal ranks and the hydrogen, oxygen, nitrogen, and sulfur in coal all could obviously affect the acetylene yield. The mole fraction of acetylene is the maximum when the ratio value of atom H/C was 2. The content of oxygen was related to the acetylene yield, but it does not compete with CO formation. These agreed with the experimental results, and they could help to select the coal type for the production of acetylene through plasma pyrolysis process.

  8. Semiempirical molecular orbital estimation of the relative stability of bianthryls produced by anthracene pyrolysis

    SciTech Connect

    Mulholland, J.A.; Mukherjee, J.; Wornat, M.J.; Sarofim, A.F.; Rutledge, G.C. . Dept. of Chemical Engineering)

    1993-08-01

    The pyrolysis of pure anthracene at temperatures between 1,200 and 1,500 K produced all six bianthryl isomers whose relative yields appear to be related to steric factors. To evaluate the hypothesis that thermodynamic factors govern the product distribution of bianthryls in this system, the relative enthalpies and entropies of biaryl isomers were estimated by molecular orbital modeling, using the semiempirical AM1 (Austin Model 1). Computational analysis of several isomer sets demonstrates that the relative stabilities of a large number of biaryl isomers are determined largely by steric interactions caused by structural features defined as bays, coves, and fjords. These steric factors affect both the degree of biaryl twist in the preferred conformation and the freedom of internal rotation. Molecular orbital modeling supports the hypothesis that a thermodynamic distribution of bianthryl isomers is produced by anthracene pyrolysis.

  9. Catalytic pyrolysis of wood biomass in an auger reactor using calcium-based catalysts.

    PubMed

    Veses, A; Aznar, M; Martínez, I; Martínez, J D; López, J M; Navarro, M V; Callén, M S; Murillo, R; García, T

    2014-06-01

    Wood catalytic pyrolysis using calcium-based materials was studied in an auger reactor at 450°C. Two different catalysts, CaO and CaO·MgO were evaluated and upgraded bio-oils were obtained in both cases. Whilst acidity and oxygen content remarkable decrease, both pH and calorific value increase with respect to the non-catalytic test. Upgrading process was linked to the fact that calcium-based materials could not only fix the CO2-like compounds but also promoted the dehydration reactions. In addition, process simulation demonstrated that the addition of these catalysts, especially CaO, could favour the energetic integration since a lowest circulation of heat carrier between combustor and auger reactor should be needed. An energy self-sustained system was obtained where thermal energy required for biomass drying and for pyrolysis reaction was supplied by non-condensable gas and char combustion, respectively.

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

    PubMed

    Hübner, Tobias; Mumme, Jan

    2015-05-01

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

  11. Phenols from pyrolysis and co-pyrolysis of tobacco biomass components.

    PubMed

    Kibet, Joshua K; Khachatryan, Lavrent; Dellinger, Barry

    2015-11-01

    Phenol and its derivatives (phenol, o-, m-, p-cresols, catechol, hydroquinone, methoxy substituted phenols, etc. referred to as phenolic compounds or phenols) are well-known toxicants that exist in the environment and affect both human and natural ecosystems. This study explores quantitatively the yields of phenolic compounds from the thermal degradation (pyrolysis and oxidative pyrolysis) of common tobacco biomass components (lignin, tyrosine, ethyl cellulose, sodium alginate, and laminarin) as well as some mixtures (lignin/tyrosine, ethyl cellulose/tyrosine and sodium alginate/tyrosine) considered important in high temperature cooking, tobacco smoking, and forest fires. Special attention has been given to binary mixtures including those containing tyrosine-pyrolysis of binary mixtures of tyrosine with lignin and ethyl cellulose results in significant reductions in the yields of majority phenols relative to those from the thermal degradation of tyrosine. These results imply that the significant reductions of phenol yields in mixtures are not only dependent upon the mass fractions of the components but also the synergetic inhibition effect of biomass components on the thermal degradation of tyrosine. A mechanistic description of this phenomenon is suggested. The results may also be implied in tobacco industry that the cigarette paper (as ethyl cellulose derivative) may play a critical role in reducing the concentration of phenolic compounds released during tobacco burning.

  12. The direct pyrolysis and catalytic pyrolysis of Nannochloropsis sp. residue for renewable bio-oils.

    PubMed

    Pan, Pan; Hu, Changwei; Yang, Wenyan; Li, Yuesong; Dong, Linlin; Zhu, Liangfang; Tong, Dongmei; Qing, Renwei; Fan, Yong

    2010-06-01

    Nannochloropsis sp. (a kind of green microalga) residue was pyrolyzed without catalyst or with different amount of HZSM-5 catalyst in a fixed bed reactor in nitrogen flow. The effects of pyrolysis parameters such as temperature and catalyst-to-material ratio on product yields were studied. The bio-oils obtained were analyzed by elemental, GC-MS and FTIR analysis. The results indicated that the bio-oils from catalytic pyrolysis of Nannochloropsis sp. residue (BOCP) had lower oxygen content (19.5 wt.%) and higher heating-value (32.7 MJ kg(-1)) than those obtained from direct pyrolysis (BODP) which had an oxygen content of 30.1 wt.% and heating-value of 24.6 MJ kg(-1). The BODP mainly consisted of long carbon chain compounds with various terminal groups (LCTG), while the BOCP mainly consisted of aromatic hydrocarbons. These properties of bio-oils demonstrated that the Nannochloropsis sp. residue can be used as a renewable energy resource and chemical feedstock.

  13. Sulfur emission from Victorian brown coal under pyrolysis, oxy-fuel combustion and gasification conditions.

    PubMed

    Chen, Luguang; Bhattacharya, Sankar

    2013-02-05

    Sulfur emission from a Victorian brown coal was quantitatively determined through controlled experiments in a continuously fed drop-tube furnace under three different atmospheres: pyrolysis, oxy-fuel combustion, and carbon dioxide gasification conditions. The species measured were H(2)S, SO(2), COS, CS(2), and more importantly SO(3). The temperature (873-1273 K) and gas environment effects on the sulfur species emission were investigated. The effect of residence time on the emission of those species was also assessed under oxy-fuel condition. The emission of the sulfur species depended on the reaction environment. H(2)S, SO(2), and CS(2) are the major species during pyrolysis, oxy-fuel, and gasification. Up to 10% of coal sulfur was found to be converted to SO(3) under oxy-fuel combustion, whereas SO(3) was undetectable during pyrolysis and gasification. The trend of the experimental results was qualitatively matched by thermodynamic predictions. The residence time had little effect on the release of those species. The release of sulfur oxides, in particular both SO(2) and SO(3), is considerably high during oxy-fuel combustion even though the sulfur content in Morwell coal is only 0.80%. Therefore, for Morwell coal utilization during oxy-fuel combustion, additional sulfur removal, or polishing systems will be required in order to avoid corrosion in the boiler and in the CO(2) separation units of the CO(2) capture systems.

  14. Physical pretreatment of biogenic-rich trommel fines for fast pyrolysis.

    PubMed

    Eke, Joseph; Onwudili, Jude A; Bridgwater, Anthony V

    2017-09-15

    Energy from Waste (EfW) technologies such as fluidized bed fast pyrolysis, are beneficial for both energy generation and waste management. Such technologies, however face significant challenges due to the heterogeneous nature, particularly the high ash contents of some municipal solid waste types e.g. trommel fines. A study of the physical/mechanical and thermal characteristics of these complex wastes is important for two main reasons; (a) to inform the design and operation of pyrolysis systems to handle the characteristics of such waste; (b) to control/modify the characteristics of the waste to fit with existing EFW technologies via appropriate feedstock preparation methods. In this study, the preparation and detailed characterisation of a sample of biogenic-rich trommel fines has been carried out with a view to making the feedstock suitable for fast pyrolysis based on an existing fluidized bed reactor. Results indicate that control of feed particle size was very important to prevent problems of dust entrainment in the fluidizing gas as well as to prevent feeder hardware problems caused by large stones and aggregates. After physical separation and size reduction, nearly 70wt% of the trommel fines was obtained within the size range suitable for energy recovery using the existing fast pyrolysis system. This pyrolyzable fraction could account for about 83% of the energy content of the 'as received' trommel fines sample. Therefore there was no significant differences in the thermochemical properties of the raw and pre-treated feedstocks, indicating that suitably prepared trommel fines samples can be used for energy recovery, with significant reduction in mass and volume of the original waste. Consequently, this can lead to more than 90% reduction in the present costs of disposal of trommel fines in landfills. In addition, the recovered plastics and textile materials could be used as refuse derived fuel. Copyright © 2017. Published by Elsevier Ltd.

  15. Formation of NOx precursors during Chinese pulverized coal pyrolysis in an arc plasma jet

    SciTech Connect

    Wei-ren Bao; Jin-cao Zhang; Fan Li; Li-ping Chang

    2007-08-15

    The formation of NOx precursors (HCN and NH{sub 3}) from the pyrolysis of several Chinese pulverized coals in an arc plasma jet was investigated through both thermodynamic analysis of the C-H-O-N system and experiments. Results of thermodynamic analysis show that the dominant N-containing gaseous species is HCN together with a small amount of ammonia above the temperature of 2000 K. The increase of H content advances the formation of HCN and NH{sub 3}, but the yields of HCN and NH{sub 3} are decreased with a high concentration of O in the system. These results are accordant with the experimental data. The increasing of input power promotes the formation of HCN and NH{sub 3} from coal pyrolysis in an arc plasma jet. Tar-N is not formed during the process. The yield of HCN changes insignificantly with the changing of the residence time of coal particles in the reactor, but that of NH{sub 3} decreases as residence times increase because of the relative instability at high temperature. Adsorption and gasification of CO{sub 2} on the coal surface also can restrain the formation of HCN and NH{sub 3} compare to the results in an Ar plasma jet. Yields of HCN and NH{sub 3} are sensitive to the coal feeding rate, indicating that NOx precursors could interact with the nascent char to form other N-containing species. The formation of HCN and NH{sub 3} during coal pyrolysis in a H{sub 2}/Ar plasma jet are not dependent on coal rank. The N-containing gaseous species is released faster than others in the volatiles during coal pyrolysis in an arc plasma jet, and the final nitrogen content in the char is lower than that in the parent coal, which it is independent of coal type. 16 refs., 9 figs., 1 tab.

  16. Fines in fluidized bed silane pyrolysis

    NASA Technical Reports Server (NTRS)

    Hsu, G.; Hogle, R.; Rohatgi, N.; Morrison, A.

    1984-01-01

    Silicon deposition on silicon seed particles by silane pyrolysis in a fluidized-bed reactor is investigated as a low-cost, high-throughput method to produce high-purity polysilicon for solar-cell applications. Studies of fines, particles 0.1-10 microns diam, initiated from homogeneous decomposition in the reactor were conducted using 2 and 6-in-diam fluidized beds. The studies show functional dependences of fines elutriation on silane feed concentration, temperature, gas velocity, and bubble size. The observation that the fines elutriation is generally below 10 percent of the silicon-in-silane feed is attributed to scavenging by large particles in an environment of less free space for homogeneous nucleation. Preliminary results suggest that, with proper conditions and distributor design, high-silane-concentration (over 50 percent SiH4 in H2) feed may be used.

  17. Pyrolysis of vegetation by brief intense irradiation

    SciTech Connect

    Fendell, F.E.; Kung, E.Y. )

    1993-09-01

    When nonreflected intense visible radiation of about 4 x 10 exp 6 J/(sq m-sec) is incident on a dense vegetative layer (about 3-kg/sq m loading, 0.3-m height) for even a second or two, the absorbing leafy matter can be desiccated and gasified. Simple unsteady 1D models are formulated and solved to characterize the rate of propagation earthward of the pyrolysis front, at which the vegetative population under consideration totally disappears. Distinct treatments are undertaken for temperate-cereal-like layers which contain only foliage (hay, wheat, grass) and brush-like layers, in which not only effectively pyrolyzable leafy matter but also partially pyrolyzable woody-stem matter exist. Qualitative remarks consider soot formation in the pyrolyzate and/or combustion of the hydrocarbon-vapor pyrolyzate with interstitial air. 7 refs.

  18. Fluidized bed selective pyrolysis of coal

    DOEpatents

    Shang, Jer Y.; Cha, Chang Y.; Merriam, Norman W.

    1992-01-01

    The present invention discloses a process for the pyrolysis of coal which comprises the effective utilization of two zonal inclined fluidized beds, where said zones can be selectively controlled as to temperature and heating rate. The first zonal inclined fluidized bed serves as a dryer for crushed coal and additionally is controlled to selectively pyrolyze said coal producing substantially carbon dioxide for recycle use. The second zonal inclined fluidized bed further pyrolyzes the coal to gaseous, liquid and char products under controlled temperature and heating rate zones designed to economically integrate the product mix. The gas and liquid products are recovered from the gaseous effluent stream while the char which remains can be further treated or utilized in a subsequent process step.

  19. Fluidized bed selective pyrolysis of coal

    DOEpatents

    Shang, J.Y.; Cha, C.Y.; Merriam, N.W.

    1992-12-15

    The present invention discloses a process for the pyrolysis of coal which comprises the effective utilization of two zonal inclined fluidized beds, where said zones can be selectively controlled as to temperature and heating rate. The first zonal inclined fluidized bed serves as a dryer for crushed coal and additionally is controlled to selectively pyrolyze said coal producing substantially carbon dioxide for recycle use. The second zonal inclined fluidized bed further pyrolyses the coal to gaseous, liquid and char products under controlled temperature and heating rate zones designed to economically integrate the product mix. The gas and liquid products are recovered from the gaseous effluent stream while the char which remains can be further treated or utilized in a subsequent process step. 9 figs.

  20. Making Activated Carbon by Wet Pressurized Pyrolysis

    NASA Technical Reports Server (NTRS)

    Fisher, John W.; Pisharody, Suresh; Wignarajah, K.; Moran, Mark

    2006-01-01

    A wet pressurized pyrolysis (wet carbonization) process has been invented as a means of producing activated carbon from a wide variety of inedible biomass consisting principally of plant wastes. The principal intended use of this activated carbon is room-temperature adsorption of pollutant gases from cooled incinerator exhaust streams. Activated carbon is highly porous and has a large surface area. The surface area depends strongly on the raw material and the production process. Coconut shells and bituminous coal are the primary raw materials that, until now, were converted into activated carbon of commercially acceptable quality by use of traditional production processes that involve activation by use of steam or carbon dioxide. In the wet pressurized pyrolysis process, the plant material is subjected to high pressure and temperature in an aqueous medium in the absence of oxygen for a specified amount of time to break carbon-oxygen bonds in the organic material and modify the structure of the material to obtain large surface area. Plant materials that have been used in demonstrations of the process include inedible parts of wheat, rice, potato, soybean, and tomato plants. The raw plant material is ground and mixed with a specified proportion of water. The mixture is placed in a stirred autoclave, wherein it is pyrolized at a temperature between 450 and 590 F (approximately between 230 and 310 C) and a pressure between 1 and 1.4 kpsi (approximately between 7 and 10 MPa) for a time between 5 minutes and 1 hour. The solid fraction remaining after wet carbonization is dried, then activated at a temperature of 500 F (260 C) in nitrogen gas. The activated carbon thus produced is comparable to commercial activated carbon. It can be used to adsorb oxides of sulfur, oxides of nitrogen, and trace amounts of hydrocarbons, any or all of which can be present in flue gas. Alternatively, the dried solid fraction can be used, even without the activation treatment, to absorb

  1. Pressure passivation of mild pyrolysis char

    SciTech Connect

    Ochs, T.; Summers, C.; Schroeder, K.; Sands, W.

