WO2015106634A1 - 一种金属相载体负载型催化剂及其制备方法和用途 - Google Patents

一种金属相载体负载型催化剂及其制备方法和用途 Download PDF

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WO2015106634A1
WO2015106634A1 PCT/CN2015/000020 CN2015000020W WO2015106634A1 WO 2015106634 A1 WO2015106634 A1 WO 2015106634A1 CN 2015000020 W CN2015000020 W CN 2015000020W WO 2015106634 A1 WO2015106634 A1 WO 2015106634A1
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catalyst
metal
phase carrier
metal phase
reaction
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PCT/CN2015/000020
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English (en)
French (fr)
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路勇
李亚坤
柴瑞娟
刘晔
徐彬
周晓莹
萧锦诚
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易高环保能源研究院有限公司
华东师范大学
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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • 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
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide 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
    • C01B2203/0205—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
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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

Definitions

  • the invention belongs to the technical field of catalysis, relates to a catalyst and a preparation method and application thereof, in particular to a metal phase supported catalyst, a preparation method thereof and a use thereof, the catalyst can be used for catalyzing carbon monoxide or (and) carbon dioxide addition. Hydrogen is reacted with synthetic methane and methane reforming to syngas.
  • Natural gas is a safe and clean high-quality energy source. Its main component is methane (CH 4 ), which has the advantages of high calorific value and low pollution. It is widely used in power generation, chemical industry and civil use. Since Sabatier and Senderens first synthesized methane using carbon monoxide and hydrogen on a nickel-based catalyst in 1902, the methanation reaction has developed rapidly and is widely used in gas purification processes.
  • CH 4 methane
  • prior art methanation catalysts employ essentially oxides as supports such as trialumina, silica, titania, zirconia, and the like.
  • methane synthesis gas is one of the important ways to realize methane chemical utilization.
  • steam reforming, partial oxidation, carbon dioxide reforming and autothermal reforming have been developed, but the above processes all have strong thermal effects.
  • the problem of (strong heat absorption or strong exotherm), their thermodynamic studies show that it is easy to produce side-effect carbon deposits at low temperatures.
  • the effective heat transfer coefficient in the conventional fixed-bed reaction tube is generally low, even if the tube wall temperature is as high as 800 ° C, there is still a cold spot in the bed, and carbon deposition is difficult to avoid.
  • the metal phase carrier structure catalyst has been applied in the field of environmental catalysis and pollution control due to its advantages of large specific surface area, good transfer performance, and reduced bed lamination. By using this excellent transfer performance, the metal phase carrier structure catalyst can be applied to the strong release/endothermic reaction in the chemical industry, which can greatly improve the energy utilization efficiency, realize the process integration, and achieve the purpose of process strengthening. Methanation reaction and methane synthesis gas reaction have strong thermal effects, so the prior art Attempts have been made in the art to provide a metal phase support structure methanation catalyst and a methane synthesis gas catalyst. However, these prior art catalysts have defects such as low melting point, high chemical activity, insufficient catalytic activity, complicated preparation, and serious contamination in the preparation process.
  • the object of the present invention is to provide a catalyst with high catalytic activity, high stability, excellent thermal conductivity, convenient use, simple preparation and the like, and a preparation method and application thereof, which are suitable for methane preparation reaction and methane system with strong thermal effect. Syngas reaction.
  • the present invention provides a metal phase supported catalyst comprising an active component metal oxide supported on a metal phase carrier and a promoter metal oxide and having the formula xM 1 O-yM 2 O/ ZT, wherein M 1 O represents the active component metal oxide, M 2 O represents the auxiliary metal oxide, ZT represents the metal phase carrier, x represents the mass fraction of the catalyst of the active component metal oxide, and y represents the promoter metal The oxide constitutes the mass percent of the catalyst.
  • the active component metal oxide M 1 O accounts for 1 to 15% by mass of the catalyst
  • the auxiliary metal oxide M 2 O accounts for 1 to 15% by mass of the catalyst. %, the rest is the metal phase carrier ZT.
  • the values of x, y can be 1, 3, 5, 6, 7.5, 9, 10, 13, 15, both of which achieve the objectives of the present invention.
  • the metal phase carrier is metallic nickel, metallic copper, metallic iron or metallic white copper.
  • the metal phase carrier is a fiber having a diameter of 4 to 150 micrometers and a length of 2 to 10 millimeters, a three-dimensional porous structural monolithic metal fiber carrier sintered from the fiber, or a three-dimensional porous structural monolithic metal. Foam carrier.
  • the active component metal oxide M 1 O in the catalyst of the present invention is at least one of nickel and iron oxides.
  • the auxiliary metal oxide M 2 O in the catalyst of the present invention is at least one of oxides of aluminum, lanthanum, cerium, molybdenum, manganese, tungsten, magnesium, calcium, sodium and potassium.
  • Another aspect of the invention provides a method of preparing a catalyst comprising the steps of:
  • the metal phase carrier has the same volume, and then dried to disperse the aluminum powder particles on the surface of the metal phase carrier, and then solid-solid alloying reaction between the aluminum powder particles and the metal phase carrier surface layer at 550 to 650 ° C (for example)
  • the reaction is carried out for 1 to 10 hours) (the reaction can be carried out, for example, in a high-purity protective atmosphere, for example, a purity equal to or higher than 99.999% of nitrogen, hydrogen, argon or helium, or can be carried out in a vacuum) to obtain a surface alloyed metal phase carrier.
