EP2723678A1 - Élimination/conversion simultanée d'hydrocarbures de type goudron et contenant du soufre - Google Patents

Élimination/conversion simultanée d'hydrocarbures de type goudron et contenant du soufre

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Publication number
EP2723678A1
EP2723678A1 EP12729118.5A EP12729118A EP2723678A1 EP 2723678 A1 EP2723678 A1 EP 2723678A1 EP 12729118 A EP12729118 A EP 12729118A EP 2723678 A1 EP2723678 A1 EP 2723678A1
Authority
EP
European Patent Office
Prior art keywords
tar
gas
containing hydrocarbons
catalyst
sulfur
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.)
Ceased
Application number
EP12729118.5A
Other languages
German (de)
English (en)
Inventor
Andrea DE TONI
Norbert Modl
Georg Anfang
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.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
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 Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP2723678A1 publication Critical patent/EP2723678A1/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/049—Composition of the impurity the impurity being carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • C01B2203/107—Platinum catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials

Definitions

  • the present invention relates to a process for the purification of gases obtained from a thermochemical gasification process of carbonaceous feedstocks, the gases containing tar and / or tar-containing hydrocarbons and / or olefins and sulfur-containing hydrocarbons, with a catalyst.
  • the invention is further directed to the use of a catalyst for the simultaneous conversion of tar or tar-containing hydrocarbons and / or olefins to synthesis gas and sulfur-containing hydrocarbons to hydrogen sulphide.
  • the invention further relates to a reactor arrangement for carrying out the method.
  • Gasification gas synthesis gases are usually so heavily polluted with sulfur and tarry hydrocarbons that they can not be used directly for downstream applications (e.g., FT fuels, methanol, synthetic methane, etc.).
  • cold gas processes such as gas scrubbers, adsorbers or catalytic hot gas processes can be used.
  • a common removal of tars and sulfur-containing hydrocarbons, for example, has already been realized in the cold gas purification.
  • FIG. 1 FIG. 1, FIG. 1, FIG However, this method from an energetic point of view very expensive and therefore not very efficient.
  • DE 102008021081 Al discloses a method for reducing the tar content in gases obtained from a thermochemical gasification process of carbonaceous starting materials.
  • the gas is treated with a noble metal-containing catalyst.
  • This method could previously be used only for the removal of tar-containing compounds.
  • a disclosure regarding a simultaneous removal of sulfur-containing hydrocarbons can not be found in this document.
  • DE 102008021084 A1 merely discloses the removal or reduction of the tar content of gases from gasification processes by means of a noble metal-containing gas
  • Sulfur compounds eg, mercaptans, thiophenes
  • H 2 S hydrogen sulfide
  • hydrodesulfurization all sulfur-containing hydrocarbons are usually converted by a hydrogenation of C0 / M02 or ⁇ / ⁇ 2 in H2 S and this chemisorbiert following activated carbons, metals or metal oxides. These metal / metal oxides are usually a member of the elements Zn, Cu Co, Ni, Cr or Mn or their oxides and mixtures of these materials.
  • FIG. 2 shows schematically a hot gas cleaning according to the method described above with a tar removal combined with a supporting desulfurization.
  • the purification and follow-up processes shown in FIG. 2 are outlined purely by way of example.
  • the described multistage process thus furthermore requires the use of a plurality of different catalysts and adsorption materials as well as procedural procedures, for example frequent heating / cooling and compression of the process gas, frequent regeneration and replacement of the catalysts or sorption materials, which the gasification makes more complex and trouble-prone.
  • this should be done by reducing the necessary process steps and thus more efficient temperature control (eg continuously along a temperature profile / temperature gradient) in order to optimize the synthesis gas production and use as a whole.
  • the object of the present invention was therefore to provide a process for reducing the tar / olefin content and the content of sulfur-containing hydrocarbons in a gas obtained from a thermochemical gasification of carbonaceous starting materials.
  • the object has been achieved by a process for the purification of gases obtained from the thermochemical gasification of carbonaceous starting materials, comprising the steps of: a) contacting one from a thermochemical gasification of carbonaceous
  • Hydrocarbons can be made from gases in one step. In this case, predominantly CO and H 2 (syngas) and H 2 S are formed.
  • the gases are preferably obtained from a thermochemical gasification of carbonaceous starting materials, for example coal or biomass, most preferably from biomass.
  • the temperature range for simultaneous conversion in the process according to the invention depends on the gasification process and is usually 700 ° C. to 1000 ° C. However, the process control can also deviate from these ranges, for example 500 to 1000 ° C.
  • the process is performed continuously on a temperature profile or Temeraturgradienten along.
  • the preferred one Temperature range is in the range of 500 to 1000 ° C, more preferably 600 to 950 ° C, even more preferably 700 to 900 ° C and most preferably 750 to 900 ° C.
  • the temperature profile or the temperature gradient is preferably driven in increments of 10 ° C, 20 ° C, 30 ° C, 40 ° C or 50 ° C.
  • no external oxygen or air is introduced into the process.
  • the method can also be carried out in a range of 1 bar to 100 bar.