    1999-07-01

    Low-rank coals that have been thermally dried in the mild pyrolysis process have a tendency to spontaneously combust. The spontaneous combustion of coals and chars has been linked to their affinity for oxygen. The USDOE has developed a method for the passivation of mild pyrolysis char derived from a low-rank coal using pressure differentials to control the oxidation of the active sites in the char rapidly and safely. Initial experiments performed by the USDOE show that the affinity of the coal for oxygen uptake (residual oxygen demand, ROD) is reduced by exposure of the coal-char to high-pressure gas mixtures including air or oxygen-enriched air. Laboratory-scale tests have shown that the ROD can be rapidly reduced by cycling the active coals between low-pressure (atmospheric pressure or less) and high-pressure (500 psi to 1,500 psi) regimes. Cycling the pressure of the treatment gas provides rapid passivation resulting from two effects: The high-pressure cycle forces fresh oxygen into the pores which have been purged of adsorbed gases and reaction products. The pores of coal are small enough to prohibit free convection and force oxygen exchange to take place by way of diffusion under ambient conditions. The forced introduction of fresh process gas under high pressure overcomes the restrictions due to diffusion limits while the removal of adsorbed products clears the way to active surface sites. The high pressure increases the number of oxygen molecules with sufficient energy to overcome the activation barrier of the passivation reaction, due to the increased number of molecules per unit volume of the high-pressure gas. Combined, the two effects rapidly produce a coal with a significantly reduced ROD.

  2. Screw pyrolysis technology for sewage sludge treatment.

    PubMed

    Tomasi Morgano, Marco; Leibold, Hans; Richter, Frank; Stapf, Dieter; Seifert, Helmut

    2017-06-07

    Sewage sludge quantities have grown continuously since the introduction of the European Directive (UWWTD 91/271/EEC) relating to the treatment of urban wastewater. In the present, most of the sewage sludge is combusted in single fuels incineration plants or is co-fired in waste incineration or coal power plants. The combustion of sewage sludge is a proven technology. Other treatments, such as fluidized bed gasification, were successfully adopted to produce suitable syngas for power production. Besides, the number of large wastewater treatment plants is relatively small compared to the local rural ones. Moreover, alternative technologies are arising with the main target of nutrients recovery, with a special focus on phosphorus. The aforementioned issues, i.e. the small scale (below 1MW) and the nutrients recovery, suggest that pyrolysis in screw reactors may become an attractive alternative technology for sewage sludge conversion, recovery and recycling. In this work, about 100kg of dried sewage sludge from a plant in Germany were processed at the newly developed STYX Reactor, at KIT. The reactor combines the advantages of screw reactors with the high temperature filtration, in order to produce particle and ash free vapors and condensates, respectively. Experiments were carried out at temperatures between 350°C and 500°C. The yield of the char decreased from 66.7wt.% to 53.0wt.%. The same trend was obtained for the energy yield, while the maximum pyrolysis oil yield of 13.4wt.% was obtained at 500°C. Besides mercury, the metals and the other minerals were completely retained in the char. Nitrogen and sulfur migrated from the solid to the condensate and to the gas, respectively. Based on the energy balance, a new concept for the decentral production of char as well as heat and power in an externally fired micro gas turbine showed a cogeneration efficiency up to about 40%. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. Pyrolysis, combustion and gasification characteristics of Nannochloropsis gaditana microalgae.

    PubMed

    Sanchez-Silva, L; López-González, D; Garcia-Minguillan, A M; Valverde, J L

    2013-02-01

    Pyrolysis, combustion and gasification characteristics of Nannochloropsis gaditana microalgae (NG microalgae) were investigated by thermogravimetric analysis (TGA). NG microalgae pyrolysis and combustion could be divided into three main stages: dehydration, proteins and polysaccharides degradation and char decomposition. The effects of the initial sample mass, particle size and gas flow on the pyrolysis and combustion processes were studied. In addition, gasification operation conditions such as temperature, initial sample mass, particle size, sweep gas flow and steam concentration, were experimentally evaluated. The evolved gases were analyzed online using mass spectroscopy (MS). In pyrolysis and combustion processes, most of the gas products were generated at the second degradation step. N-compounds evolution was associated with the degradation of proteins. Furthermore, SO(2) release from combustion could be related to sulphated polysaccharides decomposition. The main products detected during gasification were CO(2), CO, H(2), indicating that oxidation reactions, water gas and water gas shift reactions, were predominant.

  4. TG-DSC-FTIR Analysis of Cyanobacteria Pyrolysis

    NASA Astrophysics Data System (ADS)

    Supeng, Luo; Guirong, Bao; Hua, Wang; Fashe, Li; Yizhe, Li

    Pyrolysis of cyanobacteria from Dianchi lake was investigated by TG-DSC-FTIR analysis at different heating rates (10, 20, 40°C/min). The results indicated that the pyrolysis of cyanobacteria can be divided into four stages: evaporation, depolymerization, devolatilization and carbonization. Meanwhile, the initial weight-loss temperature, weight-loss extreme position, endothermic and exothermic peaks were moved to higher temperature with the increaseing of the heating rate. The kinetic analysis was made with Popescu method. It indicated that the best kinetic model for the pyrolysis of cyanobacteria was the cylindrical symmetry of the phase boundary reaction model. The main pyrolysis gases checked with real-time online FTIR were HCN, NH3, CO, CO2, water vapor and hydrocarbons.

  5. Pyrolysis process for the treatment of food waste.

    PubMed

    Grycová, Barbora; Koutník, Ivan; Pryszcz, Adrian

    2016-10-01

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

  6. Acidity of biomass fast pyrolysis bio-oils

    SciTech Connect

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

    2010-12-17

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

  7. Influence of mineral matter on pyrolysis of palm oil wastes

    SciTech Connect

    Yang, Haiping; Chen, Hanping; Zheng, Chuguang; Yan, Rong; Lee, Dong Ho; Liang, David Tee

    2006-09-15

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

  8. Auto shredder residue recycling: Mechanical separation and pyrolysis

    SciTech Connect

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

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer In this work, we exploited mechanical separation and pyrolysis to recycle ASR. Black-Right-Pointing-Pointer Pyrolysis of the floating organic fraction is promising in reaching ELV Directive targets. Black-Right-Pointing-Pointer 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.

  9. Production of valuable hydrocarbons by flash pyrolysis of oil shale

    DOEpatents

    Steinberg, M.; Fallon, P.T.

    1985-04-01

    A process for the production of gas and liquid hydrocarbons from particulated oil shale by reaction with a pyrolysis gas at a temperature of from about 700/sup 0/C to about 1100/sup 0/C, at a pressure of from about 400 psi to about 600 psi, for a period of about 0.2 second to about 20 seconds. Such a pyrolysis gas includes methane, helium, or hydrogen. 3 figs., 3 tabs.

  10. Basic studies on the pyrolysis of lignin compounds

    Treesearch

    Byung-ho Hwang

    2003-01-01

    By pyrolyzing lignin model compounds 1-lV at 315°C, an investigation was carried out with some results. In the pyrolysis of lignin model compound I and 11, 0.47 mol of guaiacol, 0.57 mol of dimethoxyphenol (DMP), and 0.12 and 0.23 mol of dimethoxyaceton ophenone (DMAP) were produced respectively. In the pyrolysis of lignin model compound lll and lV, 0.26 mol of...

  11. Sulfur Transformation during Microwave and Conventional Pyrolysis of Sewage Sludge.

    PubMed

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

    2017-01-03

    The sulfur distributions and evolution of sulfur-containing compounds in the char, tar and gas fractions were investigated during the microwave and conventional pyrolysis of sewage sludge. Increased accumulation of sulfur in the char and less production of H2S were obtained from microwave pyrolysis at higher temperatures (500-800 °C). Three similar conversion pathways were identified for the formation of H2S during microwave and conventional pyrolysis. The cracking of unstable mercaptan structure in the sludge contributed to the release of H2S below 300 °C. The decomposition of aliphatic-S compounds in the tars led to the formation of H2S (300-500 °C). The thermal decomposition of aromatic-S compounds in the tars generated H2S from 500 to 800 °C. However, the secondary decomposition of thiophene-S compounds took place only in conventional pyrolysis above 700 °C. Comparing the H2S contributions from microwave and conventional pyrolysis, the significant increase of H2S yields in conventional pyrolysis was mainly attributed to the decomposition of aromatic-S (increasing by 10.4%) and thiophene-S compounds (11.3%). Further investigation on the inhibition mechanism of H2S formation during microwave pyrolysis confirmed that, with the special heating characteristics and relative shorter residence time, microwave pyrolysis promoted the retention of H2S on CaO and inhibited the secondary cracking of thiophene-S compounds at higher temperatures.

  12. Kinetics of scrap tyre pyrolysis under vacuum conditions

    SciTech Connect

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

    2009-10-15

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

  13. Generate rigorous pyrolysis models for olefins production by computer

    SciTech Connect

    Klein, M.T.; Broadbelt, L.J.; Grittman, D.H.

    1997-04-01

    With recent advances in the automation of the model-building process for large networks of kinetic equations, it may become feasible to generate computer pyrolysis models for naphthas and gas oil feedstocks. The potential benefit of a rigorous mechanistic model for these relatively complex liquid feedstocks is great, due to diverse characterizations and yield spectrums. An ethane pyrolysis example is used to illustrate the computer generation of reaction mechanism models.

  14. Kinetics of scrap tyre pyrolysis under vacuum conditions.

    PubMed

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

    2009-10-01

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

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

    NASA Technical Reports Server (NTRS)

    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.

  16. Non-discriminating flash pyrolysis and thermochemolysis of heavily contaminated sediments from the Hamilton Harbor (Canada).

    PubMed

    Poerschmann, J; Parsi, Z; Gorecki, T

    2008-04-04

    Analytical pyrolysis of sediments contaminated with pollutants of medium to high molecular weights (up to approximately 500 Da) is very challenging when using conventional pyrolysis systems due to discrimination of high molecular weight analytes. In the framework of this contribution, non-discriminating pyrolysis and thermochemolysis using rapid heating in a Silcosteel capillary were applied to study organic pollutants in heavily contaminated sediments taken from the Hamilton Harbor. The novel pyrolysis approach, requiring very small amounts of sample, turned out to be very useful as a rapid screening method, e.g. for risk assessment studies, proving superior to commonly used solvent extraction. Main pollutants in the sediments under study included aromatic hydrocarbons, chiefly originating from coal tar and petroleum. Polycyclic aromatic hydrocarbons (PAHs) beyond six-rings, including coronene and truxene, could be detected. Sequential tetramethyl ammonium hydroxide-induced thermochemolysis performed at 500 and 750 degrees C enabled the differentiation between organic pollutants sorbed onto the sediment matrix on the one hand, and structural moieties of the condensed polymeric humic sediment matrix along with bound residues on the other hand. Thermochemolysis at 500 degrees C removed sorbates quantitatively, leaving only bare polymeric humic matrix. Significant PAH source indicators provided evidence that the lipidic fraction sorbed onto the sediments originated from PAHs formed chiefly in coal combustion processes. The polymeric humic organic matter network of the less polluted sediment was mainly of petrogenic origin, whereas black carbon, kerogen, etc. contributed to the organic carbon of the heavily polluted sediment. Thermochemolysis at 500 degrees C was also used to study fatty acid profiles of the sediments. The fatty acid methyl ester patterns obtained for the two sites under study differed significantly, with strong indications that microbial attenuation

  17. Influence of inorganic salts on the primary pyrolysis products of cellulose.

    PubMed

    Patwardhan, Pushkaraj R; Satrio, Justinus A; Brown, Robert C; Shanks, Brent H

    2010-06-01

    Processing bio-oil with the help of currently existing petroleum refinery infrastructure has been considered as a promising alternative to produce sustainable fuels in the future. The feasibility of bio-oil production and upgrading processes depend upon its chemical composition which in turn depends on the biomass composition and the process conditions of the fast pyrolysis reactions. The primary goal of this paper was to investigate the effect of mineral salts including mixtures of salts in the form of switchgrass ash on the chemical speciation resulting from primary pyrolysis reactions of cellulose and to gain an insight of the underlying mechanisms. Various concentrations of inorganic salts (NaCl, KCl, MgCl(2), CaCl(2), Ca(OH)(2), Ca(NO(3))(2), CaCO(3) and CaHPO(4)) and switchgrass ash were impregnated on pure cellulose. These samples were pyrolyzed in a micro-pyrolyzer connected to a GC-MS/FID system. Effects of minerals on the formation of (a) low molecular weight species - formic acid, glycolaldehyde and acetol, (b) furan ring derivatives - 2-furaldehyde and 5-hydroxy methyl furfural and (c) anhydro sugar - levoglucosan are reported exclusively. Further, the effect of reaction temperature ranging from 350 to 600 degrees C on the pyrolysis speciation of pure and ash-doped cellulose is also reported. The pyrolysis speciation revealed the competitive nature of the primary reactions. Mineral salts and higher temperatures accelerated the reactions that led to the formation of low molecular weight species from cellulose as compared to those leading to anhydro sugars.

  18. Rapid detection of bacteria with miniaturized pyrolysis-gas chromatographic analysis

    NASA Astrophysics Data System (ADS)

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

    2002-02-01

    Rapid detection and identification of bacteria and other pathogens is important for many civilian and military applications. The profiles of biological markers such as fatty acids can be used to characterize biological samples or to distinguish bacteria at the gram-type, genera, and even species level. Common methods for whole cell bacterial analysis are neither portable nor rapid, requiring lengthy, labor intensive sample preparation and bench-scale instrumentation. These methods chemically derivatize fatty acids to produce more volatile fatty acid methyl esters (FAMEs) that can be separated and analyzed by a gas chromatograph (GC)/mass spectrometer. More recent publications demonstrate decreased sample preparation time with in situ derivatization of whole bacterial samples using pyrolysis/derivatization. Ongoing development of miniaturized pyrolysis/GC instrumentation by this department capitalizes on Sandia advances in the field of microfabricated chemical analysis systems ((mu) ChemLab). Microdevices include rapidly heated stages capable of pyrolysis or sample concentration, gas chromatography columns, and surface acoustic wave (SAW) sensor arrays. We will present results demonstrating the capabilities of these devices toward fulfilling the goal of portable, rapid detection and early warning of the presence of pathogens in air or water.

  19. Coupling DAEM and CFD for simulating biomass fast pyrolysis in fluidized beds

    DOE PAGES

    Xiong, Qingang; Zhang, Jingchao; Wiggins, Gavin; ...

    2015-12-03

    We report results from computational simulations of an experimental, lab-scale bubbling bed biomass pyrolysis reactor that include a distributed activation energy model (DAEM) for the kinetics. In this study, we utilized multiphase computational fluid dynamics (CFD) to account for the turbulent hydrodynamics, and this was combined with the DAEM kinetics in a multi-component, multi-step reaction network. Our results indicate that it is possible to numerically integrate the coupled CFD–DAEM system without significantly increasing computational overhead. It is also clear, however, that reactor operating conditions, reaction kinetics, and multiphase flow dynamics all have major impacts on the pyrolysis products exiting themore » reactor. We find that, with the same pre-exponential factors and mean activation energies, inclusion of distributed activation energies in the kinetics can shift the predicted average value of the exit vapor-phase tar flux and its statistical distribution, compared to single-valued activation-energy kinetics. Perhaps the most interesting observed trend is that increasing the diversity of the DAEM activation energies appears to increase the mean tar yield, all else being equal. As a result, these findings imply that accurate resolution of the reaction activation energy distributions will be important for optimizing biomass pyrolysis processes.« less

  20. Tabletop Femtosecond VUV Photoionization and PEPICO Detection of Microreactor Pyrolysis Products

    DOE PAGES

    Couch, David E.; Buckingham, Grant T.; Baraban, Joshua H.; ...