  • the temperature of the solid-solid alloying reaction may be 550, 570, 600, 630, 650 ° C, the reaction time can be 1, 2, 3, 5, 7, 8, 10 hours or less or longer, can achieve the object of the present invention
  • step 2 The product prepared in step 1 is subjected to aluminum extraction treatment (for example, 1 to 6 hours) with a hydrochloric acid or sodium hydroxide aqueous solution having a concentration of 5 to 20% at a temperature of from room temperature to 60 ° C, rinsed with distilled water, and air-dried. After drying, the surface layer porous metal phase carrier is obtained (in different embodiments of the present invention, the temperature of this step may be 20, 30, 40, 50, 60 ° C, and the concentration of the hydrochloric acid or sodium hydroxide aqueous solution may be 5, 5.5, 7, 10, 14, 18, 20%, the aluminum extraction treatment time may be 1, 2, 4, 5, 6 hours or shorter or longer, and the object of the present invention can be achieved);
  • the product obtained in the step 2 is immersed in an equal volume at room temperature or equivalent conditions in an aqueous solution containing a salt of the active component M1 metal element and a salt of the auxiliary component M2 metal element (the impregnation here may be step 2)
  • the obtained product is impregnated in the same solution containing both the active component and the auxiliary component, or the product obtained in the step 2 may be separately impregnated in the first solution containing only one component, and then included in the
  • the second solution of the other component is impregnated, and after baking, calcining at 300 to 600 ° C (for example, 0.5 to 2 hours) to obtain the metal phase carrier metal phase carrier-supported catalyst (in different embodiments)
  • the calcination temperature in this step may be 300, 350, 400, 500, 600 ° C, and the calcination time may be 0.5, 1, 1.5, 2 hours or shorter or longer, and the object of the present invention can be achieved.
  • the aluminum powder used in the surface layer alloying process of the metal phase carrier has a particle diameter of 1 to 3 ⁇ m, and the aluminum powder/metal phase carrier has a mass ratio of 0.5 to 10/100 (in different embodiments, aluminum powder)
  • the mass ratio of the metal phase carrier may be 0.5/100, 1/100, 3/100, 5/100, 8/100, 10/100, all of which can achieve the object of the present invention).
  • Another aspect of the invention is the use of the metal phase supported catalyst for the production of methane from the hydrogenation of carbon monoxide and/or carbon dioxide.
  • Another aspect of the invention is the use of the metal phase supported catalyst for the preparation of synthesis gas from methane, especially as a catalyst for the preparation of synthesis gas from methane-carbon dioxide reforming or methane autothermal reforming.
  • the metal phase carrier supported catalyst provided by the invention has the advantages of stable structure, good thermal conductivity and high permeability, and has the advantages of easy molding, easy filling, easy storage, and the like, and the preparation method thereof is simple.
  • the raw materials are easy to obtain and the structure is controllable.
  • the large porosity of the monolithic metal-supported catalyst of the present invention can greatly reduce the pressure drop across the bed, and the high thermal conductivity can make the bed The temperature in the layer is more uniform and can fully meet the catalytic performance requirements of the methanation reaction of the synthesis gas.
  • Example 1 is an optical photograph of a sintered metal nickel fiber-supported nickel oxide-alumina catalyst 10NiO-10Al 2 O 3 /8-Ni-SMF-450 prepared in Example 1.
  • Example 2 is a SEM photograph of a sintered metal nickel fiber-supported nickel oxide-alumina catalyst 10NiO-10Al 2 O 3 /8-Ni-SMF-450 prepared in Example 1.
  • Example 3 is an XRD spectrum of a sintered metal nickel fiber-supported nickel oxide-alumina catalyst 10NiO-10Al 2 O 3 /8-Ni-SMF-450 prepared in Example 1.
  • Example 4 is an optical photograph of a metal copper fiber-supported iron oxide-alumina catalyst 10Fe 2 O 3 -5Al 2 O 3 /30-Cu-fiber-300 prepared in Example 3.
  • Example 5 is a SEM photograph of a metal copper fiber-supported iron oxide-alumina catalyst 10Fe 2 O 3 -5Al 2 O 3 /30-Cu-fiber-300 prepared in Example 3.
  • Figure 6 is an optical photograph of a metal foam nickel supported nickel oxide-alumina-yttria catalyst 10NiO-5Al 2 O 3 -5CeO 2 /Ni-foam-600 prepared in Example 8.
  • Example 7 is a SEM photograph of a metal foam nickel supported nickel oxide-alumina-yttria catalyst 10NiO-5Al 2 O 3 -5CeO 2 /Ni-foam-600 prepared in Example 8.
  • Figure 8 is a nickel-nickel fiber-supported nickel oxide and magnesium oxide catalyst 8NiO-8Al 2 O 3 -2MgO/8-Ni-SMF-600 and a comparative particulate catalyst 10NiO-5MgO/ ⁇ -Al 2 prepared in Example 6. A comparison of the temperature distribution of O 3 in the reactor.
  • Figure 9 is a graph showing the results of a 1000 hour stability test of a carbon monoxide methanation reaction of a 5NiO-5Al 2 O 3 -2.5CeO 2 /8-Ni-SMF-500 catalyst prepared in Example 5.
  • Figure 10 is a graph showing the results of a 3000 hour stability test of a carbon monoxide methanation reaction of a 5NiO-5Al 2 O 3 -2.5CeO 2 /8-Ni-SMF-500 catalyst prepared in Example 5.
  • Figure 11 is a graph showing the results of a 1000 hour stability test of a carbon dioxide methanation reaction of a 5NiO-5Al 2 O 3 -2.5CeO 2 /8-Ni-SMF-500 catalyst prepared in Example 5.
  • This embodiment provides the preparation of a sintered nickel metal fiber supported nickel oxide-alumina catalyst.
  • the sintered metal nickel fiber carrier prepared in the step 1 was cut into a 16 mm diameter disc and 5 g was weighed into a 50 ml beaker. At room temperature, an equal volume of impregnated metal phase carrier containing 0.1 g of aluminum powder (aluminum powder/metal phase carrier mass ratio of 2/100) having a particle diameter of 1 to 3 ⁇ m was removed and dried to obtain aluminum powder particles. After being dispersed on the surface of the metal phase carrier, the aluminum powder particles and the metal phase carrier surface layer are subjected to solid-solid alloying reaction at 600 ° C for 2 hours in a high-purity protective atmosphere to obtain a surface alloyed metal phase carrier;
  • step 3 The product obtained in the step 2 is subjected to aluminum extraction treatment for 1 hour at room temperature to 60 ° C with a 15% aqueous sodium hydroxide solution, rinsed with distilled water, and dried in the air to obtain a surface porous metal phase carrier;
  • FIG. 1 An optical photograph of 10NiO-10Al 2 O 3 /8-Ni-SMF-450 is shown in Fig. 1, a scanning electron microscope (SEM) photograph is shown in Fig. 2, and an X-ray diffraction (XRD) pattern is shown in Fig. 3.
