EP0820497A1 - Gazeification supercritique catalytique de biomasses mouillees - Google Patents

Gazeification supercritique catalytique de biomasses mouillees

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Publication number
EP0820497A1
EP0820497A1 EP96910689A EP96910689A EP0820497A1 EP 0820497 A1 EP0820497 A1 EP 0820497A1 EP 96910689 A EP96910689 A EP 96910689A EP 96910689 A EP96910689 A EP 96910689A EP 0820497 A1 EP0820497 A1 EP 0820497A1
Authority
EP
European Patent Office
Prior art keywords
carbon
catalyst
feedstock
organic matter
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96910689A
Other languages
German (de)
English (en)
Other versions
EP0820497A4 (fr
Inventor
Michael J. Antal, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Hawaii
Original Assignee
University of Hawaii
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Hawaii filed Critical University of Hawaii
Publication of EP0820497A1 publication Critical patent/EP0820497A1/fr
Publication of EP0820497A4 publication Critical patent/EP0820497A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/008—Processes carried out under supercritical conditions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/06—Catalysts as integral part of gasifiers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0979—Water as supercritical steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/1269—Heating the gasifier by radiating device, e.g. radiant tubes
    • C10J2300/1276—Heating the gasifier by radiating device, e.g. radiant tubes by electricity, e.g. resistor heating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • Hydrogen has enormous potential as a fuel source, due to its high energy value and cleanliness, if it can be produced economically. Hydrogen is also a very useful chemical reactant.
  • thermochemical conversion techniques such as oxidation or pyrolysis
  • reaction rates have been too slow for commercial exploitation as a means for hydrogen production.
  • wet biomass that is, plants with a high moisture content, such as water hyacinth, banana tree, cattails, green alga, and kelp, though plentiful, relatively inexpensive, and renewable, has not been considered useful feedstock for such thermochemical conversion techniques.
  • the disadvantage of wet biomass is the high cost of water removal often required before thermochemical conversion can be carried out.
  • the variety of carbohydrates and other chemical species in these plants and the number of mechanisms through which they can react have obscured understanding of the means by which wet biomass may be most efficiently decomposed to form the desired gaseous products without tar or char byproducts.
  • Dairy waste has been converted in a supercritical water medium, at temperatures between 400°C and 450°C and pressures as high as 34.5 MPa, over catalysts containing alkali carbonates and nickel into a methane-rich gas.
  • an object of the present invention to provide a method for converting organic matter such as biomass or organic waste to desirable products without the need for drying prior to treatment. It is another object of the present invention to provide a method for gasifying biomass or other organic matter that achieves a high efficiency of conversion of the organic matter to desirable gaseous products, and particularly hydrogen, at economical rates. It is yet another object of the present invention to achieve a high degree of gasification using an inexpensive, stable catalyst.
  • An additional object of the present invention is to gasify concentrated organic matter feedstocks to hydrogen, methane and other simple hydrocarbons.
  • a further object of the present invention is to destroy organic waste efficiently and completely.
  • the present invention achieves these and other objects by catalytically decomposing organic matter, such as wet biomass and organic waste, in a reaction medium, producing a hydrogen-enriched product and substantially no tar or char residues.
  • the present invention provides a method that includes contacting a feedstock in a reaction medium with a carbon-containing catalyst for a time sufficient to gasify the feedstock, wherein the feedstock includes organic matter and the medium includes water at a pressure of 22.1 MPa or greater and a temperature of 374 °C or greater.
  • the catalyst may be an activated carbon or a charcoal.
  • the present invention provides a method in which a carbon-containing catalyst is provided in a reaction zone in a reactor, preheating and pressurizing the reaction zone, introducing a water-containing feedstock into the preheated and pressurized reaction zone, in which zone, water in the feedstock has a temperature of 374°C or greater and a pressure of 22.1 MPa or greater and wherein the feedstock includes organic matter and contacting the feedstock with the catalyst in the reaction zone to yield a product containing water, hydrogen, methane, carbon dioxide or mixtures thereof.
  • Suitable organic matter feedstocks for use in methods according to the present invention include biomass, organic waste and mixtures thereof.
  • Suitable reaction media include water, whether in pure form or in a mixture with other substances, at supercritical conditions that preferably are substantially free of oxygen.
  • the present invention achieves numerous advantages. Numerous types of feedstocks may be utilized, including organic wastes and biomass having a high moisture content. Hydrogen yields and conversion of carbon in the feedstock to gas are high even at high feedstock flow rates and concentrations. Virtually complete gasification is achieved in relatively short periods of time.
  • the reaction product may be substantially free of tar or char, even when the feedstock has a high carbon concentration.
  • the carbon-based catalyst is relatively inexpensive compared to other catalysts, is stable in the environment of a supercritical water medium and maintains activity over long periods of time.