  • a reduction of process steps can be effected, wherein one of the catalytic tar reforming downstream catalytic hydrogenation of sulfur-containing hydrocarbons is eliminated.
  • FIG. 1 A preferred process procedure is shown in FIG. 1
  • olefins for example ethylene and propylene
  • olefins are converted into synthesis gas in the same process step.
  • Olefins are known to be useful in catalytic sequential applications (eg FT fuels, Methanol, etc.) lead to coking reactions. This usually reduces the service life of the catalyst and leads to a complex regeneration and even replacement of the catalyst.
  • the catalyst comprises at least one noble metal selected from the group consisting of Pt, Pd, Rh, Ir, Os, Ru and Re, and / or the metal Ni.
  • a noble metal-containing catalyst which comprises Pt and Rh.
  • a noble metal-containing catalyst comprises a combination of platinum and rhodium, wherein the ratio of platinum to rhodium can occur in any proportion.
  • the catalyst may comprise as the sole active component a noble metal such as, for example, palladium, iridium, rhenium or a non-noble metal such as nickel.
  • Rhodium is preferably used as a combination with a further noble metal such as, for example, platinum or iridium or together with nickel.
  • nickel is also suitable as an active component, especially when it is doped with one or more precious metals, preferably with platinum, rhodium, ruthenium or a mixture thereof.
  • a nickel to noble metal weight ratio of 5: 1 to 20: 1 is used, more preferably from 7: 1 to 13: 1.
  • the metal is preferably present on a carrier or carrier material.
  • the support is preferably a metal oxide, preferably selected from the group consisting of cerium oxide (CeO x), lanthanum oxide (La 2 Ü3), alumina (Al 2 O 3), yttrium oxide (Y 2 0 3), titanium oxide (Ti0 2), zirconium oxide (Zr0 2 ), silica (Si0 2 ) or mixtures thereof.
  • the metal is supported on the carrier or carrier material.
  • the metals can also be applied directly to bulk material, for example to simple -Al 2 C> 3 supports or other high-temperature-stable supports such as calcium aluminate,
  • Hexaaluminates or similar ceramic carrier systems for example, previously formed into spheres, tablets, extrudates, Triholes or other forms.
  • A1 2 C> 3 and other oxides such as Ce oxides, Zr oxides, Ti oxides, La oxides and mixtures of the oxides and optionally additional promoters are conceivable.
  • concentration and temperature of the impregnating solution, the porosity of the carrier and the impregnation process itself can be used to control the penetration depth and the concentration of the catalytically active noble metals on the carrier.
  • the catalyst according to the invention can be prepared by impregnating a support with an aqueous solution of salts of the desired active component. The impregnated catalyst is then dried and calcined, if necessary, these steps are repeated one or more times.
  • Supported catalysts can be prepared in which the catalytically active components are applied in highly dispersed form on support materials.
  • support materials are used which have a large specific surface area for receiving the catalytically active components. It is finely divided, i. powdery, temperature-stable metal oxides, which are also referred to as washcoat.
  • washcoat main constituents are aluminum oxides, cerium oxides, zirconium oxides and others
  • Metal oxides Additional promoters to stabilize the high surface area and to suppress or promote side reactions may also be present.
  • aluminum oxides with BET surface areas of about 50 to about 250 m 2 / g are used.
  • the carrier materials are applied in the form of a coating to inert carrier bodies, so-called honeycomb bodies, of ceramic (for example cordierite) or metal carriers.
  • honeycomb bodies of ceramic (for example cordierite) or metal carriers.
  • the carrier materials are, for example, dispersed in water and, for example, homogenized by a grinding process.
  • the walls of the honeycomb bodies are then coated by one or more immersions in the coating dispersion with subsequent drying and calcination.
  • the catalytically active components can be applied at different times to the specific surface of the support materials. For example.
  • the catalytically active components can be only after coating the honeycomb body with the Dispersion coating can be deposited by immersing the coated honeycomb body in an aqueous solution of soluble precursors of the catalytically active components on the support materials.
  • the catalytically active components may be used in a preparation of the
  • Dispersion coating upstream working step are applied to the powdered carrier materials.
  • the support material is previously treated as described e.g. coated on monolithic cordierite honeycomb, dried and calcined. In one or more further impregnation, drying and calcination steps, the
  • honeycomb monolithic carriers are known to those skilled in the art. Examples of various monolithic supports are described in Handbook of Heterogenous Catalysis 4-Environmental Catalysis, pages 1575-1583. Other suitable methods for applying the active components to the supports are impregnation, spraying, ion exchange, dipping and any other methods known in the art.
  • the catalysts used in the invention are stable to hydrogen sulfide.
  • the activity of the catalyst is at most somewhat reduced by hydrogen sulfide, but there is no complete deactivation.
  • the gas to be treated in the context of the process according to the invention usually comprises carbon monoxide, carbon dioxide, methane, hydrogen, water vapor and nitrogen as main components.
  • it contains impurities selected from tar compounds, tar-containing hydrocarbons, olefins and sulfur-containing hydrocarbons.
  • the tar or the Tar-containing hydrocarbons are in particular a mixture of cyclic and polycyclic aromatics and olefins.