  • SEM scanning electron microscope
  • XRD X-ray diffraction
  • the sintered metal Ni fiber structured catalyst skeleton accounts for 5% by volume and the porosity is 95. %.
  • the nickel metal fiber used in the first step of the present embodiment may have a diameter of 4 ⁇ m, and the remaining conditions are unchanged, and the obtained catalyst is represented by 10NiO-10Al 2 O 3 /4-Ni-SMF-450.
  • the mass of the aluminum powder in the second step of the present embodiment may be 0.025 to 0.10 g or 0.10 to 0.50 g, and the remaining conditions are unchanged.
  • the solid-solid alloying reaction temperature may be 550 to 600 ° C or 600 to 650 ° C
  • the solid-solid alloying reaction time may be 1 to 2 hours or 2 to 10 hours, and the remaining conditions are unchanged.
  • the concentration of the sodium hydroxide solution in the third step of the embodiment may be 5 to 15% or 15 to 20%, and the remaining conditions are unchanged.
  • the aluminum extraction treatment time may be 1 to 6 hours, and the remaining conditions are unchanged.
  • the calcination temperature in the fourth step of the present embodiment may be 600 ° C, and the remaining conditions are unchanged, and the obtained catalyst is represented by 10NiO-10Al 2 O 3 /8-Ni-SMF-600.
  • the calcination time in the fourth step of the present embodiment may be 0.5 to 2 hours, and the remaining conditions are unchanged.
  • the content of Ni(NO 3 ) 2 ⁇ 6H 2 O and Al(NO 3 ) 3 ⁇ 9H 2 O in an aqueous solution for immersing 3 g of the support in an equal volume may be 0.146 g and 1.864 g. Or 2.183 g and 0.124 g, or 0.719 g and 1.228 g, the rest of the conditions are unchanged, the catalyst obtained is expressed as 1NiO-15Al 2 O 3 /8-Ni-SMF-450, 15NiO-1Al 2 O 3 /8- Ni-SMF-450, 5NiO-10Al 2 O 3 /8-Ni-SMF-450.
  • This embodiment provides the preparation of a sintered copper-copper fiber carrier-supported nickel oxide-alumina catalyst.
  • the sintered metal copper fiber carrier prepared in the step 1 was cut into a 16 mm diameter disc and 5 g was weighed into a 50 ml beaker. At room temperature, an equal volume of impregnated metal phase carrier containing 0.4 g of aluminum powder having a particle diameter of 1 to 3 ⁇ m is removed and dried to disperse the aluminum powder particles on the surface of the metal phase carrier, and then in a high-purity protective atmosphere. The aluminum powder particles and the metal phase carrier surface layer were subjected to solid-solid alloying reaction at 600 ° C for 2 hours to obtain a surface alloyed metal phase carrier;
  • step 3 The product obtained in the step 2 is subjected to aluminum extraction treatment with a 20% hydrochloric acid aqueous solution at room temperature to 60 ° C for 6 hours, rinsed with distilled water and dried in the air to obtain a surface porous metal phase carrier;
  • the weight of NiO in the catalyst prepared in the present example was 9.6%, and the weight content of Al 2 O 3 was 5.3%.
  • the catalyst prepared in this example was expressed as 10NiO- 5Al 2 O 3 /8-Cu-SMF-300.
  • the sintered metal Cu fiber structured catalyst skeleton accounts for 38% by volume and the porosity is 62. %.
  • the diameter of the copper metal fiber in the first step of the present embodiment may be 30 ⁇ m, and the remaining conditions are unchanged, and the obtained catalyst is represented by 10NiO-5Al 2 O 3 /30-Cu-SMF-300.
  • This embodiment provides a preparation of a copper fiber supported iron oxide-alumina catalyst.
  • step 2 The product obtained in the step 1 is subjected to aluminum extraction treatment at room temperature to 60 ° C for 1 hour with a hydrochloric acid aqueous solution having a concentration of 5%, and rinsed with distilled water and dried in the air to obtain a surface-porous metal phase carrier;
  • the content of Fe 2 O 3 in the catalyst prepared in this example was 10.6%, and the weight content of Al 2 O 3 was 4.8%.
  • the catalyst prepared in this example was represented by plasma inductively coupled atomic emission spectrometry. It is 10Fe 2 O 3 -5Al 2 O 3 /30-Cu-fiber-300 (wherein the mantissa "300" indicates that the calcination temperature of the catalyst in the step 3 is 300 ° C, the same applies hereinafter).
  • FIG. 4 An optical photograph of 10Fe 2 O 3 -5Al 2 O 3 /30-Cu-fiber-300 is shown in Fig. 4, and a scanning electron microscope (SEM) photograph is shown in Fig. 5.
  • SEM scanning electron microscope
  • the diameter of the copper metal fiber in the first step of the embodiment may be 150 micrometers (indicated as 150-Cu-fiber), and the remaining conditions are unchanged, and the obtained catalyst is represented by 10Fe 2 O 3 -5Al 2 O 3 /150-Cu-fiber. -300.
  • This example provides the preparation of an iron metal fiber supported nickel oxide-alumina catalyst.
  • step 2 The product obtained in the step 1 is subjected to aluminum extraction treatment at room temperature to 60 ° C for 1 hour with a sodium hydroxide aqueous solution having a concentration of 5%, washed with distilled water and dried in the air to obtain a porous metal phase carrier. ;
  • the content of NiO in the catalyst prepared in this example was 5.2% by weight and the weight content of Al 2 O 3 was 5.3%.
  • the catalyst prepared in this example was expressed as 5NiO-. 5Al 2 O 3 /80-Fe-fiber-400.
  • the metal fiber used in this embodiment may be an 80 ⁇ m white copper fiber (expressed as 80-BT-fiber), and the remaining conditions are unchanged, and the obtained catalyst is represented by 5NiO-5Al 2 O 3 /80-BT-fiber-400, respectively.