    2017-06-29

    Here, we report the combination of tabletop vacuum ultraviolet photoionization with photoion--photoelectron coincidence spectroscopy for sensitive, isomer-specific detection of nascent products from a pyrolysis microreactor. Results on several molecules demonstrate two essential capabilities that are very straightforward to implement: the ability to differentiate isomers, and to distinguish thermal products from dissociative ionization. We derive vacuum ultraviolet light is from a commercial tabletop femtosecond laser system, allowing data to be collected at 10 kHz; this high repetition rate is critical for coincidence techniques. The photoion—photoelectron coincidence spectrometer uses the momentum of the ion to identify dissociative ionization events, and coincidence techniquesmore » to provide a photoelectron spectrum specific to each mass, which is used to distinguish different isomers. We also have used this spectrometer to detect the pyrolysis products that result from the thermal cracking of acetaldehyde, cyclohexene, and 2-butanol. The photoion—photoelectron spectrometer can detect and identify organic radicals and reactive intermediates that result from pyrolysis. Direct comparison of laboratory and synchrotron data illustrate the advantages and potential of this approach.« less

  1. Coupling DAEM and CFD for simulating biomass fast pyrolysis in fluidized beds

    SciTech Connect

    Xiong, Qingang; Zhang, Jingchao; Wiggins, Gavin; Daw, C. Stuart; Xu, Fei

    2015-12-03

    We report results from computational simulations of an experimental, lab-scale bubbling bed biomass pyrolysis reactor that include a distributed activation energy model (DAEM) for the kinetics. In this study, we utilized multiphase computational fluid dynamics (CFD) to account for the turbulent hydrodynamics, and this was combined with the DAEM kinetics in a multi-component, multi-step reaction network. Our results indicate that it is possible to numerically integrate the coupled CFD–DAEM system without significantly increasing computational overhead. It is also clear, however, that reactor operating conditions, reaction kinetics, and multiphase flow dynamics all have major impacts on the pyrolysis products exiting the reactor. We find that, with the same pre-exponential factors and mean activation energies, inclusion of distributed activation energies in the kinetics can shift the predicted average value of the exit vapor-phase tar flux and its statistical distribution, compared to single-valued activation-energy kinetics. Perhaps the most interesting observed trend is that increasing the diversity of the DAEM activation energies appears to increase the mean tar yield, all else being equal. As a result, these findings imply that accurate resolution of the reaction activation energy distributions will be important for optimizing biomass pyrolysis processes.

  2. A newly designed ultrasonic spray pyrolysis device to fabricate YBCO tapes

    NASA Astrophysics Data System (ADS)

    Liu, M.; Zhou, M. L.; Zhai, L. H.; Liu, D. M.; Gao, X.; Liu, W.

    2003-04-01

    A newly designed ultrasonic spray pyrolysis device has been manufactured to fabricate YBCO tapes. The apparatus is primarily composed of four zones: the ultrasonic generator, the atomization chamber, the pyrolysis chamber and the rotating equipment. Every part of them is designed and fabricated by us. The whole system costs far less than the ready-made equipment facility in which there is always a vacuum apparatus. This apparatus with processing parameters accurately controlled can fabricate short and long YBCO tapes. In this paper, we mainly focused on how to design and manufacture four parts of the ultrasonic spray pyrolysis. We have deposited c-axis aligned short YBCO tapes on biaxially textured Ag {1 1 0}<1 1 0> substrates with Jc=10 3 A/cm 2 using this method with our device. The method is very promising in terms of its precise control of metal compositions, high deposition rate and low cost non-vacuum approach. Improvements of this technique are being carried out to fabricate long YBCO tapes.

  3. Molecular characterization and comparison of shale oils generated by different pyrolysis methods

    USGS Publications Warehouse

    Birdwell, Justin E.; Jin, Jang Mi; Kim, Sunghwan

    2012-01-01

    Shale oils generated using different laboratory pyrolysis methods have been studied using standard oil characterization methods as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI) and atmospheric photoionization (APPI) to assess differences in molecular composition. The pyrolysis oils were generated from samples of the Mahogany zone oil shale of the Eocene Green River Formation collected from outcrops in the Piceance Basin, Colorado, using three pyrolysis systems under conditions relevant to surface and in situ retorting approaches. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules and the distribution of nitrogen-containing compound classes. Comparison of FT-ICR MS results to other oil characteristics, such as specific gravity; saturate, aromatic, resin, asphaltene (SARA) distribution; and carbon number distribution determined by gas chromatography, indicated correspondence between higher average double bond equivalence (DBE) values and increasing asphaltene content. The results show that, based on the shale oil DBE distributions, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions, and under high pressure, moderate temperature conditions in the presence of water. We also report, for the first time in any petroleum-like substance, the presence of N4 class compounds based on FT-ICR MS data. Using double bond equivalence and carbon number distributions, structures for the N4 class and other nitrogen-containing compounds are proposed.

  4. Validation Results for Core-Scale Oil Shale Pyrolysis

    SciTech Connect

    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.

  5. Effects of torrefaction and densification on switchgrass pyrolysis products

    DOE PAGES

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

    2014-12-01

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

  6. Fast Pyrolysis of Agricultural Wastes in a Fluidized Bed Reactor

    NASA Astrophysics Data System (ADS)

    Wang, X. H.; Chen, H. P.; Yang, H. P.; Dai, X. M.; Zhang, S. H.

    Solid biomass can be converted into liquid fuel through fast pyrolysis, which is convenient to be stored and transported with potential to be used as a fossil oil substitute. In China, agricultural wastes are the main biomass materials, whose pyrolysis process has not been researched adequately compared to forestry wastes. As the representative agricultural wastes in China, peanut shell and maize stalk were involved in this paper and pine wood sawdust was considered for comparing the different pyrolysis behaviors of agricultural wastes and forestry wastes. Fast pyrolysis experiments were carried out in a bench-scale fluidized-bed reactor. The bio-oil yieldsof peanut shell and maize stalk were obviously lower than that ofpine sawdust. Compared with pine sawdust, the char yields of peanut shell and maize stalk were higher but the heating value of uncondensable gaswas lower. This means that the bio-oil cost will be higher for agricultural wastes if taking the conventional pyrolysis technique. And the characteristic and component analysis resultsof bio-oil revealed that the quality of bio-oil from agricultural wastes, especially maize stalk, was worse than that from pine wood. Therefore, it is important to take some methods to improve the quality of bio-oilfrom agricultural wastes, which should promote the exploitation of Chinese biomass resources through fast pyrolysis in afluidized bed reactor.

  7. Production and characterization of chars from cherry pulp via pyrolysis.

    PubMed

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

    2017-12-01

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

  8. Cheap carbon sorbents produced from lignite by catalytic pyrolysis

    SciTech Connect

    Kuznetsov, B.N.; Schchipko, M.L.

    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.

  9. Analyzing peat pyrolysis by in-situ FTIR

    SciTech Connect

    Fen, J.; Li, W.Y.; Li, F.; Xie, K.C.

    1997-12-31

    Coal pyrolysis is complex process that includes many small reactions. Being complicated, it is difficult to study the pyrolysis mechanism with high rank coal directly. Peat is a rudimentary coal which has the most simple structure with lower polymerization. Some researchers think that the key to understanding coal structure is in an appreciation of the molecular components of the original peat swamp and how these might be modified. It is generally agreed that the chemical diversity of various coals will affect rate of coal combustion through the devolatilization process. Upon heating, some of the chemical bonds in coal undergo cracking and result in the release of light gases and the production of tar. Through analysis of peat which is best model compound of coal, some basic step reactions of coal can be understood. The objective of this study is to analyze peat pyrolysis using a in-situ pyrolysis-FTIR and to establish the pyrolysis model. The results show that during rapid peat pyrolysis, all the functional groups produced have almost the same activity energy; the difference among them is the degree of reaction.

  10. Laser pyrolysis products: sampling procedures, cytotoxic and genotoxic effects.

    PubMed

    Stocker, B; Meier, T; Fliedner, T M; Plappert, U

    1998-01-30

    The use of lasers in medical applications has grown enormously in the last few years. Recent chemical analysis of the laser pyrolysis products revealed that aerosols generated by pyrolytic decomposition of tissue could be health hazards. Therefore we analysed the genotoxic and mutagenic effects of laser pyrolysis products from different types of porcine tissue. The tissues were irradiated with a surgical CO2 laser and the generated aerosols were sampled as particulate fractions as well as low and highly volatile fractions. Then human leukocytes were incubated with the pyrolysis products and subjected to the comet assay. The results of the comet assay indicated the pyrolysis products being inducers of DNA damage. The ability to induce genotoxic effects turned out to be strongly dependent on the type of tissue that had been irradiated during laser treatment. To check whether the pyrolysis products also have mutagenic properties the Salmonella mutagenicity assay was performed. The particulate aerosol fractions of skin, muscle tissue and liver tissue clearly proved to be mutagenic in TA98 in the presence of S9 mix. There was no mutagenic effect detectable without metabolic activation. In conclusion, our experiments showed that the laser pyrolysis products originating from porcine tissues induced very potent genotoxic as well as mutagenic effects and therefore they could be potential health hazards for humans.

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

    PubMed

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

    2011-03-01

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

  12. Experimental investigation of pyrolysis process of woody biomass mixture

    NASA Astrophysics Data System (ADS)

    Kosanić, Tijana R.; Ćeranić, Mirjana B.; Đurić, Slavko N.; Grković, Vojin R.; Milotić, Milan M.; Brankov, Saša D.

    2014-06-01

    This paper describes an experimental investigation of pyrolysis of woody biomass mixture. The mixture consists of oak, beech, fir, cherry, walnut and linden wood chips with equal mass fractions. During the experiment, the sample mass inside the reactor was 10 g with a particle diameter of 5-10 mm. The sample in the reactor was heated in the temperature range of 24-650°C. Average sample heating rates in the reactor were 21, 30 and 54 °C/min. The sample mass before, during and after pyrolysis was determined using a digital scale. Experimental results of the sample mass change indicate that the highest yield of pyrolytic gas was achieved at the temperature slightly above 650°C and ranged from 77 to 85%, while char yield ranged from 15 to 23%. Heating rate has significant influence on the pyrolytic gas and char yields. It was determined that higher pyrolysis temperatures and heating rates induce higher yields of pyrolytic gas, while the char mass reduces. Condensation of pyrolytic gas at the end of the pyrolysis process at 650°C produced 2.4-2.72 g of liquid phase. The results obtained represent a starting basis for determining material and heat balance of pyrolysis process as well as woody biomass pyrolysis equipment.

  13. Thermal decomposition and gasification of biomass pyrolysis gases using a hot bed of waste derived pyrolysis char.

    PubMed

    Al-Rahbi, Amal S; Onwudili, Jude A; Williams, Paul T

    2016-03-01

    Chars produced from the pyrolysis of different waste materials have been investigated in terms of their use as a catalyst for the catalytic cracking of biomass pyrolysis gases during the two-stage pyrolysis-gasification of biomass. The chars were produced from the pyrolysis of waste tyres, refused derived fuel and biomass in the form of date stones. The results showed that the hydrocarbon tar yields decreased significantly with all the char materials used in comparison to the non-char catalytic experiments. For example, at a cracking temperature of 800°C, the total product hydrocarbon tar yield decreased by 70% with tyre char, 50% with RDF char and 9% with biomass date stones char compared to that without char. There was a consequent increase in total gas yield. Analysis of the tar composition showed that the content of phenolic compounds decreased and polycyclic aromatic hydrocarbons increased in the product tar at higher char temperatures.

  14. Pyrolysis of waste electrical and electronic equipment: effect of antinomy trioxide on the pyrolysis of styrenic polymers.

    PubMed

    Hall, W J; Bhaskar, T; Merpati, N M M; Muto, A; Sakata, Y; Williams, P T

    2007-09-01

    This work has investigated the effect that antimony trioxide has on the pyrolysis of styrenic polymers and the effect that different types of brominated flame retardants used in plastics have on the composition of the pyrolysis products. Brominated high impact polystyrene (Br-HIPS) which contained either 5% or 0% antimony trioxide and either decabromodiphenyl oxide (DDO) or decabromodiphenyl ethane (DDE) was pyrolysed in a fixed bed reactor at 430 degrees C. Some experiments on the fixed bed reactor involved mixing the Br-HIPS with polystyrene. The gaseous products were analysed by GC-FID and GC-TCD and it was found that antimony trioxide caused an increase in the proportion of ethane and ethene and suppressed the proportion of butane and butene. When DDE was the flame retardant increased proportions of ethane and ethene were found in the pyrolysis gas compared to when DDO used. When polystyrene was mixed with the Br-HIPS it suppressed the trends observed in the gas composition during the pyrolysis of Br-HIPS. The pyrolysis oils were characterised using FT-IR, GC-MS, GC-FID, and GC-ECD. It was found that the plastic which did not contain antimony trioxide pyrolysed to form mainly toluene, ethylbenzene, styrene, cumene, and alpha-methylstyrene. The oils produced from the pyrolysis of the plastic that contained antimony trioxide did not contain any styrene or alpha-methylstyrene, but instead contained greater concentrations of ethylbenzene and cumene. The absence of styrene and alpha-methylstyrene from the pyrolysis oil occurred even when the Br-HIPS was mixed with polystyrene. GC-ECD analysis of the oils showed that the plastics which did not contain antimony trioxide pyrolysed to form (1-bromoethyl)benzene, which was totally absent from the pyrolysis oils when antimony trioxide was present in the plastic.

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

    NASA Astrophysics Data System (ADS)

    Xiao, Li

    Despite the great passion and endless efforts on development of renewable energy from biomass, the commercialization and scale up of biofuel production is still under pressure and facing challenges. New ideas and facilities are being tested around the world targeting at reducing cost and improving product value. Cutting edge technologies involving analytical chemistry, statistics analysis, industrial engineering, computer simulation, and mathematics modeling, etc. keep integrating modern elements into this classic research. One of those challenges of commercializing biofuel production is the complexity from chemical composition of biomass feedstock and the products. Because of this, feedstock selection and process optimization cannot be conducted efficiently. This dissertation attempts to further evaluate biomass thermal decomposition process using both traditional methods and advanced technique (Pyrolysis Molecular Beam Mass Spectrometry). Focus has been made on data base generation of thermal decomposition products from biomass at different temperatures, finding out the relationship between traditional methods and advanced techniques, evaluating process efficiency and optimizing reaction conditions, comparison of typically utilized biomass feedstock and new search on innovative species for economical viable feedstock preparation concepts, etc. Lab scale quartz tube reactors and 80il stainless steel sample cups coupled with auto-sampling system were utilized to simulate the complicated reactions happened in real fluidized or entrained flow reactors. Two main high throughput analytical techniques used are Near Infrared Spectroscopy (NIR) and Pyrolysis Molecular Beam Mass Spectrometry (Py-MBMS). Mass balance, carbon balance, and product distribution are presented in detail. Variations of thermal decomposition temperature range from 200°C to 950°C. Feedstocks used in the study involve typical hardwood and softwood (red oak, white oak, yellow poplar, loblolly pine

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

    DOEpatents

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

    2013-08-27

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

  17. Pyrolysis of safflower (Charthamus tinctorius L.) seed press cake: part 1. The effects of pyrolysis parameters on the product yields.

    PubMed

    Sensöz, Sevgi; Angin, Dilek

    2008-09-01

    Safflower (Charthamus tinctorius L.) seed press cake was pyrolysed in a fixed-bed reactor. The effects of pyrolysis temperature, heating rate and sweep gas flow rates on the yields of the products were investigated. Pyrolysis runs were performed using pyrolysis temperatures between 400 and 600 degrees C with heating rates of 10, 30 and 50 degrees C min(-1). The obtained bio-char, gas and bio-oil yields ranged between 25 and 34 wt%, 19 and 25 wt%, and 28 and 36 wt%, respectively, at different pyrolysis conditions. The highest liquid yield was obtained at 500 degrees C pyrolysis temperature with a heating rate of 50 degrees C min(-1) under the sweep gas of N(2) with a flow rate of 100 cm(3)min(-1). Employing the higher heating rate of 50 degrees C min(-1) results in maximum bio-oil yield, probably due to the decrease in mass transfer limitations. According to the results obtained under the conditions of this study, the effects of pyrolysis temperature and sweep gas flow rate are more significant than the effect of heating rate on the yields.

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

    PubMed

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

    2017-01-01

    The magnetic biochars were easily fabricated by thermal pyrolysis of Fe(NO3)3 and distillation residue derived from rice straw pyrolysis oil at 400, 600 and 800°C. The effects of pyrolysis temperature on characteristics of magnetic biochars as well as adsorption capacity for aromatic contaminants (i.e., anisole, phenol and guaiacol) were investigated carefully. The degree of carbonization of magnetic biochars become higher as pyrolysis temperature increasing. The magnetic biochar reached the largest surface area and pore volume at the pyrolysis temperature of 600°C due to pores blocking in biochar during pyrolysis at 800°C. Based on batch adsorption experiments, the used adsorbent could be magnetically separated and the adsorption capacity of anisole on magnetic biochars was stronger than that of phenol and guaiacol. The properties of magnetic biochar, including surface area, pore volume, aromaticity, grapheme-like-structure and iron oxide (γ-Fe2O3) particles, showed pronounced effects on the adsorption performance of aromatic contaminants.

