US20020051747A1 - Catalysts for oxidative steam reforming of methanol as a new and efficient method for the selective production of hydrogen for fuel cells and their synthesis method - Google Patents

Catalysts for oxidative steam reforming of methanol as a new and efficient method for the selective production of hydrogen for fuel cells and their synthesis method Download PDF

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US20020051747A1
US20020051747A1 US09/729,103 US72910300A US2002051747A1 US 20020051747 A1 US20020051747 A1 US 20020051747A1 US 72910300 A US72910300 A US 72910300A US 2002051747 A1 US2002051747 A1 US 2002051747A1
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methanol
catalyst
oxide
steam reforming
cuznalzr
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Kenzi Suzuki
Velu Subramani
Toshihiko Osaki
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National Institute of Advanced Industrial Science and Technology AIST
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    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • 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
    • 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
    • C01B2203/1076—Copper or zinc-based catalysts
    • 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 novel oxide catalysts, methods of producing the same, and methods of producing hydrogen gas by simultaneously performing partial oxidation and steam reforming of methanol (this reaction is called oxidative steam reforming of methanol), and in further detail, relates to novel oxide catalysts, methods of producing these catalysts from a hydrotalcite-like layered double hydroxide and the like, and methods of producing hydrogen gas with a high conversion rate and selectivity using these catalysts, each of with which it is possible to produce hydrogen gas containing no CO whatsoever, or containing only very little CO, by simultaneously promoting partial oxidation and steam reforming of methanol.
  • the present invention provides novel oxide catalysts, methods of producing these catalysts from a hydrotalcite-like layered double hydroxide and the like, and methods of producing hydrogen gas with a high conversion rate and selectivity using these catalysts.
  • Hydrogen is receiving attention as a new energy source that will replace fossil fuels today when there is a fear of exhausting fossil fuels.
  • Hydrogen is the fuel in fuel cells and is replacing electrical energy. In this case, it is a clean energy source because the only waste product after generation of electricity is water, as well as in terms of measures against global warming.
  • hydrogen is an energy source that favors the environment because nitrogen oxides, sulfur compounds, hydrocarbons, etc., which are a burden to the environment, are not emitted.
  • There are two systems of fuel cells fixed systems that are large and have high output and mobile systems that are small and lightweight, but the fuel cells being studied for use in automobiles, etc., are the latter mobile systems.
  • the method whereby a CuOZnO catalyst is used is a method of producing hydrogen by partial oxidation of methanol (T. Huang and S. Wang, Appl. Catal., Vol 24, (1986) p. 287).
  • the reaction temperature is 200 to 230° C. and the oxygen/methanol ratio is 0.06.
  • the Pd concentration of this Pd-supporting ZnO catalyst is 1 to 5 wt % and the reaction temperature is 230 to 270° C.
  • the inventors proceeded with intense studies in order to develop methods of producing hydrogen gas at a high conversion rate and high selectivity by simultaneously performing partial oxidation and steam reforming of methanol in light of the above-mentioned conventional technology and successfully completed the present invention upon (1) discovering methods of preparing oxide catalysts by making catalyst precursors consisting of a hydrotalcite-like layered double hydroxide and the like by coprecipitation and heating these at a temperature of about 450° C. , and (2) successfully producing hydrogen gas containing no CO at all, or containing only very little CO, when oxidative steam reforming of methanol was performed using these oxide catalysts.
  • the object of the present invention is to provide catalysts for producing hydrogen by oxidative steam reforming of methanol, methods of producing the same, and methods of producing hydrogen gas using these catalysts, and this is accomplished by a method of producing a CuZnAlZr oxide catalyst consisting of reacting an aqueous NaOH solution and aqueous NACO 3 solution with a mixture of aqueous solutions of each nitrate of Cu, Zn, Al, and Zr, producing a precipitate by coprecipitation, aging, filtering, washing and drying this precipitate to prepare a catalyst precursor consisting of a CuZnAlZr layered double hydroxide, and then obtaining a CuZnAlZr oxide by calcining this precursor in an air ambient atmosphere, a CuZnAlZr oxide catalyst, a CuZnZrCe oxide catalyst, a CoCuZnAl oxide catalyst for producing hydrogen by oxidative steam reforming of methanol, and methods of producing hydrogen gas consisting of converting m
  • Another object of the present invention is to provide methods of producing the above-mentioned oxide catalysts from catalyst precursors consisting of a hydrotalcite-like layered double hydroxide and the like.