  • This embodiment provides a preparation of a sintered nickel metal fiber supported nickel oxide-alumina-rare earth oxide catalyst.
  • the sintered metal nickel fiber carrier prepared in the step 1 was cut into a 16 mm diameter disc and 5 g was weighed into a 50 ml beaker. At room temperature, an equal volume of impregnated metal phase carrier containing 0.1 g of aluminum powder (aluminum powder/metal phase carrier mass ratio of 2/100) having a particle diameter of 1 to 3 ⁇ m was removed and dried to obtain aluminum powder particles. After being dispersed on the surface of the metal phase carrier, The aluminum powder particles and the metal phase carrier surface layer are subjected to solid-solid alloying reaction at 650 ° C for 2 hours in a high-purity protective atmosphere to obtain a surface alloyed metal phase carrier;
  • step 3 The product prepared in step 2 is subjected to aluminum extraction treatment at room temperature to 60 ° C for 6 hours with a 5% aqueous solution of sodium hydroxide, rinsed with distilled water and dried in air to obtain a porous metal phase carrier. ;
  • the volume fraction of the metal nickel fiber structured catalyst skeleton is 22%, and the pore volume is 22%.
  • the rate is 78%.
  • Ni(NO 3 ) 2 ⁇ 6H 2 O, Al(NO 3 ) 3 ⁇ 9H 2 O and Ce(NO 3 ) 3 ⁇ 6H 2 are used in an aqueous solution of an equal volume of 3 g of the carrier.
  • the content of O may be 0.719 g, 0.614 g and 0.500 g, or 1.528 g, 0.652 g and 0.510 g, and the remaining conditions are unchanged, and the obtained catalyst is represented by 5NiO-5Al 2 O 3 -5CeO 2 /8-Ni- SMF-500, 10NiO-5Al 2 O 3 -5CeO 2 /8-Ni-SMF-500.
  • the salt of the rare earth element in the aqueous solution for immersing 3 g of the support in an equal volume may be La(NO 3 ) 3 ⁇ 6H 2 O, and the content thereof may be 0.120 g or 0.230 g, and the remaining conditions are unchanged.
  • the catalyst obtained was represented by 5NiO-5Al 2 O 3 -2.5La 2 O 3 /8-Ni-SMF-500, 5NiO-5Al 2 O 3 -5La 2 O 3 /8-Ni-SMF-500.
  • This embodiment provides a nickel metal fiber carrier loaded with different contents of a nickel oxide-alumina-alkaline earth metal oxide agent.
  • the sintered metal nickel fiber carrier prepared in the step 1 was cut into a 16 mm diameter disc and 5 g was weighed into a 50 ml beaker. At room temperature, an equal volume of impregnated metal phase carrier containing 0.025 g of aluminum powder (aluminum powder/metal phase carrier mass ratio of 0.5/100) having a particle diameter of 1 to 3 ⁇ m was removed and dried to obtain aluminum powder particles. After being dispersed on the surface of the metal phase carrier, the aluminum powder particles and the surface layer of the metal phase carrier are subjected to solid-solid alloying reaction at 500 ° C for 2 hours in a high-purity protective atmosphere to obtain a surface alloyed metal phase carrier;
  • step 2 The product obtained in step 2 is subjected to aluminum extraction treatment at room temperature to 60 ° C for 1 hour with a 5% aqueous solution of sodium hydroxide, rinsed with distilled water and dried in air to obtain a porous metal phase carrier. ;
  • the volume fraction of the metal nickel fiber structured catalyst skeleton is 28%, and the porosity is 72%.
  • the salt of the alkaline earth metal element in the aqueous solution for immersing 5 g of the carrier in an equal volume may be Ca(NO 3 ) 2 ⁇ 4H 2 O, the content of which is 0.519 g, and the remaining conditions are unchanged.
  • the catalyst is represented by 8NiO-8Al 2 O 3 -2CaO/8-Ni-SMF-600.
  • This embodiment provides a preparation of a sintered nickel metal fiber supported nickel oxide-alumina-alkali metal oxide catalyst.
  • the sintered metal nickel fiber carrier prepared in the step 1 was cut into a 16 mm diameter disc and 5 g was weighed into a 50 ml beaker. At room temperature, an equal volume of impregnated metal phase carrier containing 0.025 g of aluminum powder (aluminum powder/metal phase carrier mass ratio of 0.5/100) having a particle diameter of 1 to 3 ⁇ m was removed and dried to obtain aluminum powder particles. After being dispersed on the surface of the metal phase carrier, the aluminum powder particles and the metal phase carrier surface layer are subjected to solid-solid alloying reaction at 550 ° C for 2 hours in a high-purity protective atmosphere to obtain a surface alloyed metal phase carrier;
  • step 2 The product obtained in step 2 is subjected to aluminum extraction treatment at room temperature to 60 ° C for 1 hour with a 5% aqueous solution of sodium hydroxide, rinsed with distilled water and dried in air to obtain a porous metal phase carrier. ;
  • the volume fraction of the metal nickel fiber structured catalyst skeleton is 28%, and the pore volume is 28%.
  • the rate is 72%.
  • the salt of the alkaline earth metal element in the aqueous solution for equal volume impregnation of 3 g of the carrier may be KNO 3 , the content of which is 0.090 g, and the remaining conditions are unchanged, and the obtained catalyst is represented by 8NiO-8Al 2 . O 3 -2K 2 O/8-Ni-SMF-600.
  • This embodiment provides a preparation of a metal foam nickel supported nickel oxide-alumina-yttria catalyst.
  • Ni-foam nickel foam metal
  • the metal phase carrier containing 0.3 g of aluminum powder with a particle size of 1 to 10 ⁇ m and dry it to make aluminum powder.
  • the aluminum powder particles and the metal phase carrier surface layer are subjected to solid-solid alloying reaction at 600 ° C for 2 hours in a high-purity protective atmosphere to obtain a surface alloyed metal phase carrier;
  • step 2 The product obtained in the step 1 was subjected to aluminum extraction treatment for 1 hour at room temperature to 60 ° C with a 15% aqueous solution of sodium hydroxide, rinsed with distilled water, and dried in air to obtain a porous nickel metal foam.