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

    DOE PAGES

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

    2016-12-25

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

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

    PubMed Central

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

    2016-01-01

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

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

    SciTech Connect

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

    2016-12-25

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

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

    PubMed

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

    2016-12-25

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

  3. Cascade approach of red macroalgae Gracilaria gracilis sustainable valorization by extraction of phycobiliproteins and pyrolysis of residue.

    PubMed

    Francavilla, M; Manara, P; Kamaterou, P; Monteleone, M; Zabaniotou, A

    2015-05-01

    Phycobiliproteins extraction (primary refining) from Gracilaria gracilis seaweed, harvested in Lesina Lagoon (Italy) and further valorization of the residual algal via pyrolysis (secondary refining), were investigated with a cascade biorefinery approach. R-phycoerythrin (7 mg/g d.w.), allophycocyanin (3.5 mg/g d.w.) and phycocyanin (2 mg/g d.w.) were the main phycobiliproteins extracted. Pyrolysis of G.gracilis residue followed, aiming to investigate the production of bio-oil and biochar within a pyrolysis temperature range of 400-600 °C. Results showed that the bio-oil yield is high (∼65 wt%) at pyrolysis temperature ∼500 °C, but its high content in nitrogenous compounds prevents its use as a biofuel, unless some further de-nitrogenation takes place. Biochar yield ranged between 33 wt% (400 °C) and 26.5 wt% (600 °C). Interestingly, inorganic nutrients including P, K, Ca, Fe and Mg were detected in biochar, suggesting its potential use as recovering system of natural mineral resources from the oceanic reservoir.

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

    SciTech Connect

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

    2016-01-01

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

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

    DOEpatents

    Baird, Lance Awender; Brandvold, Timothy A.

    2015-11-24

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

  6. Sustainability assessment of water hyacinth fast pyrolysis in the Upper Paraguay River basin, Brazil.

    PubMed

    Buller, Luz Selene; Ortega, Enrique; Bergier, Ivan; Mesa-Pérez, Juan Miguel; Salis, Suzana Maria; Luengo, Carlos Alberto

    2015-11-01

    Fast pyrolysis of naturally produced water hyacinth was assessed through Emergy accounting approach. Two analyses were carried out to evaluate the influence of additional services and externalities on Emergy indicators for a pyrolysis plant unit able to process 1000 kg of dry biomass per hour. The initial approach was a traditional Emergy assessment in which financial fluxes and externalities were not considered. The second approach included taxes and fees of the Brazilian government, interests related to financing operations and assumes a reserve financial fund of 5% of the total investment as externalities cost. For the first evaluation, the renewability of 86% indicates that local and renewable resources mainly support the process and the Emergy Yield Ratio of 3.2 shows that the system has a potential contribution to the regional economy due to the local resources use. The inclusion of financial fluxes and externalities in the second evaluation reduces both renewability and Emergy Yield Ratio, whereas it increases the Emergy Investment Ratio which means a higher dependence on external resources. The second analysis allows portraying significant forces of the industrial and financial systems and the evaluation of the externalities' impact on the general system Emergy behavior. A comparison of the renewability of water hyacinth fast pyrolysis with other biofuels like soybean biodiesel and sugarcane ethanol indicates that the former is less dependent on fossil fuel resources, machinery and fertilizers. To complement the sustainability assessment provided by the Emergy method, a regular financial analysis for the second defined system was done. It shows that the system is financially attractive even with the accounting of additional costs. The results obtained in this study could be used as the maximum and minimum thresholds to subsidize regulatory policies for new economic activities in tropical wetlands involving natural resources exploitation and bio

  7. Investigating pyrolysis/incineration as a method of resource recovery from solid waste

    NASA Technical Reports Server (NTRS)

    Robertson, Bobby J.; Lemay, Christopher S.

    1993-01-01

    Pyrolysis/incineration (P/I) is a physicochemical method for the generation of recoverable resources from solid waste materials such as inedible plant biomass (IPB), paper, plastics, cardboard, etc. P/I permits the collection of numerous gases with a minimal amount of solid residue. Pyrolysis, also known as starved air incineration, is usually conducted at relatively high temperatures (greater than 500 deg C) in the absence of oxygen. Incineration is conducted at lower temperatures in the presence of oxygen. The primary purpose of this study was to design, construct, and test a model P/I. The system design includes safety requirements for temperature and pressure. The objectives of this study were: (1) to design and construct a P/I system for incorporation with the Hybrid Regenerative Water Recovery System; (2) to initiate testing of the P/I system; (3) to collect and analyze P/I system data; (4) to consider test variables; and (5) to determine the feasibility of P/I as an effective method of resource recovery. A P/I system for the recovery of reuseable resources from solid waste materials was designed, constructed, and tested. Since a large amount of inedible plant biomass (IPB) will be generated in a space-based habitat on the lunar surface and Mars, IPB was the primary waste material tested in the system. Analysis of the effluent gases was performed to determine which gases could be used in a life support system.

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

    NASA Astrophysics Data System (ADS)

    Bennion, Edward P.

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

  9. Kinetic Model Development for Lignin Pyrolysis

    SciTech Connect

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

    2012-01-01

    Lignin pyrolysis poses a significant barrier to the formation of liquid fuel products from biomass. Lignin pyrolyzes at higher temperatures than other biomass components (e.g. cellulose and hemi-cellulose) and tends to form radicals species that lead to cross-linking and ultimately char formation. A first step in the advancement of biomass-to-fuel technology is to discover the underlying mechanisms that lead to the breakdown of lignin at lower temperatures into more stable and usable products. We have investigated the thermochemistry of the various inter-linkage units found in lignin (B-O4, a-O4, B-B, B-O5, etc) using electronic structure calculations at the M06-2x/6-311++G(d,p) on a series of dimer model compounds. In addition to bond homolysis reactions, a variety of concerted elimination pathways are under investigation that tend to produce closed-shell stable products. Such a bottom-up approach could aid in the targeted development of catalysts that produce more desirable products under less severe reactor conditions.

  10. Combustion fundamentals of pyrolysis oil based fuels

    SciTech Connect

    Calabria, R.; Chiariello, F.; Massoli, P.

    2007-04-15

    The combustion behavior of emulsions of pyrolysis oil in commercial diesel oil was studied. The emulsions were different in terms of concentration and size of the dispersed phase. The study was carried out in a single droplet combustion chamber. The size of droplets varied between 400 {mu}m and 1200 {mu}m. They were suspended to a bare thermocouple and, hence, their temperature during combustion was measured. High-speed digital shadowgraphy was used to follow droplets evolution. The main features of the droplet combustion were recognized. The general combustion behavior of emulsions is intermediate with respect to pure PO and commercial diesel oil. Emulsion droplets underwent strong swelling and microexplosion phenomena. However, under the investigated conditions, the microexplosions were ineffective in destroying droplets. The size distribution of the dispersed PO droplets in the range 3-10 {mu}m was not effective either for determining the overall thermal behavior or for the efficacy of the microexplosions. The homogeneous combustion phase resulted identical for emulsions and diesel oil despite the emulsions composition (i.e., concentration of oil, surfactant and co-surfactant, as well as the size of the oil droplets in the emulsion) and the different structure of the flame and also its time and spatial evolution. (author)

  11. Pyrolysis of Large Black Liquor Droplets

    NASA Technical Reports Server (NTRS)

    Bartkus, Tadas P.; T'ien, James S.; Dietrich, Daniel L.; Wessel, Richard A.

    2007-01-01

    This paper presents the results of experiments involving the pyrolysis of large black liquor droplets in the NASA KC-135 reduced gravity aircraft. The reduced gravity environment facilitated the study of droplets up to 9 mm in diameter extending the results of previous studies to droplet sizes that are similar to those encountered in recovery boilers. Single black liquor droplets were rapidly inserted into a 923 K oven. The primary independent variables were the initial droplet diameter (0.5 mm to 9 mm), the black liquor solids content (66.12% - 72.9% by mass), and the ambient oxygen mole fraction (0.0 - 0.21). Video records of the experiments provided size and shape of the droplets as a function of time. The results show that the particle diameter at the end of the drying stage (D(sub DRY) ) increases linearly with the initial particle diameter (D(sub O)). The results further show that the ratio of the maximum swollen diameter (D(sub MAX)) to D(sub O) decreases with increasing D(sub O) for droplets with D(sub O) less than 4 mm. This ratio was independent of D(sub O) for droplets with D(sub O) greater than 4 mm. The particle is most spherical at the end of drying, and least spherical at maximum swollen size, regardless of initial sphericity and droplet size.

  12. Pyrolysis of Large Black Liquor Droplets

    NASA Technical Reports Server (NTRS)

    Bartkus, Tadas P.; Dietrich, Daniel L.; T'ien, James S.; Wessel, Richard A.

    2007-01-01

    This paper presents the results of experiments involving the pyrolysis of large black liquor droplets in the NASA KC-135 reduced gravity aircraft. The reduced gravity environment facilitated the study of droplets up to 9 mm in diameter extending the results of previous studies to droplet sizes that are similar to those encountered in recovery boilers. Single black liquor droplets were rapidly inserted into a 923 K oven. The primary independent variables were the initial droplet diameter (0.5 mm to 9 mm), the black liquor solids content (66.12% - 72.9% by mass), and the ambient oxygen mole fraction (0.0 - 0.21). Video records of the experiments provided size and shape of the droplets as a function of time. The results show that the particle diameter at the end of the drying stage (D(sub DRY)) increases linearly with the initial particle diameter (D(sub O)). The results further show that the ratio of the maximum swollen diameter (D(sub MAX)) to D(sub O) decreases with increasing D(sub O) for droplets with D(sub O) less than 4 mm. This ratio was independent of D(sub O) for droplets with D(sub O) greater than 4 mm. The particle is most spherical at the end of drying, and least spherical at maximum swollen size, regardless of initial sphericity and droplet size.

  13. Combustion of char from plastic wastes pyrolysis

    NASA Astrophysics Data System (ADS)

    Saptoadi, Harwin; Rohmat, Tri Agung; Sutoyo

    2016-06-01

    A popular method to recycle plastic wastes is pyrolysis, where oil, gas and char can be produced. These products can be utilized as fuels because they are basically hydrocarbons. The research investigates char properties, including their performance as fuel briquettes. There are 13 char samples from PE (Polyethylene) pyrolyzed at temperatures of around 450 °C, with and without a catalyst. Some of the samples were obtained from PE mixed with other types, such as Polystyrene (PS), Polypropylene (PP), Polyethylene Terephthalate (PET), and Others. Char properties, such as moisture, ash, volatile matter, and fixed carbon contents, are revealed from the proximate analysis, whereas calorific values were measured with a bomb calorimeter. Briquettes are made by mixing 4 g of char with 0.5 - 1 g binder. Briquettes are hollow cylinders with an outer and inner diameter of around 1.75 cm and 0.25 cm, respectively. Combustion is carried out in a furnace with wall temperatures of about 230°C and a constant air velocity of 0.7 m/s. Five out of 13 char briquettes are not feasible because they melt during combustion. Briquettes made from 100% PE wastes burn in substantially shorter duration than those from mixed plastic wastes. Char #1 and #5 are excellent due to their highest energy release, whereas #10 show the worst performance.

  14. Pyrolysis of Municipal Solid Waste for Syngas Production by Microwave Irradiation

    SciTech Connect

    Gedam, Vidyadhar V.; Regupathi, Iyyaswami

    2012-03-15

    In the present study, we discuss the application of microwave-irradiated pyrolysis of municipal solid waste (MSW) for total recovery of useful gases and energy. The MSW pyrolysis under microwave irradiation highly depends on the process parameters, like microwave power, microwave absorbers, and time of irradiation. The thoroughness of pyrolysis and product recovery were studied by changing the abovesaid variables. Pyrolysis of MSW occurs in the power rating range of 450-850 W-outside this power rating range, pyrolysis is not possible. Experiments were carried out using various microwave absorbers (i.e., graphite, charcoal, and iron) to enhance the pyrolysis even at lower power rating. The results show that the pyrolysis of MSW was possible even at low power ratings. The major composition of the pyrolysis gaseous product were analyzed with GC-MS which includes CO{sub 2}, CO, CH{sub 4}, etc.

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

    PubMed

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

    2017-03-01

    Co-pyrolysis conversion of seaweed (Enteromorpha clathrat and Sargassum fusiforme) polysaccharides and cellulose has been investigated. From the Py-GC/MS results, Enteromorpha clathrata (EN) polysaccharides pyrolysis mainly forms furans; while the products of Sargassum fusiforme (SA) polysaccharides pyrolysis are mainly acid esters. The formation mechanisms of H2O, CO2, and SO2 during the pyrolysis of seaweed polysaccharides were analyzed using the thermogravimetric-mass spectrometry. Meanwhile the pyrolysis of seaweed polysaccharide based on the Amber and the ReaxFF force fields, has also been proposed and simulated respectively. The simulation results coincided with the experimental results. During the fast pyrolysis, strong synergistic effects among cellulose and seaweed polysaccharide molecules have been simulated. By comparing the experimental and simulation value, it has been found that co-pyrolysis could increase the number of molecular fragments, increase the pyrolysis conversion rate, and increase gas production rate at the middle temperature range.

  16. Desulphurization of lignites by slow, fast, and flash pyrolysis and high intensity dry magnetic separation

    SciTech Connect

    Koca, H.; Kockar, O.M.; Koca, S.

    2007-07-01

    Slow, fast and flash pyrolysis followed by high intensity dry magnetic (HIDM) separation experiments were conducted to obtain improved solid fuels. Pyrolysis experiments were performed in three different apparatus, and important parameters of processes, temperature, particle size, residence time and heating rate were studied to determine the optimum conditions. Desulphurization of lignites by flash pyrolysis is more successful than slow and fast pyrolysis. At optimum conditions of pyrolysis, up to 58.15, 60.24, and 62.31% sulphur reductions were obtained in slow, fast and flash pyrolysis, respectively. Char, obtained from the pyrolysis experiments, was further cleaned by a Permroll HIDM separator. Sulphur reduction enhanced up to 82.68, 84.40, and 86.55% in the char of slow, fast and flash pyrolysis, respectively.

  17. Cellulose pyrolysis kinetics in a simulated solar environment

    SciTech Connect

    Tobatabaie-Raissi, A. ); Mok, W.S.- L; Antal, M.J., Jr. . Dept. of Mechanical Engineering)

    1989-06-01

    The instrumentation and methods required to study rapid, radiative decomposition of highly reactive biopolymers are described and used to determine the kinetic parameters for the pyrolysis of Avicel PH105 microcrystalline cellulose. Experiments were carried out at heating rates greater than 2K/s in a specially fabricated thermogravimetric analyzer system which employed a 30-kW{sub e}/2-kW/th downward-facing beam, arc-image furnace as a heat source. The thermogravimetric data were interpreted assuming a simple, single-step reaction mechanism and using a nonlinear least-squares kinetic analysis. Based on the results, and apparent activation energy of 100.5 {plus minus} 3kJ/mol, a preexonential factor of in (A (s{sup 1})) = 14 {plus minus} 0.5, and nearly a first-order (n = 0.9 {plus minus} 0.05) reaction were obtained. The extent of char formation was determined experimentally and found to be in the range 6.6-8.4% by weight of original dry material depending upon the prevailing reaction conditions.