  • Figure 1 is a schematic diagram for a method according to the present invention for gasifying biomass in a supercritical water-containing medium; and Figure 2 depicts tar yield from catalytic gasification of glucose in supercritical water at increasing reaction temperature.
  • organic matter as used herein will denote biomass, such as plant species, sewage sludge, agricultural or forestry waste, and organic waste such as organic solvents, organic acids and the like.
  • Exemplary plant species include those having relatively high moisture contents such as water hyacinth, banana tree, cattails, green alga, kelp or other aquatic species.
  • critical point refers to the thermodynamic state of a substance in which its liquid and gaseous phases co-exist in equilibrium at the highest possible temperature.
  • the critical point is a temperature of 647K (374°C) and a pressure of 221 bar (22.1 MPa).
  • supercritical refers to a thermodynamic state at conditions beyond those recognized as the "critical point" of a substance.
  • pure water at the supercritical condition has a temperature greater than 374°C and a pressure greater than 22.1 MPa.
  • the density of water is a function of both temperature and pressure.
  • Supercritical water acts as a dense gas with the solvation characteristics of a nonpolar organic. Thus, organic compounds and gases are completely miscible with it, but inorganic substances such as salts are immiscible.
  • nonoxidizing refers to the condition of being substantially free of oxygen or air.
  • a method according to the present invention generally involves contacting organic matter in a supercritical water-containing medium with a catalyst to produce hydrogen, carbon dioxide and other desired gaseous species.
  • organic waste or biomass having a high water content may be utilized as is for a feedstock or may be put in a form, e.g., a slurry with water, that facilitates adequate flow and contact with the catalyst.
  • the feedstock is contacted with the catalyst at suitable temperature and pressure conditions so that the water is at supercritical conditions.
  • the temperature is about 600°C and the pressure is 22.1 MPa or greater.
  • the organic matter in the feedstock is rapidly and virtually completely gasified to produce hydrogen and other gases such as methane or other hydrocarbons, carbon monoxide and carbon dioxide, e.g., from thermal decomposition of the organic matter.
  • gases such as methane or other hydrocarbons, carbon monoxide and carbon dioxide, e.g., from thermal decomposition of the organic matter.
  • less than 1 wt% of the reaction product is in the form of tars or chars.
  • the gas phase of the reaction product may be separated from the rest of the reaction product by conventional gas-liquid separation techniques. To reduce any hazards of explosion, the gases may be cooled.
  • thermodynamic paths may be followed in order to achieve supercritical conditions for water.
  • a feedstock containing a biomass and water mixture may be heated until supercritical conditions are reached.
  • a method according to the present invention can be carried out in a constant pressure reactor scheme such as illustrated in Figure 1.
  • the reactor scheme includes a feedstock supply and a heated flow-type reactor housing a catalyst and capable of maintaining conditions associated with a supercritical reaction medium.
  • substantially deaerated water having little or no oxygen therein is fed into a reactor and then the pressure is increased to a desired level.
  • a feedstock 12, e.g., a slurry of biomass and water, can then be supplied to the reactor scheme from a feeding system 14. Flow rate of the feedstock out of the feeding system 14 and to a reactor 16 is controlled, e.g., by a pump 18.
  • Reactor 16, which may be a flow-type reactor, contains a heating zone 20, containing catalyst bed 22 through which the feedstock flows.
  • a suitable form for such a reactor is a metal tube (0.375 inch OD, 0.187 inch ID and 18.9 inches long) made of a material such as INCONEL 625.
  • Catalyst bed 22 may occupy a substantial portion of the reactor, e.g., about two-thirds of the heating zone of the reactor.
  • an inert material such as alumina beads may be used to confine the catalyst to the heating zone and to minimize action of the carbon- containing catalyst as an adsorbent.
  • Conditions within the reactor as the conversion proceeds may be monitored, such as via thermocouples, not shown, located along the length of and inside the reactor, and by other conventional means, such as pressure transducer 23.
  • the feedstock Upon entry into heating zone 20, the feedstock is heated rapidly. For example, heating may be achieved by coils or resistance heater 24, or both, on the outside of the reactor. After the water in the feedstock reaches supercritical conditions, pyrolysis products of the feedstock contact catalyst bed 22 in the heating zone and decompose to gases. The decomposition products then pass out of the reactor via line 26 and the pressure of the reactor effluent may be reduced from the supercritical condition to atmospheric, such as through a back pressure regulator 27. Separation of the reactor effluent into gaseous and liquid phases may be achieved by a conventional separator 28, if desired. Such a separator also provides a convenient point for sampling.
  • Hydrogen is produced at high pressure, avoiding considerable expense of compression needed for commercial use.
  • the transformation of feedstocks containing organic matter and water in a method according to the present invention involves a catalytic thermal decomposition mechanism such as pyrolysis, rather than oxidation, using a carbon-based catalyst.
  • a catalytic thermal decomposition mechanism such as pyrolysis, rather than oxidation, using a carbon-based catalyst.