  • Carrier
  • the metal nickel foam skeleton accounts for 20% by volume and the porosity is 80%.
  • the metal foam material in this embodiment may be foamed white copper (denoted as BT-foam), foamed copper (expressed as Cu-foam), foamed iron (expressed as Fe-foam), and the remaining conditions are unchanged, and the obtained catalysts are respectively It is represented by 10NiO-5Al 2 O 3 -5CeO 2 /BT-foam-600, 10NiO-5Al 2 O 3 -5CeO 2 /Cu-foam-600, 10NiO-5Al 2 O 3 -5CeO 2 /Fe-foam-600.
  • This embodiment provides a preparation of a metal foam nickel support-supported nickel oxide-alumina-manganese oxide catalyst.
  • Ni-foam nickel foam
  • metal phase carrier with a volume of 0.3 g of aluminum powder with a particle size of 1 to 10 ⁇ m at room temperature and dry to make aluminum powder.
  • the aluminum powder particles and the metal phase carrier surface layer are subjected to solid-solid alloying reaction at 600 ° C for 2 hours in a high-purity protective atmosphere to obtain a surface alloyed metal phase carrier;
  • step 2 The product obtained in the step 1 was subjected to aluminum extraction treatment for 1 hour at room temperature to 60 ° C with a 15% aqueous solution of sodium hydroxide, rinsed with distilled water, and dried in air to obtain a porous nickel metal foam.
  • Carrier
  • the aqueous solution for immersing 3 g of the support in an equal volume may be 1.528 g, 0.652 g and 0.250 g of Ni(NO 3 ) 2 ⁇ 6H 2 O, Al(NO 3 ) 3 ⁇ 9H 2
  • An aqueous solution of O and Mo(NO 3 ) 3 .5H 2 O is impregnated with an equal volume at room temperature, dried at 100 ° C, and calcined at 600 ° C for 2 hours in the air, and the remaining conditions are unchanged, that is, the nickel foam carrier is obtained.
  • NiO, Al 2 O 3 and MoO 3 in the catalyst are 10%, 5% and 5%, respectively, and the catalyst is represented by 10NiO-5Al 2 O 3 -5MoO 3 / Ni-foam-600.
  • an equal volume of an aqueous solution containing 1.528 g and 0.652 g of Ni(NO 3 ) 2 ⁇ 6H 2 O and Al(NO 3 ) 3 ⁇ 9H 2 O is firstly immersed in an equal volume at room temperature.
  • the gram carrier after drying at 100 ° C, is again impregnated with an equal volume of an aqueous solution containing 0.230 g of Na 2 WO 4 ⁇ 2H 2 O, and then dried at 100 ° C and calcined at 600 ° C for 2 hours in the air, the remaining conditions are unchanged.
  • the nickel foam-supported nickel oxide-alumina-tungsten oxide-sodium oxide catalyst is obtained, wherein the weight contents of NiO, Al 2 O 3 , WO 3 and Na 2 O in the catalyst are 10%, 5, respectively. %, 4% and 1%, the catalyst is represented by 10NiO-5Al 2 O 3 -4WO 3 -1Na 2 O/Ni-foam-600.
  • the inventors of the present application found that the catalyst obtained by supporting the porous metal phase carrier NiO or the like in the present invention is superior to the oxide carrier-supported NiO-based catalyst such as Al 2 O 3 in catalytic performance and thermal conductivity.
  • the following are catalysts for comparative experiments made by the inventors of the present application.
  • the catalytic performance of the catalyst of the present invention for the methanation of carbon monoxide under different reaction conditions was investigated on a fixed bed reactor.
  • the reaction materials were carbon monoxide and hydrogen, and the molar ratio of carbon monoxide to hydrogen was 1:3.
  • the fixed bed reactor is a quartz tube with an inner diameter of 16 mm.
  • the carbon monoxide and hydrogen are mixed before entering the reaction tube, and after mixing, they are introduced into the catalyst bed for reaction.
  • the reaction product was condensed in a cold trap and the gas phase product was subjected to chromatography, which was analyzed using a thermal conductivity cell detector (TCD).
  • TCD thermal conductivity cell detector
  • the catalytic performance of the catalyst of the present invention for the methanation of carbon dioxide under different reaction conditions was examined on a fixed bed reactor.
  • the reaction materials were carbon dioxide and hydrogen, and the molar ratio of carbon dioxide to hydrogen was 1:4.
  • the fixed bed reactor is a quartz tube with an inner diameter of 16 mm.
  • the carbon dioxide and hydrogen are mixed before entering the reaction tube, and after mixing, they are introduced into the catalyst bed for reaction.
  • the reaction product was condensed in a cold trap and the gas phase product was subjected to chromatography, which was analyzed using a thermal conductivity cell detector (TCD).
  • TCD thermal conductivity cell detector
  • the reaction apparatus, the reaction raw materials, and the amount of the catalyst were the same as those in Application Example 1.
  • the catalyst of the present invention was investigated on a fixed bed reactor for carbon monoxide and carbon dioxide under different conditions.
  • the catalytic performance of the alkylation reaction, the reaction raw material is a mixture of carbon monoxide, carbon dioxide, methane and hydrogen, and the molar ratio of carbon monoxide, carbon dioxide, methane and hydrogen is 17:20:10:53.
  • the fixed bed reactor is a quartz tube with an inner diameter of 16 mm. Carbon monoxide, carbon dioxide, methane and hydrogen are mixed before entering the reaction tube, and after mixing, they are introduced into the catalyst bed for reaction.
  • the reaction product was condensed in a cold trap and the gas phase product was subjected to chromatography, which was analyzed using a thermal conductivity cell detector (TCD).
  • TCD thermal conductivity cell detector
  • the catalytic performance of the catalyst of the present invention for the reforming reaction of methane and carbon dioxide under different conditions was examined on a fixed bed reactor.