  • the process according to the invention is preferably used after the thermochemical gasification of biomass and / or coal, more preferably immediately after the gasification and preferably before the further use of the gas in subsequent processes, such as e.g. methanation for CNG, Fischer-Tropsch, methanol synthesis and the like.
  • subsequent processes such as e.g. methanation for CNG, Fischer-Tropsch, methanol synthesis and the like.
  • a process step in which the tar-containing hydrocarbons and sulfur-containing hydrocarbons are converted another process step for the removal of hydrogen sulfide.
  • the removal of the hydrogen sulfide is preferably carried out in a subsequent step by treating the gas obtained from step b) of the process according to the invention in a scrubber, by contacting the gas with a metal, metal oxide, activated carbon or by a combination of these methods. It is further preferred that the inventive method preferably no additional / downstream process step for
  • the contacting of the gas to be treated with the catalyst can be carried out either directly in the gasification zone of a reactor or in an external reactor.
  • At least a portion of the gas obtained from the gas production is brought into contact with the catalyst.
  • the contacting takes place in particular by passing the gas stream through or over the catalyst.
  • the entire gas obtained from the gas production is treated by the process according to the invention.
  • the process according to the invention preferably takes place immediately after a thermochemical
  • the inventive method has a high yield.
  • the tar cleaning rate is in the range of 60 to 100%.
  • the purification rate of the sulfur-containing hydrocarbons in the range of 60 to 100%, as well as the other components (olefins, etc.) in the range 60 to 100%.
  • the catalysts used are also high temperature stable (up to 1000 ° C), which is why the process can be used directly after gasification without cooling the gas or biogas.
  • the process is carried out in total preferably at 500 to 1000 ° C, more preferably at 600 to 800 ° C and most preferably at 650 to 850 ° C.
  • space velocities of from 1,000 to 10,000 are preferred
  • volumetric flow rate / volume more preferably in the range from 3000 to 6000, and more preferably from 2000 to 5000.
  • the invention further provides for the use of a catalyst for the simultaneous conversion of tar or tar-containing hydrocarbons contained in the gas Synthesis gas and sulfur-containing hydrocarbons to hydrogen sulfide (H 2 S), the gas from a thermochemical gasification of carbon-containing
  • Another object of the invention is also a reactor arrangement for the simultaneous conversion of tar contained in gas and / or tarry hydrocarbons and / or olefins to synthesis gas and sulfur-containing hydrocarbons to hydrogen sulfide (H 2 S), the reactor arrangement only a single catalyst stage, preferably with a noble metal-containing catalyst.
  • the gas is preferably obtained from a thermochemical gasification of carbonaceous starting materials.
  • Yet another object of the invention is therefore the use of the above-mentioned reactor arrangement for the simultaneous conversion of tar or tar-containing hydrocarbons in the gas to synthesis gas and sulfur-containing hydrocarbons to hydrogen sulfide (H 2 S), the gas is obtained from a thermochemical gasification of carbonaceous starting materials ,
  • Flue gas cleaning must also be removed.
  • Figure 1 is a schematic representation of a cold gas cleaning for biomass gasification according to the prior art
  • Figure 2 is a schematic representation of a hot gas cleaning for biomass gasification according to the prior art.
  • FIG. 3 shows a possible process control according to the invention including subsequent steps.
  • Figure 4 shows an RI flow chart of a test facility used and a schematic representation of the furnace used.
  • Figure 5 shows the conversion of methane, toluene and naphthalene as a function of gas inlet temperature, the gas composition corresponds to that given in Table 1 and 200 ppm H 2 S contains.
  • FIG. 6 shows a course of concentration for methane.
  • Figure 7 Concentration gradients for toluene and naphthalene.
  • the catalyst used in the embodiment is a Pt / Rh catalyst on one
  • FIG. 1 A flow diagram of the measuring apparatus and a schematic structure of the furnace are shown in FIG.
  • the temperature was recorded at three different locations in the monolith and at the reactor entrance, providing a complete temperature profile.
  • the temperature was measured by thermocouples NiCr-Ni (Type K) Class 1.
  • the space velocity is defined as:
  • Feed gas flow [Nl / h] / catalyst volume [1] 1 / h
  • Table 2 Educt and product gas composition for different gas inlet temperatures for a noble metal-containing catalyst.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé pour épurer du biogaz qui contient du goudron et/ou des hydrocarbures contenant du goudron ainsi que des hydrocarbures contenant du soufre avec un catalyseur contenant un métal noble. L'invention concerne également l'utilisation d'un catalyseur contenant un métal noble pour la conversion simultanée de goudron ou d'hydrocarbures contenant du goudron présents dans du biogaz en gaz de synthèse et d'hydrocarbures contenant du soufre en sulfure d'hydrogène. L'invention concerne en outre un système de réacteur pour mettre en oeuvre le procédé.
EP12729118.5A 2011-06-22 2012-06-21 Élimination/conversion simultanée d'hydrocarbures de type goudron et contenant du soufre Ceased EP2723678A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201110105353 DE102011105353A1 (de) 2011-06-22 2011-06-22 Multifunktionaler Katalysator zur simultanen Entfernung/Umwandlung von teerartigen und schwefelhaltigen Kohlenwasserstoffen
PCT/EP2012/061996 WO2012175625A1 (fr) 2011-06-22 2012-06-21 Élimination/conversion simultanée d'hydrocarbures de type goudron et contenant du soufre