  • samples of the effluent are substantially free of tar or char, that is, has less than about 1 weight per cent of such substances, as measured by conventional analytical techniques.
  • the reaction medium is desirably substantially free of oxygen.
  • Concentration ranges for the organic matter contacting the catalyst may be adjusted by altering any or all of the following: the feedstock composition, its flow rate into the reactor, or the amount of catalyst in the reactor. For example, for glucose, a concentration up to about 22 wt% in water may be utilized. Also, a given type of biomass, as a whole or only certain portions, may be fed to the reactor, as collected or may be ground into a slurry before introduction into the reactor. In addition, the feedstock may contain other components other than water that become part of the reaction medium but do not interfere with the decomposition at supercritical conditions.
  • Catalysts useful in the present invention are carbon-based materials such as charcoals and activated carbons having high surface areas. Desirably, surface areas are about 1000 m/g.
  • An exemplary charcoal is one based on wood or macadamia shell.
  • coconut shell or coal activated carbons are other useful types of carbon-based catalysts.
  • the catalyst may be powdery or granular.
  • a preferred coconut shell activated carbon is designated Type PE, a granular (12 x 30 mesh) activated carbon commercially available from Barnebey & Sutcliffe Co. of Columbus, Ohio. Table I presents comparative data exemplifying the performance of these types of carbon catalysts in a method according to the present invention.
  • the time of exposure of the feedstock to the catalyst is generally that which is sufficient to effect virtually complete gasification.
  • the time over which contact with the catalyst is carried out may be adjusted to take into account variations in the composition of the feedstock, and pressure and temperature of the supercritical water medium.
  • the dimensions of the conversion zone can be altered, e.g, by fabricating the reactor of tubes of relatively larger or smaller diameters, in order to reduce or extend residence times.
  • Factors influencing efficient conversion of organic matter, such as biomass and organic waste, in a feedstock and production of desirably high gas yields include reaction temperature, residence time and feedstock concentration. Tables II through IX set forth the results of a number of tests run to provide guidelines useful in carrying out the present invention. Since glucose mimics the reaction chemistry of many carbohydrates that, together with lignin, compose biomass, it serves as a suitable model for the study of thermochemical conversion of carbohydrates, as presented in several of the following Tables.
  • Table II presents the results of a study of glucose gasification, with and without an activated carbon catalyst. As can be seen from this table, for the same glucose concentration, the conversion of carbon in the feedstock to gaseous product increases considerably by carrying out the gasification reaction over a carbon-containing catalyst such as activated carbon according to the present invention.
  • WHSV weight hourly space velocity in g glucose/hr-g catalyst
  • Catalyst coconut shell activated carbon
  • Table III shows the effect of the ratio of the amount of glucose feedstock and that of the catalyst on gaseous product yield. Increasing the flow rate of feedstock relative to the catalyst, i.e., WHSV, hydrogen and carbon monoxide yields increase. Carbon conversion was very high.
  • Figure 2 illustrates that tar yield from the gasification of 1.0 M glucose is also a function of temperature.
  • the lowest tar yield was obtained at 600°C while tar yield at 500°C was more than ten times higher.
  • process conditions should be such that the water in the reaction medium is at supercritical conditions.
  • Table IV shows the effect of reaction temperature on glucose conversion. All of the temperatures were in the supercritical range. Pressure and WHSV were held constant. The highest carbon conversion and hydrogen yield were obtained at 600°C and tar yields were very low for each run at the different supercritical temperatures tested. More significantly, carbon conversion increased from 51% to 98% and hydrogen yields increased dramatically as the temperature was increased from 550°C to 600°C.
  • WHSV weight hourly space velocity in g glucose/hr-g catalyst
  • Table V shows the effect of reaction pressure on glucose conversion. As can be seen, the highest carbon conversion and hydrogen yield were obtained at 34.5 MPa.
  • WHSV weight hourly space velocity in g glucose/hr-g catalyst
  • Table VI sets forth results of the gasification of cellobiose, a dimer of glucose. Superior hydrogen yield and carbon conversion were obtained during the first three hours of operation, after which some catalyst deactivation was observed.
  • WHSV weight hourly space velocity in g glucose/hr-g catalyst
  • Catalyst coconut shell activated carbon
  • Table VII sets forth results of gasification of other biomass feedstocks, depithed bagasse liquid extract and water 25. hyacinth. Nearly a third of the product from the bagasse extract was hydrogen and carbon conversion was high.
  • Table VIII sets forth results of gasification of sewage sludge. As can be seen, carbon catalysts can be effective in the thermal decomposition of such materials.
  • WHSV weight hourly space velocity in g glucose/hr-g catalyst
  • Catalyst coconut shell activated carbon
  • Table IX shows that carbon-containing catalysts as used in a method according to the present invention effectively treat organic wastes such as methanol, methyl ethyl ketone, ethylene glycol and acetic acid. Hydrogen yields and carbon conversion were very high. Table IX Catalytic Destruction of Representative Military Wastes over 2.824g Activated Carbon Catalyst in Supercritical Water at 600°C, 34.5 MPa
  • WHSV weight hourly space velocity in g waste/hr-g catalyst