  • the reaction raw material was a mixture of carbon dioxide and methane, and the molar ratio of methane to carbon dioxide was 1:1.
  • the fixed bed reactor is a quartz tube with an inner diameter of 16 mm. Methane and carbon dioxide are mixed before entering the reaction tube, and after mixing, they are introduced into the catalyst bed for reaction.
  • the reaction product was condensed in a cold trap and the gas phase product was subjected to chromatography, which was analyzed using a thermal conductivity cell detector (TCD).
  • TCD thermal conductivity cell detector
  • the catalytic performance of the catalyst of the present invention for the autothermal reforming reaction of methane under different conditions was investigated on a fixed bed reactor.
  • the reaction raw material was a mixture of methane, water vapor and oxygen, and the molar ratio of methane, water vapor and oxygen was 3:10:2.
  • the fixed bed reactor is a quartz tube with an inner diameter of 16 mm. Methane, water vapor and oxygen are mixed before entering the reaction tube, and after mixing, they are introduced into the catalyst bed for reaction.
  • the reaction product was condensed in a cold trap and the gas phase product was subjected to chromatography, which was analyzed using a thermal conductivity cell detector (TCD).
  • TCD thermal conductivity cell detector
  • This embodiment demonstrates the excellent effect of the high thermal conductivity of the catalyst of the present invention on heat transfer enhancement and elimination of high temperature hot spots by CFD simulation.
  • the reaction apparatus, the reaction raw materials, and the amount of the catalyst were the same as those in Application Example 1.
  • the reaction apparatus, the reaction raw materials, and the amount of the catalyst were the same as those in Application Example 1.
  • the reaction apparatus and the reaction raw materials were the same as in Application Example 1, and the amount of the catalyst was 10.4 ml.
  • This application example is based on the 5NiO-5Al 2 O 3 -2.5CeO 2 /8-Ni-SMF-500 catalyst prepared in Example 5, using a mixture of carbon monoxide and hydrogen in a molar ratio of 1:3 as a raw material, at 330
  • the stability of the carbon monoxide methanation reaction was investigated for 3000 hours under the reaction temperature of °C and 5000h -1 gas hourly space velocity. The results are shown in Figure 10.
  • the catalyst of the present invention has excellent reaction stability as well as activity and selectivity for methanation of carbon monoxide.
  • the reaction apparatus and the reaction raw materials were the same as in Application Example 1, and the amount of the catalyst was 10.2 ml.
  • the catalyst of the present invention can be applied to the chemical industry.

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Abstract

一种金属相载体负载型催化剂及其制备方法和用于催化一氧化碳或(和)二氧化碳制备甲烷以及甲烷制合成气反应的用途。所述金属相载体负载型催化剂包括负载于金属相载体的活性组分金属氧化物和助剂金属氧化物，并具如下通式：xM1O-yM2O/ZT，其中M1O表示活性组分金属氧化物，M2O表示助剂金属氧化物，ZT表示金属相载体，x表示活性组分金属氧化物所占催化剂的质量百分数，y表示助剂金属氧化物占催化剂的质量百分数。本发明所述的催化剂具有高活性、高稳定性、优良的导热性、渗透性高、使用方便、寿命长、制备简单等优点，可有效解决化工领域中的强放/吸热反应中的热效应难题，可作为甲烷化过程以及甲烷制合成气反应的催化剂。

