EP1515910A1 - Procede de production de gaz contenant de l'hydrogene - Google Patents

Procede de production de gaz contenant de l'hydrogene

Info

Publication number
EP1515910A1
EP1515910A1 EP03740195A EP03740195A EP1515910A1 EP 1515910 A1 EP1515910 A1 EP 1515910A1 EP 03740195 A EP03740195 A EP 03740195A EP 03740195 A EP03740195 A EP 03740195A EP 1515910 A1 EP1515910 A1 EP 1515910A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
containing gases
catalyst
production
gases according
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Withdrawn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
EP03740195A
Other languages
German (de)
English (en)
Inventor
Helge Wessel
Markus HÖLZLE
Klaus Harth
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1515910A1 publication Critical patent/EP1515910A1/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Withdrawn legal-status Critical Current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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/005—Spinels
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • 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
    • C01B3/40—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 characterised by the catalyst
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • 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
    • 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
    • C01B2203/1082—Composition of support materials
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for producing hydrogen-containing gases by reacting hydrocarbons with air and / or water at elevated temperatures.
  • EP-A-1 157 968 discloses a process for the autothermal steam reforming of hydrocarbons (production of hydrogen-containing gases) over catalyst compositions which contain at least one platinum group metal on an oxidic support or on a zeolite.
  • the object of the present invention was therefore to remedy the disadvantages mentioned above.
  • the method according to the invention can be carried out as follows:
  • the hydrocarbon or the alcohol and water at temperatures of 300 to 1000 ° C are preferred.
  • the starting material mixture of hydrocarbon, air and / or water can be introduced into the reaction space without preheating or preferably preheated (for example 100 to 600 ° C.).
  • a special embodiment consists in that the required temperature - for the production of hydrogen-containing gases - is generated by partial oxidation of the hydrocarbon with oxygen, preferably air, and only then is water added to the educt stream (autothermal Da reforming).
  • Any hydrocarbons are suitable as hydrocarbons, for example crude oil, natural gas, gasoline, diesel, liquid gas, propane or waste hydrocarbons from chemical processes. These hydrocarbons should be largely sulfur-free.
  • Suitable catalysts according to the invention are spinels, preferably all aluminum spinels, particularly preferably spinels of the general formula M X A10 4 in which M Cu or mixtures of Cu with Zn or Cu with Mg and x have a value of 0.8 to 1.5, before is 0.9 to 1.2, particularly preferably 0.95 to 1.1.
  • These spinels generally contain 0 to 5% by weight, preferably 0 to 3.5% by weight, of free oxides in crystalline form, such as MO (M, for example Cu, Zn, Mg) and A1 2 0 3 .
  • the catalysts according to the invention show favorable aging behavior, i.e. the catalyst remains active for a long time without being thermally deactivated.
  • the catalysts according to the invention contain copper in oxidic form, calculated as copper oxide, CuO, in an amount of generally from 0 to 54% by weight, preferably from 5 to 40% by weight, particularly preferably from 10 to 30% by weight on the overall catalyst.
  • the catalyst according to the invention can contain further doping, in particular Zr, La, Ti, Ce or mixtures thereof in oxidic form. Doping with Zr, La or mixtures thereof generally increases the thermal stability of the catalysts according to the invention.
  • the content of the doping compounds in the catalyst according to the invention is generally between 0.01 and 10% by weight, preferably between 0.05 and 2% by weight.
  • the catalyst according to the invention can also contain further metallic active components.
  • metallic active components are preferably metals of subgroup VIII of the Periodic Table of the Elements, particularly preferably palladium, platinum, ruthenium and rhodium, in particular rhodium.
  • the proportion of metals of subgroup VIII in the catalyst according to the invention is generally 0.01 to 7.5% by weight, preferably 0.1 to 2% by weight.
  • the supported catalysts according to the invention can be in the form of pellets, honeycombs, rings, grit, solid and hollow strands or in other geometric shapes, preferably in the form of honeycomb bodies.
  • the catalysts according to the invention can be produced from oxidic starting materials or from starting materials which change into the oxidic form during the final calcination. They can be produced by a process in which the starting materials containing Al, Cu and, if appropriate, Zn and / or Mg, and, if appropriate, further additives, are mixed in one step, shaped to give shaped articles and, if appropriate, treated at temperatures above 500 ° C.
  • a mixture of the starting materials can be processed to corresponding shaped articles, for example by drying and tableting. These can then be heated to temperatures between 500 and 1000 ° C for 0.1 to 10 hours (calcination).
  • a deformable mass can be produced in a kneader or mix-miller, which is extruded or extruded into corresponding shaped bodies.
  • the moist moldings can be dried and then calcined as previously described.
  • the catalysts of the invention can be prepared by a process which comprises the following steps:
  • a support can be produced from Cu in the form of Cu (N0 3 ) and / or CuO and an Al component.
  • the starting materials can be mixed, for example dry or with the addition of water.
  • Zn and / or Mg components can be applied to the carrier by one or more impregnations.
  • the catalysts of the invention is obtained after drying and calcination at temperatures from 500 to 1000 ° C, preferably from 600 to 950 ° C.
  • Cu can be used as a mixture of CuO and Cu (N0 3 ), for example.
  • the catalysts produced in this way have a higher mechanical stability than the catalysts produced only from CuO or only from Cu (N0 3 ).
  • oxides and nitrates pure oxides can also be used if acidic shaping aids such as formic acid or oxalic acid are also added. It is very advantageous to use mixtures of oxides and nitrates, in particular in the production of the catalysts according to the invention in one step, in which all starting materials are mixed and further processed to form foreign bodies.
  • a mixture of A10 3 and AlOOH can be used as the aluminum component.
  • Suitable AI components are described in EP-A-652 805.
  • Metals of subgroup VIII of the Periodic Table of the Elements are also applied to the catalysts. These elements can be applied using known manufacturing methods, e.g. by impregnation, precipitation, electroless deposition, CVD methods, vapor deposition. These precious metals are preferably applied in the form of their nitrates via an impregnation step. After the impregnation, the decomposition takes place at temperatures of 200 to 1000 ° C and, if necessary, reduction to the elementary precious metal. Other known methods can also be used to apply the noble metals.
  • the process according to the invention is suitable in so-called reformer units for the production of hydrogen.
  • the process according to the invention represents only part of an overall process for the production of hydrogen for fuel cells.
  • the overall process also comprises process steps for removing carbon monoxide from the hydrogen-containing reformate stream by, for example, one or more water gas shift steps and, if appropriate, selective oxidation.
  • the process steps for removing carbon monoxide are known, for example, from WO-A-00766486, WO-A-00/78669 and WO-A-97/25752. Examples
  • 510 liters of methane and 1210 liters of air were each heated to 500 ° C. in a reactor and passed over 28 ml of the catalyst prepared according to Example A, in order first to bring it to the required operating temperature (670 to 710 ° C.) by catalytic partial oxidation Gas outlet temperature). Then 510 liters / h of methane, 1210 liters / h of air and 1020 liters / h of water vapor were metered into the reactor in stationary operation.
  • the dry reformate contained 47% by volume of hydrogen, 5% by volume of carbon monoxide, 13% by volume of carbon dioxide and 35% by volume of nitrogen.
  • the dry reformate contained 39% by volume of hydrogen, 14% by volume of carbon monoxide, 7% by volume of carbon dioxide, 37% by volume of nitrogen and 3% by volume of methane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de gaz contenant de l'hydrogène, consistant à faire réagir des hydrocarbures avec de l'air et/ou de l'eau, à des températures comprises entre 300 et 1000 °C et une pression située entre 1 et 20 bars, en présence d'un catalyseur. L'invention est caractérisée en ce que le catalyseur utilisé est un spinelle qui comporte au moins un élément du VIIIème sous-groupe de la classification périodique des éléments.
EP03740195A 2002-06-11 2003-06-06 Procede de production de gaz contenant de l'hydrogene Withdrawn EP1515910A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10225945 2002-06-11
DE10225945A DE10225945A1 (de) 2002-06-11 2002-06-11 Verfahren zur Herstellung von wasserstoffhaltigen Gasen
PCT/EP2003/005938 WO2003104143A1 (fr) 2002-06-11 2003-06-06 Procede de production de gaz contenant de l'hydrogene