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

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

    PubMed Central

    2014-01-01

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

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

    PubMed

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

    2014-01-01

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

  1. Catalytic microwave pyrolysis of biomass for renewable phenols and fuels

    NASA Astrophysics Data System (ADS)

    Bu, Quan

    Bio-oil is an unstable intermediate and needs to be upgraded before its use. This study focused on improving the selectivity of bio-oilby catalytic pyrolysis of biomass using activated carbon (AC) catalysts. Firstly, the effects of process conditions on product quality and product yield were investigated by catalytic microwave pyrolysis of biomass using AC as a catalyst. The optimized reaction condition for bio-oil and volatile was determined. Chemical composition analysis by GC/MS showed that phenols rich bio-oils were obtained. Furthermore, the effects of different carbon sources based AC catalysts on products yield and chemical composition selectivity of obtained bio-oils were investigated during microwave pyrolysis of Douglas fir pellet. The catalysts recycling test of the selected catalysts indicated that the AC catalysts can be used for 3-4 times with high concentration of phenolic compounds. The individual surface polar/acidic oxygen functional groups analysis suggested the changes of functional groups in ACs explained the reaction mechanism of this process. In addition, the potential for production of renewable phenols and fuels by catalytic pyrolysis of biomass using lignin as a model compound was explored. The main chemical compounds of the obtained bio-oils were phenols, guaiacols, hydrocarbons and esters. The thermal decomposition behaviors of lignin and kinetics study were investigated by TGA. The change of functional groups of AC catalyst indicated the bio-oil reduction was related to the reaction mechanism of this process. Finally, the effects of Fe-modified AC catalyst on bio-oil upgrading and kintic study of biomass pyrolysis were investigated. The catalytic pyrolysis of biomass using the Fe-modified AC catalyst may promote the occurrence of the fragmentation of cellulose, rather than repolymerization as in the non-catalytic pyrolysis which leads to partial of guaiacols derived from furans. Results showed that the main chemical compounds of bio

  2. Environmental impact of pyrolysis of mixed WEEE plastics part 1: Experimental pyrolysis data.

    PubMed

    Alston, Sue M; Clark, Allan D; Arnold, J Cris; Stein, Bridget K

    2011-11-01

    Growth in waste electrical and electronic equipment (WEEE) is posing increasing problems of waste management, partly resulting from its plastic content. WEEE plastics include a range of polymers, some of which can be sorted and extracted for recycling. However a nonrecyclable fraction remains containing a mixture of polymers contaminated with other materials, and pyrolysis is a potential means of recovering the energy content of this. In preparation for a life cycle assessment of this option, described in part 2 of this paper set, data were collected from trials using experimental pyrolysis equipment representative of a continuous commercial process operated at 800 °C. The feedstock contained acrylonitrile-butadiene-styrene and high impact polystyrene with high levels of additives, and dense polymers including polyvinylchloride, polycarbonate, polyphenylene oxide, and polymethyl methacrylate. On average 39% was converted to gases, 36% to oils, and 25% remained as residue. About 35% of the gas was methane and 42% carbon monoxide, plus other hydrocarbons, oxygen and carbon dioxide. The oils were almost all aromatic, forming a similar mixture to fuel oil. The residue was mainly carbon with inorganic compounds from the plastic additives and most of the chlorine from the feedstock. The results showed that the process produced around 70% of the original plastic weight as potential fuel.

  3. Pressurized pyrolysis and gasification of Chinese typical coal samples

    SciTech Connect

    Hanping Chen; Zhiwu Luo; Haiping Yang; Fudong Ju; Shihong Zhang

    2008-03-15

    This paper aims to understand the pyrolysis and gasification behavior of different Chinese coal samples at different pressures. First, the pyrolysis of four typical Chinese coals samples (Xiaolongtan brown coal, Shenfu bituminous coal, Pingzhai anthracite coal, and Heshan lean coal) were carried out using a pressurized thermogravimetric analyzer at ambient pressure and 3 MPa, respectively. The surface structure and elemental component of the resultant char were measured with an automated gas adsorption apparatus and element analyzer. It was observed that higher pressure suppressed the primary pyrolysis, while the secondary pyrolysis of coal particles was promoted. With respect to the resultant solid char, the carbon content increased while H content decreased; however, the pore structure varied greatly with increasing pressure for different coal samples. For Xiaolongtan brown coal (XLT) char, it decreased greatly, while it increased obviously for the other three char types. Then, the isothermal gasification behavior of solid char particles was investigated using an ambient thermal analyzer with CO{sub 2} as the gasifying agent at 1000{sup o}C. The gasification reactivity of solid char was decreased greatly with increasing pyrolysis pressure. However, the extent of change displayed a vital relation with the characteristics of the original coal sample. 26 refs., 5 figs., 5 tabs.

  4. Formation characteristics of PCDD and PCDF during pyrolysis processes.

    PubMed

    Weber, R; Sakurai, T

    2001-12-01

    In recent years, pyrolysis processes have become technologies developed to industrial scale and discussed as alternatives to the existing waste combustion technology. However, little information is published regarding PCDD/F formation characteristics during pyrolysis processes. Two common shredder fractions--industrial light shredder (ILS) and refrigerators (REF)--both with high chlorine and copper content were pyrolysed for this pyrolysis study using a pilot plant with a capacity of 100 kg/h. At oxygen concentrations below 2% and temperatures between 430 degrees C and 470 degrees C, considerable amounts of PCDD/F were formed during the pyrolysis. More than 90% of total TEQ was found in the oil fraction (gas phase). The PCDD/PCDF ratio and the homologue pattern differed significantly from those formed during waste incineration. Considering mono- to octachlorinated congeners, up to 400 times more PCDF were formed compared to PCDD. For the investigated pyrolysis conditions, the formation of low chlorinated congeners was highly favoured. The distribution of TEQ within the individual congeners were very similar in all investigated runs. More than 80% of total TEQ stem from 2,3,7,8-substituted T4CDF and P5CDF. The isomer pattern, however, did not show significant differences compared to the common waste incineration pattern suggesting that the basic formation routes are similar.

  5. Experimental Research of Pyrolysis Gases Cracking on Surface of Charcoal

    NASA Astrophysics Data System (ADS)

    Kosov, Valentin; Kosov, Vladimir; Zaichenko, Victor

    For several years, in the Joint Institute for High Temperatures of Russian Academy of Sciences, two-stage technology of biomass processing has been developing [1]. The technology is based on pyrolysis of biomass as the first stage. The second stage is high-temperature conversion of liquid fraction of the pyrolysis on the surface of porous charcoal matrix. Synthesis gas consisted of carbon monoxide and hydrogen is the main products of the technology. This gas is proposed to be used as fuel for gas-engine power plant. For practical implementation of the technology it is important to know the size of hot char filter for full cracking of the pyrolysis gases on the surface of charcoal. Theoretical determination of the cracking parameters of the pyrolysis gases on the surface of coal is extremely difficult because the pyrolysis gases include tars, whose composition and structure is complicated and depends on the type of initial biomass. It is also necessary to know the surface area of the char used in the filter, which is also a difficult task. Experimental determination of the hot char filter parameters is presented. It is shown that proposed experimental method can be used for different types of biomass.

  6. Distribution of nitrogen species during vitrinite pyrolysis and gasification

    SciTech Connect

    Lin, J.Y.; Li, W.Y.; Chang, L.P.; Feng, J.; Zhao, W.; Xie, K.C.

    2006-08-15

    The formation of HCN and NH3 during pyrolysis in Ar and gasification in CO{sub 2} and steam/Ar was investigated. Vitrinites were separated and purified from different rank coal from lignite to anthracite. Pyrolysis and gasification were carried out in the drop-tube/fixed-bed reactor at temperatures of 600-900{sup o}C. Results showed that with increase of reaction temperature the yield of HCN increased significantly during pyrolysis and gasification. Decrease of coal rank also increased the yield of HCN. Vitrinite from lower rank of coal with high volatile content released more HCN. The yield of NH3 was the highest at 800 {sup o}C during pyrolysis and gasification. And the yield of NH3 from gasification in steam/Ar was far higher than that from gasification in CO{sub 2}, where the hydrogen radicals play a key role. Nitrogen retained in char was also investigated. The yield of char-N decreased with an increase of pyrolysis temperature. Vitrinite from lower rank coal had lower yield of char-N than that from the high rank coal.

  7. Auto shredder residue recycling: Mechanical separation and pyrolysis.

    PubMed

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

    2012-05-01

    Directive 2000/53/EC sets a goal of 85% material recycling from end-of-life vehicles (ELVs) by the end of 2015. The current ELV recycling rate is around 80%, while the remaining waste is called automotive shredder residue (ASR), or car fluff. In Europe, this is mainly landfilled because it is extremely heterogeneous and often polluted with car fluids. Despite technical difficulties, in the coming years it will be necessary to recover materials from car fluff in order to meet the ELV Directive requirement. This study deals with ASR pretreatment and pyrolysis, and aims to determine whether the ELV material recycling target may be achieved by car fluff mechanical separation followed by pyrolysis with a bench scale reactor. Results show that flotation followed by pyrolysis of the light, organic fraction may be a suitable ASR recycling technique if the oil can be further refined and used as a chemical. Moreover, metals are liberated during thermal cracking and can be easily separated from the pyrolysis char, amounting to roughly 5% in mass. Lastly, pyrolysis can be a good starting point from a "waste-to-chemicals" perspective, but further research should be done with a focus on oil and gas refining, in order both to make products suitable for the chemical industry and to render the whole recycling process economically feasible. Copyright © 2011 Elsevier Ltd. All rights reserved.

  8. Air-assisted ultrasonic spray pyrolysis for nanoparticles synthesis

    NASA Astrophysics Data System (ADS)

    Tsai, Shirley C.; Song, Yu L.; Chen, C. Y.; Tseng, T. K.; Tsai, Chen S.

    2002-11-01

    This paper presents new findings regarding the effects of precursor drop size and concentration on product particle size and morphology in ultrasonic spray pyrolysis of zirconium hydroxyl acetate solutions. Large precursor drops (diameter >30μm) generated by ultrasonic atomization at 120kHz yielded particles with holes. Precursor drops 6-9 μm in diameter, generated by an ultrasonic nebulizer at 1.65MHz and 23.5W electric drive power, yielded uniform spherical particles 150nm in diameter under proper control of heating rate and precursor concentration. Moreover, air-assisted ultrasonic spray pyrolysis at 120kHz and 2.3W yielded spherical particles of which nearly half were smaller than those produced by the ultrasonic spray pyrolysis of the 6-9 μm precursor drops, desprite the much larger precursor drop sizes (28 μm peak diameter versus 7 μm mean diameter). These particles are much smaller than those predicted by the conventional one particle per drop mechanism, suggesting that a vapor condensation mechanism may also be involved in spray pyrolysis. It may be concluded that through this new mechanism air-assisted ultrasonic spray pyrolysis can become a viable process for mass production of nanoparticles.

  9. Microwave pyrolysis of oily sludge with activated carbon.

    PubMed

    Chen, Yi-Rong

    2016-12-01

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

  10. Solar coal gasification reactor with pyrolysis gas recycle

    DOEpatents

    Aiman, William R.; Gregg, David W.

    1983-01-01

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

  11. Hirshfeld charge analysis and model compound studies of biomass pyrolysis

    SciTech Connect

    Cutler, A.H.

    1985-01-01

    The method of partitioning molecular electron densities into atomic changes proposed by F.L. Hirshfeld has been compared to other methods and to empirical expectations. It is found to bear similarities to other theoretical methods. Previous theoretical treatments of kinetics in laminar flow reactors are discussed. It is found that the effects of diffusion on calculated kinetics are surprisingly small. The errors in the measured activation energy of a first order reaction due to experimental uncertainty are derived and discussed. High temperature pyrolysis of t-butyl alcohol (973-1113 K) and acetaldehyde (1033-1153 K) in steam at various reactant concentrations were carried out, giving activation parameters and product distributions in agreement with previous work. Acetaldehyde pyrolysis product distributions agree with previous work. It is concluded that the reactor has no effect on the kinetics or mechanisms of radical chain reactions. The kinetics and mechanism of 1,3-dioxolane pyrolysis were determined in atmospheric pressure steam between 963 K and 1093 K with reactant concentrations of 6.82 x 10/sup -7/ to 1.36 x 10/sup -4/ mol/l using a laminar flow reactor. The reaction was found to be first order. Some mechanistic aspects of levoglucosan pyrolysis are discussed in light of these results in dioxolane and recently published results on glycerol pyrolysis.

  12. The fate of sulfur during rapid pyrolysis of scrap tires.

    PubMed

    Hu, Hongyun; Fang, Yuan; Liu, Huan; Yu, Ren; Luo, Guangqian; Liu, Wenqiang; Li, Aijun; Yao, Hong

    2014-02-01

    The fate of sulfur during rapid pyrolysis of scrap tires at temperatures from 673 to 1073K was investigated. Sulfur was predominant in the forms of thiophenic and inorganic sulfides in raw scrap tires. In the pyrolysis process, sulfur in organic forms was unstable and decomposed, leading to the sulfur release into tar and gases. At 673 and 773K, a considerable amount of sulfur was distributed in tar. Temperature increasing from 773 to 973K promoted tar decomposition and facilitated sulfur release into gases. At 1073K, the interactions between volatiles and char stimulated the formation of high-molecular-weight sulfur-containing compounds. After pyrolysis, almost half of the total content of sulfur in raw scrap tires still remained in the char and was mostly in the form of sulfides. Moreover, at temperatures higher than 873K, part of sulfur in the char was immobilized in the sulfates. In the pyrolysis gases, H2S was the main sulfur-containing gas. Increasing temperature stimulated the decomposition of organic polymers in scrap tires and more H2S was formed. Besides H2S, other sulfur-containing gases such as CH3SH, COS and SO2 were produced during the rapid pyrolysis of scrap tires.

  13. Solar coal gasification reactor with pyrolysis gas recycle

    SciTech Connect

    Aiman, W.R.; Gregg, D.W.

    1983-11-15

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

  14. Pyrolysis characteristics and kinetics of the alga Saccharina japonica.

    PubMed

    Kim, Seung-Soo; Ly, Hoang Vu; Choi, Gyeong-Ho; Kim, Jinsoo; Woo, Hee Chul

    2012-11-01

    Saccharina japonica can be converted to bio-oil, gas, and char through pyrolysis. In this study, the pyrolysis characteristics of S. japonica were investigated using a thermogravimetric analyzer. Most of the materials decomposed between 200°C and 350°C at heating rates of 10-20°C/min. The apparent activation energy increased from 102.5kJmol(-1) to 269.7kJmol(-1) with increasing pyrolysis conversion. The kinetic parameters of S. japonica pyrolysis were determined using nonlinear least-squares regression of the experimental data assuming first-order kinetics. The kinetic rate constants indicated that the predominant reaction pathway was B (bio-oil) to C (gas; C(1)-C(4)), rather than A (S. japonica) to B (bio-oil) and/or to C (gas; C(1)-C(4)). The proposed lumped kinetics of S. japonica pyrolysis offers a guide for the scale-up of the process at the research and industrial level.

  15. Pyrolysis Model Development for a Multilayer Floor Covering

    PubMed Central

    McKinnon, Mark B.; Stoliarov, Stanislav I.

    2015-01-01

    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. PMID:28793556

  16. Quantitative flash pyrolysis Fourier transform infrared spectroscopy of organic materials.

    PubMed

    Court, Richard W; Sephton, Mark A

    2009-04-20

    Thermal degradation is a common technique used to investigate the nature of organic materials. However, existing methods for the Fourier transform infrared (FTIR) identification and quantification of volatile products from the thermal degradation of organic materials are limited to the technique of thermogravimetric analysis (TGA)-FTIR, which utilizes relatively low heating rates. However, the thermal degradation products of organic materials are known to vary depending on the rate of heating, with lower heating rates of biomass associated with increased yields of solid char and decreased yields of volatiles, as well as a greater opportunity for secondary reactions between the residue and the pyrolysis products. Hence, it is difficult to relate the products of organic matter thermally degraded at <100 degrees C min(-1) in TGA to the products of flash pyrolysis at up to 20,000 degrees C s(-1). We have developed and applied a novel methodology for quantitative flash pyrolysis-FTIR analysis of the volatile pyrolysis products of organic-rich materials. Calibration curves of water, carbon dioxide and methane have been constructed and used to determine absolute volatile release from wood (ash, Lat. Fraxinus). This technique is quicker and simpler than comparable pyrolysis-gas chromatography-mass spectrometry techniques, and avoids errors associated with the lower rates of temperature increase associated with techniques such as thermogravimetric analysis.