Description

一种金属相载体负载型催化剂及其制备方法和用途 技术领域
本发明属于催化技术领域，涉及一种催化剂及其制备方法和用途，具体地说是一种以金属相载体负载型催化剂及其制备方法和用途，该催化剂可用于催化一氧化碳或(和)二氧化碳加氢以合成甲烷以及甲烷重整制合成气反应。
背景技术
天然气是一种安全、清洁的优质能源，主要成分是甲烷(CH4)，具有热值高、污染小等优点，在发电、化工和民用等方面有着广泛的应用。自从1902年Sabatier和Senderens首先在镍基催化剂上利用一氧化碳和氢气合成出甲烷后，甲烷化反应发展迅速且广泛应用在气体净化过程。
甲烷化工艺的关键是开发新型高效催化剂。现有技术教导了多种甲烷化催化剂，例如中国专利200610021836.5、201010223996.4和中国专利ZL88105142.x。简言之，现有技术的甲烷化催化剂基本采用氧化物作为载体，比如三氧化铝、二氧化硅、二氧化钛、二氧化锆等。
一方面，一氧化碳甲烷化、二氧化碳甲烷化以及一氧化碳二氧化碳共甲烷化过程，都是强放热过程，而氧化物材料的导热性能较差，因此在反应过程中容易形成“热点”甚至反应器飞温，从而导致现有技术的催化剂的烧结失活甚至造成生产安全事故。实际生产中不得不采用反应气大循环比结合多段反应和段间冷却的操作工艺，以解决反应器飞温的问题，但带来了高能耗、效率低等问题。另一方面，现有技术中，为了消除在固定床反应器中气体内扩散和外扩散的限制，需要采用粒径较小的催化剂颗粒和较大的气体流速。然而这些措施会造成床层两端压降增加，带来能耗和安全方面的问题，对生产不利。
此外，甲烷制合成气是实现甲烷化工利用的重要途径之一，目前发展了蒸汽重整、部分氧化、二氧化碳重整和自热重整等制合成气工艺，但上述工艺均存在较强的热效应(强吸热或强放热)问题，针对他们的热力学研究表明，其容易在低温下发生副反应积碳。事实上，由于传统的固定床反应管内有效传热系数普遍较低，即使管壁温度高达800℃，床层内仍存在冷点，积碳难以避免。
金属相载体结构催化剂由于其比表面积大、传递性能好、床层压降低等优点，在环境催化和污染控制领域已有应用。利用这种优良的传递性能，将金属相载体结构催化剂应用于化工领域中的强放/吸热反应中，可以大幅度提高能量利用效率，实现流程集成化，达到过程强化的目的。而甲烷化反应、甲烷制合成气反应都存在强烈的热效应，因此现有技 术中已存在金属相载体结构甲烷化催化剂和甲烷制合成气催化剂的尝试。但是，这些现有技术的催化剂存在熔点低、化学活性高、催化活性不足、制备复杂、制备过程污染较严重等缺陷。
发明内容
本发明的目的在于提供一种具有高催化活性、高稳定性、优良导热性、使用方便、制备简单等优点的催化剂及其制备方法和应用，以适用于具有强烈热效应的甲烷制备反应和甲烷制合成气的反应。
为实现上述发明目的，本发明提供了一种金属相载体负载型催化剂，包括负载于金属相载体的活性组分金属氧化物和助剂金属氧化物并具有通式xM1O-yM2O/ZT，其中M1O表示活性组分金属氧化物，M2O表示助剂金属氧化物，ZT表示金属相载体，x表示活性组分金属氧化物所占催化剂的质量百分数，y表示助剂金属氧化物占催化剂的质量百分数。
作为进一步优选方案，本发明的催化剂中，活性组分金属氧化物M1O所占催化剂质量百分数x为1～15％，助剂金属氧化物M2O所占催化剂质量百分数y为1～15％，其余为金属相载体ZT。在不同的实施例中，x、y的值可以是1、3、5、6、7.5、9、10、13、15，都能实现本发明的目的。
作为更进一步优选方案，所述金属相载体为金属镍、金属铜、金属铁或金属白铜。
作为更进一步优选方案，所述金属相载体是直径为4～150微米、长度为2～10毫米的纤维、由该纤维烧结而成的三维多孔结构整体式金属纤维载体或三维多孔结构整体式金属泡沫载体。
作为更进一步优选方案，本发明的催化剂中的活性组分金属氧化物M1O为镍和铁的氧化物中的至少一种。
作为更进一步优选方案，本发明的催化剂中的助剂金属氧化物M2O为铝、铈、镧、钼、锰、钨、镁、钙、钠、钾的氧化物中的至少一种。
本发明的另一方面提供了一种催化剂的制备方法，包括如下步骤：
①用含铝粉(优选颗粒大小在1-10微米之间的超细铝粉)的悬浊液等体积浸渍金属相载体(“等体积浸渍”意味着含铝粉的悬浊液与待浸渍的金属相载体的体积相同)，然后进行干燥处理，使铝粉颗粒分散在金属相载体表面后，于550～650℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应(例如反应1～10小时)(反应例如可以在高纯保护气氛中进行，例如纯度等于或高于99.999％氮、氢、氩或氦，也可以在真空中进行)，得到表层合金化的金属相载体(在本发明的不同实施例中，固-固合金化反应的温度可以是550、 570、600、630、650℃，反应时间可以是1、2、3、5、7、8、10小时或更短或更长，都能实现本发明的目的)；
②将步骤①制得的产品，在室温至60℃的温度下用浓度为5～20％的盐酸或氢氧化钠水溶液进行抽铝处理(例如1～6小时)，经蒸馏水冲洗、空气中烘干后，得到表层多孔化的金属相载体(在本发明的不同实施例中，本步骤的温度可以是20、30、40、50、60℃，盐酸或氢氧化钠水溶液的浓度可以是5、5.5、7、10、14、18、20％，抽铝处理时间可以是1、2、4、5、6小时或更短或更长，都能实现本发明的目的)；
③将步骤②制得的产品，在室温或相当条件下等体积浸渍于含活性组分M1金属元素的盐和助剂组分M2金属元素的盐的水溶液(此处的浸渍可以是将步骤②制得的产品浸渍在同时含活性组分和助剂组分的同一溶液中，也可以是将步骤②制得的产品先后分别在只含一种组分的第一溶液中浸渍，然后在含另一种组分的第二溶液中浸渍)，经烘干后于300～600℃焙烧(例如0.5～2小时)，即得到所述的金属相载体金属相载体负载型催化剂(在不同实施例中，本步骤的焙烧温度可以是300、350、400、500、600℃，焙烧时间可以是0.5、1、1.5、2小时或更短或更长，都能实现本发明的目的)。
作为进一步优选方案，金属相载体表层合金化过程中使用的铝粉的粒径为1～3微米，铝粉/金属相载体的质量比为0.5～10/100(在不同实施例中，铝粉/金属相载体的质量比可以是0.5/100、1/100、3/100、5/100、8/100、10/100，都能实现本发明的目的)。
本发明的另一方面是将所述的金属相载体负载型催化剂用于从一氧化碳和/或二氧化碳加氢制备甲烷。
本发明的另一方面是将所述的金属相载体负载型催化剂用于从甲烷制备合成气，尤其是作为甲烷-二氧化碳重整或甲烷自热重整制备合成气的催化剂。
与现有技术相比，本发明提供的金属相载体负载型催化剂具有结构稳定、导热性好、渗透率高等优点，在使用中具有易于成型、易于装填、易于存放等优点，且其制备方法简单、原料易得、结构可控。相比传统氧化物载体负载型催化剂颗粒填充固定床的现有技术，本发明的整体式金属相载体负载型催化剂的大孔隙率可以大大降低床层两端的压降，其高导热性可以使得床层内温度更为均匀，能充分满足合成气甲烷化反应的催化性能要求。