Publications (1)

Publication Number Publication Date
EP1515910A1 true EP1515910A1 (fr) 2005-03-23

Family

ID=29594388

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03740195A Withdrawn EP1515910A1 (fr) 2002-06-11 2003-06-06 Procede de production de gaz contenant de l'hydrogene

Country Status (7)

Country Link
US (1) US20050175531A1 (fr)
EP (1) EP1515910A1 (fr)
JP (1) JP2005536421A (fr)
AU (1) AU2003274678A1 (fr)
CA (1) CA2488189A1 (fr)
DE (1) DE10225945A1 (fr)
WO (1) WO2003104143A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4774197B2 (ja) * 2003-05-20 2011-09-14 出光興産株式会社 酸素含有炭化水素の改質触媒、それを用いた水素又は合成ガスの製造方法及び燃料電池システム
US20100095591A1 (en) * 2008-10-20 2010-04-22 General Electric Company Emissions control system and method
DE102022134540A1 (de) 2022-12-22 2024-06-27 Umicore Ag & Co. Kg Reformierungskatalysator
WO2024133613A1 (fr) 2022-12-22 2024-06-27 Umicore Ag & Co. Kg Catalyseur de reformage, sa préparation, son utilisation pour la production d'hydrogène et dispositif de génération d'électricité

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL302476A (fr) * 1962-12-29
FR1549201A (fr) * 1967-03-21 1968-12-13
US3539651A (en) * 1967-11-14 1970-11-10 Phillips Petroleum Co Catalytic dehydrogenation process
JPS5274591A (en) * 1975-12-17 1977-06-22 Nippon Soken Catalysts for reforming hydrocarbon fuels
CN1502546A (zh) * 1997-10-07 2004-06-09 JFE�عɹ�˾ 制造氢或合成气体用的催化剂及制造氢或合成气体的方法
DE19848595A1 (de) * 1998-10-21 2000-04-27 Basf Ag Hochtemperaturstabile Katalysatoren zur Zersetzung von N¶2¶0
US6524550B1 (en) * 1999-05-03 2003-02-25 Prashant S. Chintawar Process for converting carbon monoxide and water in a reformate stream
EP1298089B1 (fr) * 2000-06-22 2005-01-19 Consejo Superior De Investigaciones Cientificas Procede d'obtention d'hydrogene par oxydation partielle du methanol
WO2002066403A1 (fr) * 2001-02-16 2002-08-29 Conoco Inc. Catalyseurs sur support de rhodium-oxyde de type spinelle et procede de production de gaz de synthese

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03104143A1 *

Also Published As

Publication number Publication date
JP2005536421A (ja) 2005-12-02
CA2488189A1 (fr) 2003-12-18
WO2003104143A1 (fr) 2003-12-18
AU2003274678A1 (en) 2003-12-22
US20050175531A1 (en) 2005-08-11
DE10225945A1 (de) 2003-12-24

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