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Sludge (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé de décomposition catalytique de matières organiques dans un milieu de réaction. Ce procédé permet d'obtenir une gazéification pratiquement complète dans des espaces de temps relativement courts. Il est ainsi possible de produire un gaz riche en hydrogène à partir de charges d'alimentation (12) contenant soit des biomasses mouillées, tel que de la jacinthe d'eau ou des algues, soit des déchets organiques, soit encore des mélanges de biomasses mouillées et de déchets organiques. La réaction est catalysée par un catalyseur contenant du carbone (22). Le milieu de réaction peut se composer d'eau supercritique et ne contient pratiquement pas d'oxygène. Le catalyseur contenant du carbone (22) reste stable lorsqu'il se trouve dans un environnement constitué par un milieu d'eau supercritique, et permet de conserver une activité sur de grands laps de temps. Les catalyseurs préférés contenant du carbone sont faits de charbons actifs ou de charbons de bois. Les produits de réaction (26) ne contiennent pratiquement pas de goudrons ni de charbons.
EP96910689A 1995-03-31 1996-03-28 Gazeification supercritique catalytique de biomasses mouillees Withdrawn EP0820497A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US41452395A 1995-03-31 1995-03-31
US414523 1995-03-31
PCT/US1996/004439 WO1996030464A1 (fr) 1995-03-31 1996-03-28 Gazeification supercritique catalytique de biomasses mouillees