  • Yet another object of the present invention is to provide methods of producing hydrogen gas without generating CO using these catalysts.
  • the present invention for solving the above-mentioned problems comprises the following technical means.
  • a method of producing a CuZnAlZr oxide catalyst comprising the steps of:
  • a CuZnAlZr oxide catalyst for hydrogen production by oxidative steam reforming of methanol which is produced by the method according to above (1) or (2).
  • a CuZnZrCe oxide catalyst for hydrogen production by oxidative steam reforming of methanol which is produced by the steps of:
  • a CoCuZnAl oxide catalyst for hydrogen production by oxidative steam reforming of methanol which is produced by the steps of:
  • a method of producing hydrogen gas comprising the step of:
  • oxygen/methanol (molar ratio) 0.1 to 0.5
  • FIG. 1 is a diagram explaining the device used in the examples.
  • FIG. 2 is an explanatory diagram showing the effects of reaction temperature on partial oxidation, steam reforming, and oxidative reforming of methanol using CZAZ-C catalyst.
  • FIG. 3 is an explanatory diagram showing the effects of temperature on catalytic performance over CoCuZnAl-oxide catalysts in the oxidative steam reforming of methanol reaction.
  • A MeOH conversion
  • B H 2 production rate
  • C CO production rate
  • D CO 2 production rate.
  • novel catalysts of the present invention consist of CuZnAlZr oxide, CuZnZrCe oxide, CoCuZnAl oxide.
  • this CuZnAlZr oxide catalyst is produced as follows.
  • CuZnZrCe oxide catalyst, CoCuZnAl oxide catalyst are produced in the same way.
  • a nitrate of each of Cu, Zn, Al, and Zr is prepared as the starting material.
  • a mixture of aqueous solutions of these and aqueous NaOH solution and aqueous NaCO 3 solution are reacted and a precipitate is formed by coprecipitation.
  • a precipitate is formed by adding aqueous NaOH solution, aqueous NaCO 3 solution, or a mixture of aqueous NaOH solution and aqueous NaCO 3 solution to the above-mentioned mixture a little at a time while agitating with the mixture at room temperature and pH of approximately 9.
  • the aqueous NaOH solution and aqueous NaCO 3 solution can be added separately or simultaneously and there is no particular restriction to the method of adding the same.
  • the above-mentioned precipitate is aged at approximately 65° C. and filtered and then this is washed with deionized water, etc., until the pH of the filtrate becomes neutral and dried to prepare a catalyst precursor consisting of a hydrotalcite-like CuZnAlZr layered double hydroxide.
  • a catalyst precursor consisting of a hydrotalcite-like CuZnAlZr layered double hydroxide.
  • this catalyst precursor consisting of hydrotalcite-like layered double hydroxide is calcined in an air ambient atmosphere at, for instance, approximately 450° C. to prepare the CuZnAlZr oxide.
  • the method in which the above-mentioned catalyst precursor is introduced to an electric oven and kept at approximately 450° C. for approximately 5 hours after raising temperature from room temperature at approximately 10° C. min ⁇ 1 is an ideal example of the methods and conditions of calcination.
  • hydrogen gas is produced by converting methanol to hydrogen gas by oxidative steam reforming in the presence of both air and steam using the oxide catalysts produced by the above-mentioned methods.
  • hydrogen gas is produced without any CO by-product being produced, or only very little CO by-product being produced.
  • the oxygen/methanol molar ratio is preferably 0.1 to 0.5 and the steam/methanol (molar ratio) is ideally 0.8 to 2.0. Hydrogen gas is produced at a high conversion rate and high selectivity within these ranges. Moreover, the reaction time is 200 to 250° C., more preferably 220 to 240° C.