  17. Pyrolysis of activated sludge: energy analysis and its technical feasibility.

    PubMed

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

    2015-02-01

    A comprehensive study on the potential of pyrolysis of activated sludge to generate substances that can be used to produce energy was evaluated for its technical and environmental viability. The products of the process viz., pyrolysis gas, pyrolysis oil and char can readily be used by the major energy consumers viz., electricity and transportation. Based on the results obtained it is estimated that a 1 ton capacity process for pyrolysis of activated sludge can serve the electrical needs of a maximum of 239, 95 and 47 Indian houses per day, considering lower middle class, middle class and upper middle class, respectively. In addition the process would also produce the daily methane (CNG) requirement of 128 public transport buses. The process was determined to be technically feasible at low and medium temperatures for both, pyrolysis gas and electrical energy. The gas generated could be utilized as fuel directly while the oil generated would require pretreatment before its potential application. The process is potentially sustainable when commercialized and can self-sustain in continuous mode of operation in biorefinery context.

  18. [Components of oil sludge and their influence on pyrolysis behaviors].

    PubMed

    Song, Wei; Liu, Jian-Guo; Nie, Yong-Feng

    2008-07-01

    Based on property analysis of oil sludge and its main components (mineral oil and minerals), pyrolysis process and releasing behavior of non-condensed gas of oil sludge and its main components were studied by thermogravimetric analysis-fourier transform infrared spectroscopy (TG-FTIR) and tubular resistance furnace, respectively. The results indicated that, (1) Oil sludge was characterized as relatively high heating value (15 422.41 kJ/kg), higher mineral content (61.57%) mainly composed of quartz. Mineral oil component had good thermal conversion property and adhered close with mineral in oil sludge. (2) Pyrolysis process of oil sludge included 5 stages: water volatilization and gas desorption (50-180 degrees C), light oil volatilization (180-370 degrees C), heavy oil pyrolysis (370-500 degrees C), semi-coke charring (500-600 degrees C) and mineral decomposition (higher than 600 degrees C). (3) Minerals influenced oil pyrolysis by surface function and enhancing heating conductivity, meanwhile minor elements in mineral oil could bring mineral decomposition temperature down. (4) Minerals affected the releasing behavior of non-condensed gas from mineral oil pyrolysis and resulted in lower total production and higher H2 production.

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

    EPA Science Inventory

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

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

    EPA Science Inventory

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

  1. Analysis of Microorganisms by Oxidative and Non-Oxidative Pyrolysis Gas Chromatography Ion Trap Mass Spectrometry.

    DTIC Science & Technology

    1992-04-01

    Bacillus subtilis, Bacillus pumilus , Bacillus lichenformis, and Bacillus amyloliquefaciens by Pyrolysis-gas Liquid Chromatography, Deoxyribonucleic...FIGURES Number Page 1. Curie point pyrolysis GC-ITD data for Bacillus subtilis ................... 16 2. Total Ion Chromatograms for Bacillus subtilis...under oxidative and non-oxidative pyrolysis conditions ................................... 17 3. Total Lipid Mass Spectra for Bacillus subtilis under

  2. Pyrolysis of Compositions of Mixtures of Combustible Shales and Brown Coals Deposited in Belarus

    NASA Astrophysics Data System (ADS)

    Lishtvan, I. I.; Dudarchik, V. M.; Kraiko, V. M.; Belova, Yu. V.

    2013-11-01

    This paper presents the results of investigating the pyrolysis of compositions of mixtures of brown coals and combustible shales in a close-packed and a moving layer and the yield dynamics of the pyrolysis gas and resin. A comparative analysis of the quality of pyrolysis products obtained from combustible shales and brown coal and from their mixtures has been performed.

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

    USDA-ARS?s Scientific Manuscript database

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

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

    DOE PAGES

    Xiong, Qingang; Robichaud, David J.

    2017-03-23

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

  5. Application of analytical pyrolysis-mass spectrometry in characterization of animal manures

    USDA-ARS?s Scientific Manuscript database

    Different analytical pyrolysis techniques have been used in characterizing natural organic matter and synthesized organic polymers. Most common ones are pyrolysis followed by direct detection using MS such as in Py-FIMS technique or pyrolysis followed by GC separation of pyrosates then detected by M...

  6. Structural analysis of pyrolytic lignins isolated from switchgrass fast pyrolysis oil

    USDA-ARS?s Scientific Manuscript database

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

  7. Influence of pyrolysis temperature on physicochemical properties of biochar obtained from the fast pyrolysis of pitch pine (Pinus rigida).

    PubMed

    Kim, Kwang Ho; Kim, Jae-Young; Cho, Tae-Su; Choi, Joon Weon

    2012-08-01

    The aim of this study was to investigate the influence of pyrolysis temperature on the physicochemical properties and structure of biochar. Biochar was produced by fast pyrolysis of pitch pine (Pinus rigida) using a fluidized bed reactor at different pyrolysis temperatures (300, 400 and 500 °C). The produced biochars were characterized by elemental analysis, Brunauer-Emmett-Teller (BET) surface area, particle size distributions, field-emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FTIR) spectroscopy, solid-state (13)C nuclear magnetic resonance (NMR) and X-ray diffraction (XRD). The yield of biochar decreased sharply from 60.7% to 14.4%, based on the oven-dried biomass weight, when the pyrolysis temperature rose from 300 °C to 500 °C. In addition, biochars were further carbonized with an increase in pyrolysis temperature and the char's remaining carbons were rearranged in stable form. The experimental results suggested that the biochar obtained at 400 and 500 °C was composed of a highly ordered aromatic carbon structure.

  8. The use of tyre pyrolysis oil in diesel engines.

    PubMed

    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.

  9. Pyrolysis of Softwood Carbohydrates in a Fluidized Bed Reactor

    PubMed Central

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

    2008-01-01

    In the present work pyrolysis of pure pine wood and softwood carbohydrates, namely cellulose and galactoglucomannan (the major hemicellulose in coniferous wood), was conducted in a batch mode operated fluidized bed reactor. Temperature ramping (5 °C/min) was applied to the heating until a reactor temperature of 460 °C was reached. Thereafter the temperature was kept until the release of non-condensable gases stopped. The different raw materials gave significantly different bio-oils. Levoglucosan was the dominant product in the cellulose pyrolysis oil. Acetic acid was found in the highest concentrations in both the galactoglucomannan and in the pine wood pyrolysis oils. Acetic acid is most likely formed by removal of O-acetyl groups from mannose units present in GGM structure. PMID:19325824

  10. Presence of metals in biomass residues after pyrolysis

    NASA Astrophysics Data System (ADS)

    Guehenneux, G.; Varin, S.; Baussand, P.

    2003-05-01

    In contribution to research into renewable energy, pyrolysis tests are run to develop the process of pyrolysis of biomass allowing the production of Hydrogen. Various families of combustibles (oleaginous, lignocellulosics, and seeds) have been tested at different temperatures. The pyrolysis of biomass is hampered by technical problems such as the blockage of the furnace by tars. The residues are collected and treated in a solution of chloric and nitric acid, so that the mineral part is extracted and then analysed by ICP. The first results indicate the presence ofmetals: Ni, Mg, Zn, Mn, Fe... Various proposais for the use of these residues so as to avoid pollution due to their accumulation have been put forward. These ashes can be recombined with fuels, acting as catalysts to reduce the formation of tar and increase the production of hydrogen.

  11. Methods and apparatuses for deoxygenating biomass-derived pyrolysis oil

    DOEpatents

    Baird, Lance Awender; Brandvold, Timothy A.

    2015-10-20

    Embodiments of methods and apparatuses for deoxygenating a biomass-derived pyrolysis oil are provided. In one example, a method comprises the steps of separating a low-oxygen biomass-derived pyrolysis oil effluent into a low-oxygen-pyoil organic phase stream and an aqueous phase stream. Phenolic compounds are removed from the aqueous phase stream to form a phenolic-rich diluent recycle stream. A biomass-derived pyrolysis oil stream is diluted and heated with the phenolic-rich diluent recycle stream to form a heated diluted pyoil feed stream. The heated diluted pyoil feed stream is contacted with a deoxygenating catalyst in the presence of hydrogen to deoxygenate the heated diluted pyoil feed stream.

  12. Opposite influence of haloalkanes on combustion and pyrolysis of acetylene

    NASA Astrophysics Data System (ADS)

    Drakon, A. V.; Emelianov, A. V.; Eremin, A. V.; Mikheyeva, E. Yu

    2015-11-01

    An influence of haloalkanes CF3H and CCl4 (known as inflammation and explosion suppressors) on combustion and pyrolysis of acetylene behind shock waves was experimentally studied. While ignition delay times in stoihiometric acetylene-oxygen mixtures were expectedly increased by halogenoalkanes admixtures, the induction times of carbon particle formation at acetylene pyrolysis were dramatically reduced in presence of CCl4. A simplified kinetic model was suggested and characteristic rates of diacetylene C4H2 formation were estimated as a limiting stage of acetylene polymerization. An analysis of obtained data has indicated that promoting species is atomic chlorine forming in CCl4 pyrolysis, which interacts with acetylene and produces C2H radical, initiating a chain mechanism of acetylene decomposition. The results of kinetic modeling agree well with experimental data.

  13. The destruction of halogenated organic chemicals by plasma pyrolysis.

    PubMed

    Barton, T G; Mordy, J A

    1984-08-01

    Very high destruction efficiencies for halogenated chemicals have been achieved by plasma pyrolysis. Destruction efficiencies exceeded 99.9999999% for tests with polychlorinated biphenyls (PCBs). Preliminary tests with tetrachloromethane have obtained destruction efficiencies exceeding 99.99%. The plasma pyrolysis process involved the creation of a 250-kW plasma with a temperature in excess of 25 000 degrees C. The toxic material was injected into the plasma zone at a rate between 1 and 2 L/min. Thermochemical and photochemical dissociation of the toxic materials produced atoms and ions which recombined to form primarily H2, CO, HCl, and particulate carbon. The HCl was neutralized by NaOH. The flaring of the H2 and CO should destroy to a high degree any trace residuals. The application of plasma pyrolysis for the ultimate disposal of toxicological waste was also investigated. Rat carcasses containing mean lethal dosage of PCB were pyrolyzed.

  14. Performance of rotary kiln reactor for the elephant grass pyrolysis.

    PubMed

    De Conto, D; Silvestre, W P; Baldasso, C; Godinho, M

    2016-10-01

    The influence of process conditions (rotary speed/temperature) on the performance of a rotary kiln reactor for non-catalytic pyrolysis of a perennial grass (elephant grass) was investigated. The product yields, the production of non-condensable gases as well as the biochar properties were evaluated. The maximum H2 yield was close to that observed for catalytic pyrolysis processes, while the bio-oil yield was higher than reported for pyrolysis of other biomass in rotary kiln reactors. A H2/CO ratio suitable for Fischer-Tropsch synthesis (FTS) was obtained. The biochars presented an alkaline pH (above 10) and interesting contents of nutrients, as well as low electrical conductivity, indicating a high potential as soil amendment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Fate of bromine in pyrolysis of printed circuit board wastes.

    PubMed

    Chien, Y C; Wang, H P; Lin, K S; Huang, Y J; Yang, Y W

    2000-02-01

    Behavior of Br in pyrolysis of the printed circuit board waste with valuable copper and oil recycling has been studied in the present work. Experimentally, pyrolysis of the printed circuit board waste generated approximately 40.6% of oils, 24.9% of noncondensible gases and 34.5% of solid residues that enriched in copper (90-95%). The cuts of the oils produced from pyrolysis of the printed circuit board waste into weighted boiling fraction were primarily light naphtha and heavy gas oil. Approximately 72.3% of total Br in the printed circuit board waste were found in product gas mainly as HBr and bromobenzene. However, by extended X-ray absorption fine structural (EXAFS) spectroscopy, Cu-O and Cu-(O)-Cu species with bond distance of 1.87 and 2.95 A, respectively, were observed in the solid residues. Essentially, no Cu-Br species was found.

  16. Pyrolysis kinetics of hazelnut husk using thermogravimetric analysis.

    PubMed

    Ceylan, Selim; Topçu, Yıldıray

    2014-03-01

    This study aims at investigating physicochemical properties and pyrolysis kinetics of hazelnut husk, an abundant agricultural waste in Turkey. The physicochemical properties were determined by bomb calorimeter, elemental analysis and FT-IR spectroscopy. Physicochemical analysis results showed that hazelnut husk has a high calorimetric value and high volatile matter content. Pyrolysis experiments were carried out in a thermogravimetric analyzer under inert conditions and operated at different heating rates (5, 10, 20°C/min). Three different kinetic models, the iso-conversional Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW) models and Coats-Redfern method were applied on TGA data of hazelnut husk to calculate the kinetic parameters including activation energy, pre-exponential factor and reaction order. Simulation of hazelnut husk pyrolysis using data obtained from TGA analysis showed good agreement with experimental data. Combining with physicochemical properties, it was concluded that this biomass can become useful source of energy or chemicals.

  17. Molecular Structure and Reactivity in the Pyrolysis of Aldehydes

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  18. Toxic potentiality of bio-oils, from biomass pyrolysis, in cultured cells and Caenorhabditis elegans.

    PubMed

    Chatterjee, Nivedita; Eom, Hyun-Jeong; Jung, Su-Hwa; Kim, Joo-Sik; Choi, Jinhee

    2014-12-01

    Bio-oils, which are multicomponent mixtures, were produced from two different biomass (rice straw (rice oil) and sawdust of oak tree (oak oil)) by using the slow pyrolysis process, and chemical compositional screening with GC-MS detected several hazardous compounds in both bio-oil samples. The two bio-oils vary in their chemical compositional nature and concentrations. To know the actual hazard potentialities of these bio-oils, toxicological assessments were carried out in a comparative approach by using in vitro (Jurkat T and HepG2 cell) as well as in vivo (Caenorhabditis elegans) systems. A dose-dependent increase in cytotoxicity, cell death (apoptosis), and genotoxicity were observed in cultured cell systems. Similarly, the in vivo system, C. elegans also displayed a dose-dependent decrease in survival. It was found that in comparison with rice oil, oak oil displayed higher toxicity to all models systems, and the susceptibility order of the model systems were Jurkat T > HepG2 > C. elegans. Pursuing the study further toward the underlying mechanism by exploiting the C. elegans mutants screening assay, the bio-oils seem to mediate toxicity through oxidative stress and impairment of immunity. Taken together, bio-oils compositions mainly depend on the feedstock used and the pyrolysis conditions which in turn modulate their toxic potentiality.

  19. Pyrolysis of polyolefins for increasing the yield of monomers' recovery.

    PubMed

    Donaj, Pawel J; Kaminsky, W; Buzeto, F; Yang, W

    2012-05-01

    Pyrolysis of plastic waste is an alternative way of plastic recovery and could be a potential solution for the increasing stream of solid waste. The objective of this work was to increase the yield the gaseous olefins (monomers) as feedstock for polymerization process and to test the applicability of a commercial Ziegler-Natta (Z-N): TiCl(4)/MgCl(2) for cracking a mixture of polyolefins consisted of 46%wt. of low density polyethylene (LDPE), 30%wt. of high density polyethylene (HDPE) and 24%wt. of polypropylene (PP). Two sets of experiments have been carried out at 500 and 650°C via catalytic pyrolysis (1% of Z-N catalyst) and at 650 and 730°C via only-thermal pyrolysis. These experiments have been conducted in a lab-scale, fluidized quartz-bed reactor of a capacity of 1-3kg/h at Hamburg University. The results revealed a strong influence of temperature and presence of catalyst on the product distribution. The ratios of gas/liquid/solid mass fractions via thermal pyrolysis were: 36.9/48.4/15.7%wt. and 42.4/44.7/13.9%wt. at 650 and 730°C while via catalytic pyrolysis were: 6.5/89.0/4.5%wt. and 54.3/41.9/3.8%wt. at 500 and 650°C, respectively. At 650°C the monomer generation increased by 55% up to 23.6%wt. of total pyrolysis products distribution while the catalyst was added. Obtained yields of olefins were compared with the naphtha steam cracking process and other potentially attractive processes for feedstock generation. The concept of closed cycle material flow for polyolefins has been discussed, showing the potential benefits of feedstock recycling in a plastic waste management.