Publications (2)

Publication Number Publication Date
EP0820497A1 true EP0820497A1 (fr) 1998-01-28
EP0820497A4 EP0820497A4 (fr) 1998-12-16

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP96910689A Withdrawn EP0820497A4 (fr) 1995-03-31 1996-03-28 Gazeification supercritique catalytique de biomasses mouillees

Country Status (7)

Country Link
EP (1) EP0820497A4 (fr)
JP (1) JPH11502891A (fr)
KR (1) KR19980703309A (fr)
AU (1) AU5381796A (fr)
DE (1) DE19681320C2 (fr)
SE (1) SE9703448L (fr)
WO (1) WO1996030464A1 (fr)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2979149B1 (ja) * 1998-11-11 1999-11-15 財団法人石炭利用総合センター 熱化学的分解による水素の製造方法
DE19955150B4 (de) * 1999-11-17 2010-08-05 Karlsruher Institut für Technologie Verfahren zur Erzeugung von Wasserstoff
DE10015620A1 (de) * 2000-03-29 2001-10-04 Abb Patent Gmbh Verfahren und Vorrichtung zum Erzeugen von Wärme
DE10259928B4 (de) * 2002-12-20 2006-05-24 Forschungszentrum Karlsruhe Gmbh Verfahren zur Behandlung von Biomasse
KR100569120B1 (ko) * 2004-08-05 2006-04-10 한국에너지기술연구원 바이오메스 정제연료의 저온 촉매가스화 장치 및가스제조방법
DE102004038491B4 (de) * 2004-08-07 2010-07-22 Karlsruher Institut für Technologie Verfahren zur Umsetzung von Biomasse in gasförmige Produkte
JP2006169329A (ja) * 2004-12-14 2006-06-29 Hiroshima Univ 有機物のガス化方法
EP1772202A1 (fr) * 2005-10-04 2007-04-11 Paul Scherrer Institut Procédé pour obtenir du méthane et/ou d'hydrat de méthane à partir de la biomasse
KR100780910B1 (ko) * 2007-01-24 2007-11-30 한국에너지기술연구원 니켈/활성탄 촉매 제조방법 및 니켈/활성탄 촉매를 이용한유기물질의 초임계수 기화에 의한 수소제조시스템 및 그운전방법
JP5305426B2 (ja) * 2007-07-31 2013-10-02 国立大学法人広島大学 リン酸塩回収方法
US8241605B2 (en) 2008-01-31 2012-08-14 Battelle Memorial Institute Methods and apparatus for catalytic hydrothermal gasification of biomass
US8608981B2 (en) 2008-01-31 2013-12-17 Battelle Memorial Institute Methods for sulfate removal in liquid-phase catalytic hydrothermal gasification of biomass
FR2931477B1 (fr) * 2008-05-21 2012-08-17 Arkema France Acide cyanhydrique derive de matiere premiere renouvable
DE102008049778A1 (de) 2008-09-30 2010-04-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Gewinnung von gasförmigen Kohlenwasserstoffen aus biogenen Rohstoffen
FI122817B (fi) * 2008-12-19 2012-07-13 Upm Kymmene Corp Menetelmä, järjestelmä ja käyttö lämmönvaihtoa varten
DE102009018350A1 (de) * 2009-04-23 2010-10-28 Aimes Gmbh Umwandlungsvorrichtung zum Umwandeln von Biomasse in Kohlenwasserstoffverbindungen, Verfahren zum wenigstens teilweisen Umwandeln von Biomasse in Kohlenwasserstoffverbindungen, Nutzgas und Feststoff, sowie Verfahren zum wenigstens teilweisen Umwandeln von kontaminierten Stoffen in CO2
CN101928616B (zh) * 2009-06-24 2013-04-17 新奥科技发展有限公司 一种由煤制备富甲烷气体的方法
US8624070B2 (en) 2010-12-13 2014-01-07 Exxonmobil Research And Engineering Company Phosphorus recovery from hydrothermal treatment of biomass
US8704020B2 (en) 2010-12-13 2014-04-22 Exxonmobil Research And Engineering Company Catalytic hydrothermal treatment of biomass
US8487148B2 (en) 2010-12-13 2013-07-16 Exxonmobil Research And Engineering Company Hydrothermal treatment of biomass with heterogeneous catalyst
US8704019B2 (en) * 2010-12-13 2014-04-22 Exxonmobil Research And Engineering Company Catalyst recovery in hydrothermal treatment of biomass
ITTO20110772A1 (it) * 2011-08-23 2013-02-24 Welt Company Srl Procedimento ed impianto per lo smaltimento di rifiuti di origine algale
CN102584528A (zh) * 2011-12-15 2012-07-18 北京金骄生物质化工有限公司 一种利用废弃生物质制备燃料乙醇的方法
ITRM20120548A1 (it) * 2012-11-09 2014-05-10 En E Lo Sviluppo Economico Sostenibile L "processo di trattamento di acque di vegetazione di frantoi oleari mediante reazioni di reforming, e relativo impianto"
JP6338080B2 (ja) * 2013-03-26 2018-06-06 中国電力株式会社 超臨界水によるバイオマスガス化システム
CN108431181B (zh) 2015-12-30 2021-10-01 林木汽油公司 制备气体的装置和方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1063590B (de) * 1956-05-16 1959-08-20 Metallgesellschaft Ag Verfahren zur Herstellung von Methan aus festen Brennstoffen durch Einwirkung von Wasserdampf