  • the present invention is useful as one that makes it possible to provide methods of producing hydrogen gas without producing CO by-product by oxidative steam reforming of methanol.
  • Catalyst precursor and catalyst were prepared in the present example.
  • the precipitate was aged while stirring for 30 minutes at 65° C. and filtered.
  • the precipitate was then washed several times (3 to 5 times) with deionized water until pH of the filtrate became 7. It was dried at 70° C. to prepare the CuZnAlZr layered double hydroxide (precursor catalyst).
  • this CuZnAlZr layered double hydroxide (catalyst precursor) was heated for 5 hours at 450° C. in an electric furnace with an air ambient atmosphere to prepare the CuZnAlZr oxide (catalyst of the present invention).
  • the name of the catalyst is represented by CZAZ-A through F in Table 1.
  • the molecular ratio of the metal Cu, Zn, Al, and Zr in the precursor is the result of X-ray fluorescence spectroscopy determination
  • the S BET is the surface area found by the nitrogen adsorption method
  • the amount of H 2 consumed is the result found from TPR (temperature programmed reduction) —N 2 O determinations
  • C Cu , D Cu , and t Cu are the specific surface area, degree of dispersion and Cu crystallite size, respectively.
  • the catalyst experimental device for oxidative steam reforming used in experiments of the catalysts of the present example is shown in FIG. 1.
  • This device consists of the following constituents:
  • Catalyst particle diameter 0.30 to 0.355 mm in diameter
  • Reaction temperature 180 to 290° C.
  • the CuZnAlZr oxide catalyst was subjected to reduction before the determinations of catalytic performance thereof.
  • the catalyst temperature was raised from room temperature to 300° C. at 5° C. min ⁇ 1 while running hydrogen at 10 cm 3 min ⁇ 1 through 90 mg CuZnAlZr oxide catalyst packed in the quartz glass reaction tube. After being kept for 2 hours at 300° C., temperature was lowered to the determination temperature and the product was submitted to the determinations.
  • CuZnZrCe oxide catalysts were prepared in the present example.
  • Diammonium Cerium (IV) nitrate (Ceric ammonium nitrate) salt, Ce(IV)SO 4 or Ce(III)NO 3 was used as precursor for the preparation of all catalysts. All the catalyst precursors were prepared by coprecipitation method at a constant pH of around 10 at room temperature followed by aging at 65° C. for 30 min in the same way as described in the Example 1. Catalysts were obtained after calcination of precursors at 450° C. for 5 h in a muffle furnace.
  • Outlet CO level was determined using a methanizer-FID GC assembly.
  • RH 2 /RMeOH shows ratio of rate of H 2 production to rate of methanol conversion.
  • CuZnCe- or CuZnZrCe-oxide catalysts are new for the oxidative steam reforming of methanol (OSRM) reaction. These catalysts have not been reported so far even for the traditional steam reforming of methanol (SRM) or partial oxidation of methanol (POM) reactions for H 2 production. OSRM reaction over these new series of catalysts in the temperature range 200 to 250° C. produces H 2 gas with very low outlet CO concentration.
  • CoCuZnAl oxide catalysts were prepared in the present example.
  • LDH precursors were prepared by coprecipitation method at a constant pH of around 10 at room temperature followed by aging at 65° C. for 30 min in the same way as described in the Example 1. Catalysts were obtained after calcination of precursors at 450° C. for 5 h in a muffle furnace.
  • Outlet CO level was determined using a methanizer-FID GC assembly.
  • RH 2 /RCH 3 OH shows ratio of rate of H 2 production to rate of methanol conversion.
  • CoCuZnAl-oxide catalysts are new for the oxidative steam reforming of methanol (OSRM) reaction. These catalysts have not been reported so far even for the traditional steam reforming of methanol (SRM) or partial oxidation of methanol (POM) reactions for H 2 production.
  • the present invention relates to catalysts for producing hydrogen by oxidative steam reforming of methanol, methods of producing the same, and methods of producing hydrogen gas by oxidative steam reforming of methanol using these catalysts.