  20. Complete study of the pyrolysis and gasification of scrap tires in a pilot plant reactor.

    PubMed

    Conesa, Juan A; Martín-Gullón, I; Font, R; Jauhiainen, J

    2004-06-01

    The pyrolysis and gasification of tires was studied in a pilot plant reactor provided with a system for condensation of semivolatile matter. The study comprises experiments at 450, 750, and 1000 degrees C both in nitrogen and 10% oxygen atmospheres. Analysis of all the products obtained (gases, liquids, char, and soot) are presented. In the gas phase only methane and benzene yields increase with temperature until 1000 degrees C. In the liquids the main components are styrene, limonene, and isoprene. The solid fraction (including soot) increases with temperature. Zinc content of the char decreases with increasing temperature.

  1. Upgrading of heavy oil from the San Joaquin Valley of California by aqueous pyrolysis

    SciTech Connect

    Reynolds, J.G.; Murray, A.M.; Nuxoll, E.V.; Fox, G.A.

    1995-10-01

    Midway Sunset crude oil and well-head oil were treated at elevated temperatures in a closed system with the presence of water. Mild to moderate upgrading, as measured by increase in API gravity, was observed at 400{degrees}C or above. Reduced pressure operation exhibited upgrading activity comparable to upgrading under normal aqueous pyrolysis conditions. Reduced pressure operation was obtained by the use of specific blending methods, a surfactant, and the proper amount of water. The use of additives provided additional upgrading. The best of the minimum set tested was Co(II) 2-ethylhexanoate. Fe(III) 2-ethylhexanoate also showed some activity under certain conditions.

  2. Pyrolysis and Combustion of Acetonitrile (CH{sub 3}CN)

    SciTech Connect

    Britt, P.F.

    2002-05-22

    Acetonitrile (CH{sub 3}CN) is formed from the thermal decomposition of a variety of cyclic, noncyclic, and polymeric nitrogen-containing compounds such as pyrrole and polyacrylonitrile. The pyrolysis and combustion of acetonitrile have been studied over the past 30 years to gain a more detailed understanding of the complex mechanisms involved in the release of nitrogen-containing compounds such as hydrogen cyanide (HCN) in fires and nitrogen oxides (NOx) in coal combustion. This report reviews the literature on the formation of HCN and NOx from the pyrolysis and combustion of acetonitrile and discusses the possible products found in an acetonitrile fire.

  3. Kinetic Study on Pyrolysis of Oil Palm Frond

    NASA Astrophysics Data System (ADS)

    Soon, V. S. Y.; Chin, B. L. F.; Lim, A. C. R.

    2016-03-01

    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 (EA ) 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.

  4. Effect of pyrolysis temperature and heating rate on biochar obtained from pyrolysis of safflower seed press cake.

    PubMed

    Angın, Dilek

    2013-01-01

    Biochar is carbon-rich product generated from biomass through pyrolysis. In this study, the effects of pyrolysis temperature and heating rate on the yield and physicochemical and morphological properties of biochars obtained from safflower seed press cake were investigated. The results showed that the biochar yield and quality depend principally on the applied temperature where pyrolysis at 600 °C leaves a biochar with higher fixed carbon content (80.70%) and percentage carbon (73.75%), and higher heating value (30.27 MJ kg(-1)) in comparison with the original feedstock (SPC) and low volatile matter content (9.80%). The biochars had low surface areas (1.89-4.23 m(2)/g) and contained predominantly aromatic compounds. The biochar could be used for the production of activated carbon, in fuel applications, and water purification processes.

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

    PubMed

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

    2017-06-01

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

  6. Development of a pyrolysis waste recovery model with designs, test plans, and applications for space-based habitats

    NASA Technical Reports Server (NTRS)

    Roberson, Bobby J.

    1992-01-01

    Extensive literature searches revealed the numerous advantages of using pyrolysis as a means of recovering usable resources from inedible plant biomass, paper, plastics, other polymers, and human waste. A possible design of a pyrolysis reactor with test plans and applications for use on a space-based habitat are proposed. The proposed system will accommodate the wastes generated by a four-person crew while requiring solar energy as the only power source. Waste materials will be collected and stored during the 15-day lunar darkness periods. Resource recovery will occur during the daylight periods. Usable gases such as methane and hydrogen and a solid char will be produced while reducing the mass and volume of the waste to almost infinitely small levels. The system will be operated economically, safely, and in a non-polluting manner.

  7. Viability of Applying Curie Point Pyrolysis/Gas Chromatography Techniques for Characterization of Ammonium Perchlorate Based Propellants

    SciTech Connect

    BARNETT, JAMES L.; MONTOYA, BERTHA M.

    2002-07-01

    Curie Point pyrolysis-gas chromatography was investigated for use as a tool for characterization of aged ammonium perchlorate based composite propellants (1). Successful application of the technique will support the surveillance program for the Explosives Materials and Subsystems Department (1). Propellant samples were prepared by separating the propellant into reacted (oxidated) and unreacted zones. The experimental design included the determination of system reliability followed by, reproducibility, sample preparation and analysis of pyrolysis products. Polystyrene was used to verify the reliability of the system and showed good reproducibility. Application of the technique showed high variation in the data. Modifications to sample preparation did not enhance the reproducibility. It was determined that the high concentration of ammonium perchlorate in the propellant matrix was compromising the repeatability of the analysis.

  8. One-Dimensional Ablation with Pyrolysis Gas Flow Using a Full Newton's Method and Finite Control Volume Procedure

    NASA Technical Reports Server (NTRS)

    Amar, Adam J.; Blackwell, Ben F.; Edwards, Jack R.

    2007-01-01

    The development and verification of a one-dimensional material thermal response code with ablation is presented. The implicit time integrator, control volume finite element spatial discretization, and Newton's method for nonlinear iteration on the entire system of residual equations have been implemented and verified for the thermochemical ablation of internally decomposing materials. This study is a continuation of the work presented in "One-Dimensional Ablation with Pyrolysis Gas Flow Using a Full Newton's Method and Finite Control Volume Procedure" (AIAA-2006-2910), which described the derivation, implementation, and verification of the constant density solid energy equation terms and boundary conditions. The present study extends the model to decomposing materials including decomposition kinetics, pyrolysis gas flow through the porous char layer, and a mixture (solid and gas) energy equation. Verification results are presented for the thermochemical ablation of a carbon-phenolic ablator which involves the solution of the entire system of governing equations.

  9. Pyrolysis and gasification of meat-and-bone-meal: energy balance and GHG accounting.

    PubMed

    Cascarosa, Esther; Boldrin, Alessio; Astrup, Thomas

    2013-11-01

    Meat-and-bone-meal (MBM) produced from animal waste has become an increasingly important residual fraction needing management. As biodegradable waste is routed away from landfills, thermo-chemical treatments of MBM are considered promising solution for the future. Pyrolysis and gasification of MBM were assessed based on data from three experimental lab and pilot-scale plants. Energy balances were established for the three technologies, providing different outcomes for energy recovery: bio-oil was the main product for the pyrolysis system, while syngas and a solid fraction of biochar were the main products in the gasification system. These products can be used - eventually after upgrading - for energy production, thereby offsetting energy production elsewhere in the system. Greenhouse gases (GHG) accounting of the technologies showed that all three options provided overall GHG savings in the order of 600-1000kg CO2-eq. per Mg of MBM treated, mainly as a consequence of avoided fossil fuel consumption in the energy sector. Local conditions influencing the environmental performance of the three systems were identified, together with critical factors to be considered during decision-making regarding MBM management.

  10. Pyrolysis and gasification of meat-and-bone-meal: Energy balance and GHG accounting

    SciTech Connect

    Cascarosa, Esther; Boldrin, Alessio; Astrup, Thomas

    2013-11-15

    Highlights: • GHG savings are in the order of 600–1000 kg CO{sub 2}-eq. per Mg of MBM treated. • Energy recovery differed in terms of energy products and efficiencies. • The results were largely determined by use of the products for energy purposes. - Abstract: Meat-and-bone-meal (MBM) produced from animal waste has become an increasingly important residual fraction needing management. As biodegradable waste is routed away from landfills, thermo-chemical treatments of MBM are considered promising solution for the future. Pyrolysis and gasification of MBM were assessed based on data from three experimental lab and pilot-scale plants. Energy balances were established for the three technologies, providing different outcomes for energy recovery: bio-oil was the main product for the pyrolysis system, while syngas and a solid fraction of biochar were the main products in the gasification system. These products can be used – eventually after upgrading – for energy production, thereby offsetting energy production elsewhere in the system. Greenhouse gases (GHG) accounting of the technologies showed that all three options provided overall GHG savings in the order of 600–1000 kg CO{sub 2}-eq. per Mg of MBM treated, mainly as a consequence of avoided fossil fuel consumption in the energy sector. Local conditions influencing the environmental performance of the three systems were identified, together with critical factors to be considered during decision-making regarding MBM management.

  11. Life cycle assessment of biochar application in Vietnam using two pyrolysis technologies

    NASA Astrophysics Data System (ADS)

    Mohammadi, Ali; Cowie, Annette; Mai, Thi Lan Anh; Anaya de la Rosa, Ruy; Kristiansen, Paul; Brandão, Miguel; Joseph, Stephen

    2016-04-01

    This study presents a comparative analysis of the environmental impacts of biochar systems in Vietnam using household scale and district scale pyrolysis technologies. At the household scale, pyrolytic cook-stoves were assumed to be used by households to produce biochar. The pyrolytic cook-stoves burn pyrolysis gases and use the heat for cooking. At the district scale, the BIGchar 2200 unit, a continuous operation system, is utilised to convert rice husk to biochar. This unit allows for easy capture of produced gases, which can be used to generate energy products, adding value to biochar production and decreasing environmental costs through the displacement of fossil fuels. The biochar produced from each system was assumed to be applied to paddy rice fields. Results from Life Cycle Assessment showed that biochar production at the both scales for application to the soil significantly improved environmental performance of 1 Mg of rice husk relative to the reference scenario (open burning of husk) across a range of impacts including climate change (CC), particulate matter and non-renewable energy (NRE) use. Net carbon abatement of biochar systems ranged from 355 to 427 kg CO2-eq Mg-1 of spring rice husk at the household scale and district scale, respectively. The district scale offered greater carbon abatement primarily due to the higher rate of LPG displaced by this unit.

  12. Neurotoxicity of anhydroecgonine methyl ester, a crack cocaine pyrolysis product.

    PubMed

    Garcia, Raphael Caio Tamborelli; Dati, Livia Mendonça Munhoz; Fukuda, Suelen; Torres, Larissa Helena Lobo; Moura, Sidnei; de Carvalho, Nathalia Delazeri; Carrettiero, Daniel Carneiro; Camarini, Rosana; Levada-Pires, Adriana Cristina; Yonamine, Mauricio; Negrini-Neto, Osvaldo; Abdalla, Fernando Maurício Francis; Sandoval, Maria Regina Lopes; Afeche, Solange Castro; Marcourakis, Tania

    2012-07-01

    Smoking crack cocaine involves the inhalation of cocaine and its pyrolysis product, anhydroecgonine methyl ester (AEME). Although there is evidence that cocaine is neurotoxic, the neurotoxicity of AEME has never been evaluated. AEME seems to have cholinergic agonist properties in the cardiovascular system; however, there are no reports on its effects in the central nervous system. The aim of this study was to investigate the neurotoxicity of AEME and its possible cholinergic effects in rat primary hippocampal cell cultures that were exposed to different concentrations of AEME, cocaine, and a cocaine-AEME combination. We also evaluated the involvement of muscarinic cholinergic receptors in the neuronal death induced by these treatments using concomitant incubation of the cells with atropine. Neuronal injury was assessed using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and lactate dehydrogenase (LDH) assays. The results of the viability assays showed that AEME is a neurotoxic agent that has greater neurotoxic potential than cocaine after 24 and 48 h of exposure. We also showed that incubation for 48 h with a combination of both compounds in equipotent concentrations had an additive neurotoxic effect. Although both substances decreased cell viability in the MTT assay, only cocaine increased LDH release. Caspase-3 activity was increased after 3 and 6 h of incubation with 1mM cocaine and after 6 h of 0.1 and 1.0mM AEME exposure. Atropine prevented the AEME-induced neurotoxicity, which suggests that muscarinic cholinergic receptors are involved in AEME's effects. In addition, binding experiments confirmed that AEME has an affinity for muscarinic cholinergic receptors. Nevertheless, atropine was not able to prevent the neurotoxicity produced by cocaine and the cocaine-AEME combination, suggesting that these treatments activated other neuronal death pathways. Our results suggest a higher risk for neurotoxicity after smoking crack cocaine than after

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

    PubMed

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

    2013-02-01

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

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

    PubMed

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

    2017-02-01

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

  15. Recognition of chitin and proteins in invertebrate cuticles using analytical pyrolysis/gas chromatography and pyrolysis/gas chromatography/mass spectrometry.

    PubMed

    Stankiewicz, B A; Van Bergen, P F; Duncan, I J; Carter, J F; Briggs, D E; Evershed, R P

    1996-01-01

    Flash pyrolysis/gas chromatography (py/GC) and py/GC/mass spectrometry (MS) have been utilized to characterize the cuticles of invertebrates chemically. Pyrolysis products have been identified and assigned to specific cuticular components. Acetylpyridones, acetamidofuran, 3-acetamido-5-methylfuran and 3-acetamido-(2 and 4)-pyrones are proposed as characteristic pyrolysis markers for chitin. Pyrolysis products displaying ions of m/z 70, 154, 168, 194 are thought to derive from diketopiperazine structures and provide potential markers for proteins and peptides in which proline, alanine, valine, arginine and glycine are the dominant amino acids. These products, constituting specific pyrolysis markers for invertebrate cuticles, may reflect the amino acid composition of their constituent structural proteins. The source of the various pyrolysis products of proteins has been verified by pyrolysis of reference proteins, peptides and amino acid mixtures. The presence of additional pyrolysis products related directly to histidine and catechol moieties is consistent with the chemical structure and composition proposed for arthropod cuticles based on recent work utilizing solid state 13C and 15N nuclear magnetic resonance. This study constitutes the first comprehensive chemical characterization of the pyrolysis products of invertebrate cuticles and provides the basis for future investigations requiring qualitative screening for cross-linked chitin and proteins in modern and fossil cuticles and in materials, e.g. geopolymers, that may be derived from them.

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

    PubMed

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

    2017-04-01

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

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

    PubMed

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

    2017-03-01

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

  18. Catalytic pyrolysis of palm kernel shell waste in a fluidized bed.

    PubMed

    Kim, Sung Won; Koo, Bon Seok; Lee, Dong Hyun

    2014-09-01

    The catalytic pyrolysis of palm kernel shell was investigated in a fluidized bed with zsm-5 and equilibrium FCC (Ecat) catalysts. Catalytic pyrolysis oil yields were remarkably reduced and gas yields were increased due to the higher catalytic reaction of primary volatiles compared to non-catalytic pyrolysis. Char yields were affected by temperature and the pore structure of the catalysts. The pyrolysis oil was characterized by lower H/C and O/C molar ratios due to aromatization and deoxygenation of volatiles by the catalysts. The catalytic pyrolysis oils contained more oxygen and nitrogen and less sulfur than petroleum oils. The oils had a high concentration of nitriles, with a carbon number distribution similar to fatty acids. The catalytic pyrolysis oils featured high nitriles yield with Ecat and high aromatics yield in the light fraction with zsm-5, due to characteristics of the catalyst. The catalytic pyrolysis oils showed potentials as feedstocks for bio-diesel and chemicals.

  19. Pyrolysis Oil Stabilization: Hot-Gas Filtration; Cooperative Research and Development Final Report, CRADA Number CRD-09-333

    SciTech Connect

    Baldwin, R.