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2592603A (en) * 1950-11-01 1952-04-15 Sinclair Refining Co Re-forming naphtha stocks
US2880167A (en) * 1954-06-01 1959-03-31 Exxon Research Engineering Co Production and utilization of activated carbon catalyst
US3989480A (en) * 1974-09-05 1976-11-02 The United States Of America As Represented By The United States Energy Research And Development Administration Decomposition of carbohydrate wastes
US4113446A (en) * 1975-07-22 1978-09-12 Massachusetts Institute Of Technology Gasification process
US4425256A (en) * 1979-12-28 1984-01-10 Marcoal Chemical Industries Conversion of cellulose into activated charcoal
US4558027A (en) * 1984-05-25 1985-12-10 The United States Of America As Represented By The United States Department Of Energy Catalysts for carbon and coal gasification
DK0643756T3 (da) * 1992-06-05 1999-02-15 Battelle Memorial Institute Fremgangsmåde til katalytisk omdannelse af organisk materiale til et gasprodukt
US5460792A (en) * 1992-12-23 1995-10-24 Rohm And Haas Company Removal and destruction of halogenated organic and hydrocarbon compounds with porous carbonaceous materials
US5444031A (en) * 1993-01-21 1995-08-22 Calgon Carbon Corporation Process for making catalytic carbon

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1063590B (de) * 1956-05-16 1959-08-20 Metallgesellschaft Ag Verfahren zur Herstellung von Methan aus festen Brennstoffen durch Einwirkung von Wasserdampf

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9630464A1 *

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JPH11502891A (ja) 1999-03-09
SE9703448D0 (sv) 1997-09-24
WO1996030464A1 (fr) 1996-10-03
DE19681320C2 (de) 2000-06-29
DE19681320T1 (de) 1998-03-19
SE9703448L (sv) 1997-11-25
AU5381796A (en) 1996-10-16
KR19980703309A (ko) 1998-10-15
EP0820497A4 (fr) 1998-12-16

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