  • results are realized in that 1) it is possible to provide novel oxide catalysts for hydrogen gas production by oxidative steam reforming of methanol, 2) it is possible to produce hydrogen gas with no CO by-product by oxidative steam reforming of methanol using these catalysts, 3) it is possible to provide new methods of producing hydrogen gas as a new energy source, etc.
US09/729,103 2000-06-07 2000-12-05 Catalysts for oxidative steam reforming of methanol as a new and efficient method for the selective production of hydrogen for fuel cells and their synthesis method Abandoned US20020051747A1 (en)

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US6627572B1 (en) * 2002-03-22 2003-09-30 Sud-Chemie Inc. Water gas shift catalyst
US6693057B1 (en) * 2002-03-22 2004-02-17 Sud-Chemie Inc. Water gas shift catalyst
US20060165589A1 (en) * 2003-04-01 2006-07-27 Nielsen Poul E H Process for the preparation of a hydrogen-rich stream
US20070034552A1 (en) * 2005-08-15 2007-02-15 Sub-Chemie Inc. Process for sulfur adsorption using copper-containing catalyst
US20100112397A1 (en) * 2007-04-10 2010-05-06 Idemitsu Kosan Co., Ltd Catalyst precursor substance, and catalyst using the same
WO2010138483A2 (en) 2009-05-26 2010-12-02 Basf Corporation Methanol steam reforming catalysts
WO2012068163A1 (en) * 2010-11-19 2012-05-24 Rentech, Inc. Stable slurry bed fischer-tropsch catalyst with high surface area and activity
CN115518654A (zh) * 2022-09-30 2022-12-27 四川蜀泰化工科技有限公司 一种高效率、高选择、高稳定的甲醇重整制氢催化剂及其制备工艺

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US6693057B1 (en) * 2002-03-22 2004-02-17 Sud-Chemie Inc. Water gas shift catalyst
US6627572B1 (en) * 2002-03-22 2003-09-30 Sud-Chemie Inc. Water gas shift catalyst
US7527781B2 (en) * 2003-04-01 2009-05-05 Haldor Topsoe A/S Process for the preparation of a hydrogen-rich stream
US20060165589A1 (en) * 2003-04-01 2006-07-27 Nielsen Poul E H Process for the preparation of a hydrogen-rich stream
US7749376B2 (en) 2005-08-15 2010-07-06 Sud-Chemie Inc. Process for sulfur adsorption using copper-containing catalyst
US20070034552A1 (en) * 2005-08-15 2007-02-15 Sub-Chemie Inc. Process for sulfur adsorption using copper-containing catalyst
US20100112397A1 (en) * 2007-04-10 2010-05-06 Idemitsu Kosan Co., Ltd Catalyst precursor substance, and catalyst using the same
US8088708B2 (en) 2007-04-10 2012-01-03 Idemitsu Kosan Co., Ltd. Catalyst precursor substance, and catalyst using the same
WO2010138483A2 (en) 2009-05-26 2010-12-02 Basf Corporation Methanol steam reforming catalysts
US9174199B2 (en) 2009-05-26 2015-11-03 Basf Corporation Methanol steam reforming catalysts
WO2012068163A1 (en) * 2010-11-19 2012-05-24 Rentech, Inc. Stable slurry bed fischer-tropsch catalyst with high surface area and activity
CN103221133A (zh) * 2010-11-19 2013-07-24 瑞恩泰克公司 具有高表面积和活性的稳定的浆态床费-托催化剂
US8901027B2 (en) 2010-11-19 2014-12-02 Res Usa, Llc Stable slurry bed fischer-tropsch catalyst with high surface area and activity
EA026605B1 (ru) * 2010-11-19 2017-04-28 Рес Сша Ллс Стабильный катализатор фишера-тропша для процесса в трехфазном псевдоожиженном слое, имеющий большую площадь поверхности и высокую активность
CN115518654A (zh) * 2022-09-30 2022-12-27 四川蜀泰化工科技有限公司 一种高效率、高选择、高稳定的甲醇重整制氢催化剂及其制备工艺

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US20050002858A1 (en) 2005-01-06
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