    2012-07-01

    The hypothesis that was tested in this task was that separation of char, with its associated mineral matter from pyrolysis vapors before condensation, will lead to improved oil quality and stability with respect to storage and transportation. The metric used to evaluate stability in this case was a 10-fold reduction in the rate of increase of viscosity as determined by ASTM D445 (the accelerated aging test). The primary unit operation that was investigated for this purpose was hot-gas filtration. A custom-built heated candle filter system was fabricated by the Pall Corporation and furnished to NREL for this test campaign. This system consisted of a candle filter element in a containment vessel surrounded by heating elements on the external surface of the vessel. The filter element and housing were interfaced to NREL?s existing 0.5 MTD pyrolysis Process Development Unit (PDU). For these tests the pyrolysis reactor of the PDU was operated in the entrained-flow mode. The HGF test stand was installed on a slipstream from the PDU so that both hot-gas filtered oil and bio-oil that was not hot-gas filtered could be collected for purposes of comparison. Two filter elements from Pall were tested: (1) porous stainless steel (PSS) sintered metal powder; (2) sintered ceramic powder. An extremely sophisticated bio-oil condensation and collection system was designed and fabricated at NREL and interfaced to the filter unit.

  20. Biomass pyrolysis for biochar or energy applications? A life cycle assessment.

    PubMed

    Peters, Jens F; Iribarren, Diego; Dufour, Javier

    2015-04-21

    The application of biochar as a soil amendment is a potential strategy for carbon sequestration. In this paper, a slow pyrolysis system for generating heat and biochar from lignocellulosic energy crops is simulated and its life-cycle performance compared with that of direct biomass combustion. The use of the char as biochar is also contrasted with alternative use options: cofiring in coal power plants, use as charcoal, and use as a fuel for heat generation. Additionally, the influence on the results of the long-term stability of the biochar in the soil, as well as of biochar effects on biomass yield, is evaluated. Negative greenhouse gas emissions are obtained for the biochar system, indicating a significant carbon abatement potential. However, this is achieved at the expense of lower energy efficiency and higher impacts in the other assessed categories when compared to direct biomass combustion. When comparing the different use options of the pyrolysis char, the most favorable result is obtained for char cofiring substituting fossil coal, even assuming high long-term stability of the char. Nevertheless, a high sensitivity to biomass yield increase is found for biochar systems. In this sense, biochar application to low-quality soils where high yield increases are expected would show a more favorable performance in terms of global warming.

  1. [Study on Microwave Co-Pyrolysis of Low Rank Coal and Circulating Coal Gas].

    PubMed

    Zhou, Jun; Yang, Zhe; Liu, Xiao-feng; Wu, Lei; Tian, Yu-hong; Zhao, Xi-cheng

    2016-02-01

    The pyrolysis of low rank coal to produce bluecoke, coal tar and gas is considered to be the optimal method to realize its clean and efficient utilization. However, the current mainstream pyrolysis production technology generally has a certain particle size requirements for raw coal, resulting in lower yield and poorer quality of coal tar, lower content of effective components in coal gas such as H₂, CH₄, CO, etc. To further improve the yield of coal tar obtained from the pyrolysis of low rank coal and explore systematically the effect of microwave power, pyrolysis time and particle size of coal samples on the yield and composition of microwave pyrolysis products of low rank coal through the analysis and characterization of products with FTIR and GC-MS, introducing microwave pyrolysis of low rank coal into the microwave pyrolysis reactor circularly was suggested to carry out the co-pyrolysis experiment of the low rank coal and coal gas generated by the pyrolysis of low rank coal. The results indicated that the yield of the bluecoke and liquid products were up to 62.2% and 26.8% respectively when the optimal pyrolysis process conditions with the microwave power of 800W, pyrolysis time of 40 min, coal samples particle size of 5-10 mm and circulating coal gas flow rate of 0.4 L · min⁻¹ were selected. The infrared spectrogram of the bluecoke under different microwave power and pyrolysis time overlapped roughly. The content of functional groups with -OH, C==O, C==C and C−O from the bluecoke through the pyrolysis of particle size coal samples had a larger difference. To improve microwave power, prolonging pyrolysis time and reducing particle size of coal samples were conducive to converting heavy component to light one into coal tar.

  2. [Effects of repeated skin applications of heavy pyrolysis resin on cytochrome P-450 level and glutathione transferase activity in liver microsomes and cytosol in rats in relation to the level of toxic effects of pyrolysis resin on internal organs].

    PubMed

    Kravchenko, M N; Loginov, A S; Petrova, L P; Ausheva, L Kh; Bendikov, E A

    1990-10-01

    Rats received 20 skin applications of heavy pyrolysis resin, containing about 30% of polycyclic aromatic hydrocarbons. The every exposure duration was 4 hours a day. Applications have been carried out daily 5 days a week in the course of 4 weeks. Induction of cytochrome P-450 (P-450) by 79%, significant induction of microsomal (GTm) and cytosol (GTc) glutathione-S-transferase activity (by 46 and 85%, respectively) and small increase of reduced glutathione level (by 9%) also were registered as a result of these exposures. Lipid peroxidation level determined by TBK-reactive products quantity didn't alter significantly. Close correlation between ratio values of P-450/GTm levels and P-450/GTc levels and toxic effect indices of heavy pyrolysis resin on rat immune and endocrine systems.

  3. Metals Solubility in Biochar from Different Feedstock and Pyrolysis Processes

    USDA-ARS?s Scientific Manuscript database

    Biochar is a co-product of the pyrolysis process of biomass-to-energy conversion. About 15-40% of the feedstock is recovered as biochar in the process. Further use of biochar in soil is suggested as a means to increase soil productivity, and to store and sequester much of the biochar-recalcitrant ...

  4. Toxicity of the pyrolysis products of spacecraft materials

    NASA Technical Reports Server (NTRS)

    Lawrence, W. H.

    1974-01-01

    A number of spacecraft construction materials are evaluated for the toxic effects of their thermodegradation products on rats. Pyrolysis toxicity testing of pyrolysate fumes establish carbon monoxide, carbon dioxide and hydrogen cyanide as the most common intoxicating agents. Generally, COHb levels of animals expiring in the test chamber suggest higher concentrations of CO are produced with larger samples of most materials.

  5. Pyrolysis-combustion 14C dating of soil organic matter

    USGS Publications Warehouse

    Wang, Hongfang; Hackley, Keith C.; Panno, S.V.; Coleman, D.D.; Liu, J.C.-L.; Brown, J.

    2003-01-01

    Radiocarbon (14C) dating of total soil organic matter (SOM) often yields results inconsistent with the stratigraphic sequence. The onerous chemical extractions for SOM fractions do not always produce satisfactory 14C dates. In an effort to develop an alternative method, the pyrolysis-combustion technique was investigated to partition SOM into pyrolysis volatile (Py-V) and pyrolysis residue (Py-R) fractions. The Py-V fractions obtained from a thick glacigenic loess succession in Illinois yielded 14C dates much younger but more reasonable than the counterpart Py-R fractions for the soil residence time. Carbon isotopic composition (??13C) was heavier in the Py-V fractions, suggesting a greater abundance of carbohydrate- and protein-related constituents, and ??13C was lighter in the Py-R fractions, suggesting more lignin- and lipid-related constituents. The combination of 14C dates and ??13C values indicates that the Py-V fractions are less biodegradation resistant and the Py-R fractions are more biodegradation resistant. The pyrolysis-combustion method provides a less cumbersome approach for 14C dating of SOM fractions. With further study, this method may become a useful tool for analyzing unlithified terrestrial sediments when macrofossils are absent. ?? 2003 University of Washington. Published by Elsevier Inc. All rights reserved.

  6. Quantitative 13C NMR characterization of fast pyrolysis oils

    DOE PAGES

    Happs, Renee M.; Lisa, Kristina; Ferrell, III, Jack R.

    2016-10-20

    Quantitative 13C NMR analysis of model catalytic fast pyrolysis (CFP) oils following literature procedures showed poor agreement for aromatic hydrocarbons between NMR measured concentrations and actual composition. Furthermore, modifying integration regions based on DEPT analysis for aromatic carbons resulted in better agreement. Solvent effects were also investigated for hydrotreated CFP oil.

  7. Oxalate Synthesis and Pyrolysis: A Colorful Introduction to Stoichiometry

    ERIC Educational Resources Information Center

    Vannatta, Michael W.; Richards-Babb, Michelle; Sweeney, Robert J.

    2010-01-01

    Metal oxalate synthesis and pyrolysis provides an opportunity for students to (i) learn stoichiometry, (ii) experience the consequences of proper stoichiometric calculations and experimental techniques, and (iii) be introduced to the relevance of chemistry by highlighting oxalates in context, for example, usages and health effects. At our…

  8. Fast pyrolysis of biomass thermally pretreated by torrefaction

    USDA-ARS?s Scientific Manuscript database

    Torrefied biomass samples were produced from hardwood and switchgrass pellets using the biochar experimenter’s kit (BEK) reactor and analyzed for their utility as pretreated feedstock for biofuels production via fast pyrolysis. The energy efficiency for the BEK torrefaction process with propane gas ...

  9. An Idealized Direct-Contact Biomass Pyrolysis Reactor Model

    NASA Technical Reports Server (NTRS)

    Miller, R. S.; Bellan, J.

    1996-01-01

    A numerical study is performed in order to assess the performance of biomass pyrolysis reactors which utilize direct particle-wall thermal conduction heating. An idealized reactor configuration consisting of a flat-plate turbulent boundary layer flow with particle convection along the heated wall and incorporating particle re-entrainment is considered.

  10. Application of pyrolysis to recycling organics from waste tantalum capacitors.

    PubMed

    Niu, Bo; Chen, Zhenyang; Xu, Zhenming

    2017-08-05

    Tantalum capacitors (TCs) are widely used in electronic appliances. The rapid replacement of electronic products results in generating large amounts of waste TCs (WTCs). WTCs, rich in valuable tantalum, are considered as high quality tantalum resources for recycling. However, environmental pollution will be caused if the organics of WTCs were not properly disposed. Therefore, effectively recycling the organics of WTCs is significant for recovering the valuable parts. This study proposed an argon (Ar) pyrolysis process to recycle the organics from WTCs. The organic decomposition kinetic was first analyzed by thermogravimetry. The results showed that the organics were decomposed in two major steps and the average activation energy was calculated to 234kJ/mol. Then, the suitable pyrolysis parameters were determined as 550°C, 30min and 100ml/min. The organics were effectively decomposed and converted to oils (mainly contained phenol homologs and benzene homologs) and gases (some hydrocarbon). These pyrolysis products could be reutilized as energy sources. Moreover, based on the products and bond energy theory, the pyrolysis mechanisms of the organics were also discussed. Finally, a reasonable technological process for products utilization was presented. This study contributes to the efficient recycling the organics before valuable material recovery from WTCs. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Analytical Pyrolysis-Chromatography: Something Old, Something New

    ERIC Educational Resources Information Center

    Bower, Nathan W.; Blanchet, Conor J. K.

    2010-01-01

    Despite a long history of use across multiple disciplines, analytical pyrolysis is rarely taught in undergraduate curricula. We briefly review some interesting applications and discuss the three types of analytical pyrolyzers available commercially. We also describe a low-cost alternative that can be used to teach the basic principles of…

  12. Oxalate Synthesis and Pyrolysis: A Colorful Introduction to Stoichiometry

    ERIC Educational Resources Information Center

    Vannatta, Michael W.; Richards-Babb, Michelle; Sweeney, Robert J.

    2010-01-01

    Metal oxalate synthesis and pyrolysis provides an opportunity for students to (i) learn stoichiometry, (ii) experience the consequences of proper stoichiometric calculations and experimental techniques, and (iii) be introduced to the relevance of chemistry by highlighting oxalates in context, for example, usages and health effects. At our…

  13. A computational study of pyrolysis reactions of lignin model compounds

    Treesearch

    Thomas Elder

    2010-01-01

    Enthalpies of reaction for the initial steps in the pyrolysis of lignin have been evaluated at the CBS-4m level of theory using fully substituted b-O-4 dilignols. Values for competing unimolecular decomposition reactions are consistent with results previously published for phenethyl phenyl ether models, but with lowered selectivity. Chain propagating reactions of free...

  14. Lifecycle Assessment of Biofuel Production from Wood Pyrolysis Technology

    ERIC Educational Resources Information Center

    Manyele, S. V.

    2007-01-01

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

  15. Lifecycle Assessment of Biofuel Production from Wood Pyrolysis Technology

    ERIC Educational Resources Information Center

    Manyele, S. V.

    2007-01-01

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

  16. Pyrolysis characteristics and kinetics of aquatic biomass using thermogravimetric analyzer.

    PubMed

    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.

  17. Fate of forms of arsenic in Yima coal during pyrolysis

    SciTech Connect

    Ruiqing Liu; Jianli Yang; Yong Xiao; Zhenyu Liu

    2009-04-15

    Forms of arsenic in a Chinese bituminous coal, Yima, and their transformation behaviors during coal pyrolysis were investigated. The chemical leaching method was used to characterize the forms of arsenic in the raw coal and the chars. The effect of minerals on arsenic release was also studied. It was found that about 72% arsenic in YM coal is bound to sulfide species; 16% to sulfates, phosphates, or oxides; 10% to organic species; and 2% to aluminosilicates. The organic-bound arsenic is the most releasable, while the aluminosilicates-bound arsenic is the least releasable. Aluminosilicates inhibit arsenic release due to the formation of aluminosilicates-bound arsenic during pyrolysis. Sulfides, sulfates, phosphates, or oxides may also restrain arsenic release. Carbonates and ion exchangeable minerals in Yima coal do not show any significant influence on the release of arsenic during coal pyrolysis. Secondary reactions between arsenic and the coal matrix should exist, as evidenced by significant increase in organic-bound arsenic in chars obtained from pyrolysis in a temperature range of 300-700{sup o}C. 18 refs., 5 figs., 5 tabs.

  18. High-temperature pyrolysis mechanisms of coal model compounds

    SciTech Connect

    Penn, J.H.; Owens, W.H.

    1991-01-01

    The degradation of the carboxylic acid group has been examined with respect to potential pretreatment strategies for fossil fuel conversion processes. In one potential pretreatment strategy involving cation exchange of the carboxylic acid group, a series of benzoic acid and stearic acid salts have been chosen to model the tight'' carboxylic acids of immature fossil fuel feedstocks and have been pyrolyzed with an entrained flow reactor. Our preliminary results indicate that Group I and II salts yield primarily the parent acid. Benzoate salts also yield small amounts of benzene while the stearic acid salts give no other detectable products. In two alternative treatment strategies, esterification and anhydride preparation have also been accomplished with these compounds being subjected to the entrained flow reactor conditions. The benzoate esters give a number of products, such as benzaldehyde, benzene, and low MW gases. The formation of these compounds is extremely dependent on pyrolysis conditions and alkoxy chain length. A xenon flashlamp and an entrained flow reactor have been used to heat organic substrates to varying temperatures using different heating rates. Ultrarapid flashlamp pyrolysis (heating rate>10{sup 50}C/s) has been performed. Since the ultrarapid pyrolysis products differ from those observed with traditional heating techniques and differ from the products formed photochemically, the flashlamp pyrolysis products are attributed to high temperature thermal activation.

  19. Analytical Pyrolysis-Chromatography: Something Old, Something New

    ERIC Educational Resources Information Center

    Bower, Nathan W.; Blanchet, Conor J. K.

    2010-01-01

    Despite a long history of use across multiple disciplines, analytical pyrolysis is rarely taught in undergraduate curricula. We briefly review some interesting applications and discuss the three types of analytical pyrolyzers available commercially. We also describe a low-cost alternative that can be used to teach the basic principles of…

  20. An Idealized Direct-Contact Biomass Pyrolysis Reactor Model

    NASA Technical Reports Server (NTRS)

    Miller, R. S.; Bellan, J.

    1996-01-01

    A numerical study is performed in order to assess the performance of biomass pyrolysis reactors which utilize direct particle-wall thermal conduction heating. An idealized reactor configuration consisting of a flat-plate turbulent boundary layer flow with particle convection along the heated wall and incorporating particle re-entrainment is considered.