Publications (1)

Publication Number Publication Date
EP2723678A1 true EP2723678A1 (fr) 2014-04-30

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EP12729118.5A Ceased EP2723678A1 (fr) 2011-06-22 2012-06-21 Élimination/conversion simultanée d'hydrocarbures de type goudron et contenant du soufre

Country Status (3)

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EP (1) EP2723678A1 (fr)
DE (1) DE102011105353A1 (fr)
WO (1) WO2012175625A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE102016116306A1 (de) 2016-09-01 2018-03-01 Thyssenkrupp Ag Verfahren und Vorrichtung zum Entfernen von organischen Schwefelverbindungen aus wasserstoffreichen Gasen

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
DE1186974B (de) * 1963-04-03 1965-02-11 Bergwerksverband Gmbh Verfahren zur Reinigung von Kohlendestillationsgasen unter Erzeugung eines an Kohlenoxyd und Wasserstoff reichen Brenngases
US7901566B2 (en) 2006-07-11 2011-03-08 Basf Corporation Reforming sulfur-containing hydrocarbons using a sulfur resistant catalyst
DE102008021084A1 (de) 2008-04-28 2009-10-29 Süd-Chemie AG Verwendung eines Katalysators auf Edelmetallbasis zur Verringerung des Teergehalts in Gasen aus Vergasungsprozessen
DE102008021081A1 (de) 2008-04-28 2009-10-29 Süd-Chemie AG Verfahren zur katalytischen Verringerung des Teergehalts in Gasen aus Vergasungsprozessen unter Verwendung eines Katalysators auf Edelmetallbasis
US20100147749A1 (en) 2008-12-11 2010-06-17 American Air Liquide, Inc. Multi-Metallic Catalysts For Pre-Reforming Reactions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2012175625A1 *

Also Published As

Publication number Publication date
DE102011105353A1 (de) 2012-12-27
WO2012175625A1 (fr) 2012-12-27

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