附图说明
图1是实施例1中所制的烧结金属镍纤维负载的氧化镍-氧化铝催化剂10NiO-10Al2O3/8-Ni-SMF-450的光学照片。
图2是实施例1中所制的烧结金属镍纤维负载的氧化镍-氧化铝催化剂10NiO-10Al2O3/8-Ni-SMF-450的SEM照片。
图3是实施例1中所制的烧结金属镍纤维负载的氧化镍-氧化铝催化剂10NiO-10Al2O3/8-Ni-SMF-450的XRD谱图。
图4是实施例3中所制的金属铜纤维负载的氧化铁-氧化铝催化剂10Fe2O3-5Al2O3/30-Cu-fiber-300的光学照片。
图5是实施例3中所制的金属铜纤维负载的氧化铁-氧化铝催化剂10Fe2O3-5Al2O3/30-Cu-fiber-300的SEM照片。
图6是实施例8中所制的金属泡沫镍载体负载氧化镍-氧化铝-氧化铈催化剂10NiO-5Al2O3-5CeO2/Ni-foam-600的光学照片。
图7是实施例8中所制的金属泡沫镍载体负载氧化镍-氧化铝-氧化铈催化剂10NiO-5Al2O3-5CeO2/Ni-foam-600的SEM照片。
图8是实施例6中所制的金属镍纤维负载的氧化镍和氧化镁催化剂8NiO-8Al2O3-2MgO/8-Ni-SMF-600和对比例颗粒催化剂10NiO-5MgO/γ-Al2O3在反应器内的温度分布对比图。
图9是实施例5制得的5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500催化剂催化一氧化碳甲烷化反应1000小时稳定性测试结果。
图10是实施例5制得的5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500催化剂催化一氧化碳甲烷化反应3000小时稳定性测试结果。
图11是实施例5制得的5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500催化剂催化二氧化碳甲烷化反应1000小时稳定性测试结果。
具体实施方式
下面结合实施例对本发明作进一步的阐述，其目的是为更好的理解本发明的内容。因此所举之例并不限制本发明的保护范围。
实施例1
本实施例提供一种烧结镍金属纤维载体负载的氧化镍-氧化铝催化剂的制备。
①称取直径为8微米、长度为2～5毫米的镍金属纤维15克和长度为0.1～1毫米纤维素纤维2.5克及1.5升水加入到搅拌机中，充分搅拌成均匀分散的纤维浆后转移到造纸机内，将水加到8.5升，搅拌、排水后成型；待干燥后在空气氛中于500℃焙烧1小时；再在氢气中于950℃烧结1小时，将产品的厚度通过压制控制在1毫米，得到烧结金属镍纤维载体，表示为8-Ni-SMF；
②将步骤①制得的烧结金属镍纤维载体裁剪成直径为16毫米圆片并称取5克置于50毫升烧杯中。在室温下，移取含粒径为1～3微米的0.1克铝粉(铝粉/金属相载体的质量比为2/100)的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后，在高纯保护气氛中于600℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应2小时，得到表层合金化的金属相载体；
③将步骤②制得的产品，在室温至60℃下用浓度为15％的氢氧化钠水溶液进行抽铝处理1小时，经蒸馏水冲洗、空气中烘干，得到表层多孔化的金属相载体；
④称取步骤③制得的载体3克，用等体积的含1.528克和1.305克的Ni(NO3)2·6H2O 和Al(NO3)3·9H2O的水溶液，在室温下等体积浸渍载体，100℃烘干后于空气中450℃焙烧2小时，即得到所述的烧结镍金属纤维载体负载的氧化镍-氧化铝催化剂；经等离子电感耦合原子发射光谱测定得知，本实施例所制备的催化剂中，Al2O3的重量含量为10.4％；经程序升温还原工作曲线法测定得知，本实施例所制备的催化剂中，NiO的重量含量为9.5％；本实施例所制备的催化剂表示为10NiO-10Al2O3/8-Ni-SMF-450(此处尾数“450”表示步骤④中催化剂的焙烧温度为450℃，下同)。
10NiO-10Al2O3/8-Ni-SMF-450的光学照片见图1，扫描电镜(SEM)照片见图2，X射线衍射(XRD)图见图3。
经宏观测量得知：本实施制备的整体式催化剂10NiO-10Al2O3/8-Ni-SMF-450中，烧结金属Ni纤维结构化催化剂骨架所占的体积百分比为5％，孔隙率为95％。
本实施例第①步中使用的镍金属纤维的直径可以为4微米，其余条件不变，所得催化剂表示为10NiO-10Al2O3/4-Ni-SMF-450。
本实施例第②步中铝粉的质量可以为0.025～0.10g或0.10～0.50g，其余条件不变。
本实施例第②步中固-固合金化反应温度可以是550～600℃或600～650℃，固-固合金化反应时间可以是1～2小时或2～10小时，其余条件不变。
本实施例第③步中氢氧化钠溶液浓度可以是5～15％或15～20％，其余条件不变。
本实施例第③步中抽铝处理时间可以是1～6小时，其余条件不变。
本实施例第④步中焙烧温度可以是600℃，其余条件不变，所得催化剂表示为10NiO-10Al2O3/8-Ni-SMF-600。
本实施例第④步中焙烧时间可以是0.5～2小时，其余条件不变。
本实施例第④步中，用于等体积浸渍3克载体的水溶液中Ni(NO3)2·6H2O和Al(NO3)3·9H2O的含量可以是0.146克和1.864克，或2.183克和0.124克，或0.719克和1.228克，其余条件不变，所制得的催化剂表示为1NiO-15Al2O3/8-Ni-SMF-450，15NiO-1Al2O3/8-Ni-SMF-450，5NiO-10Al2O3/8-Ni-SMF-450。
实施例2
本实施例提供一种烧结紫铜金属纤维载体负载的氧化镍-氧化铝催化剂的制备。
①称取直径为8微米、长度为2～5毫米的紫铜金属纤维15克和长度为0.1～1毫米纤 维素纤维2.5克及1.5升水加入到搅拌机中，充分搅拌成均匀分散的纤维浆后转移到造纸机内，将水加到8.5升，搅拌、排水后成型；待干燥后在空气氛中于250℃焙烧1小时；再在氢气中于900℃烧结1小时，得到烧结金属紫铜纤维载体，表示为8-Cu-SMF；
②将步骤①制得的烧结金属紫铜纤维载体裁剪成直径为16毫米圆片并称取5克置于50毫升烧杯中。在室温下，移取含粒径为1～3微米的0.4克铝粉的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后，在高纯保护气氛中于600℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应2小时，得到表层合金化的金属相载体；
③将步骤②制得的产品，在室温至60℃下用浓度为20％的盐酸水溶液进行抽铝处理6小时，经蒸馏水冲洗、空气中烘干后，得到表层多孔化的金属相载体；
④称取步骤③制得的载体3克，用等体积的含1.438克和0.614克的Ni(NO3)2·6H2O和Al(NO3)3·9H2O的水溶液，在室温下等体积浸渍载体，100℃烘干后于空气中300℃焙烧2小时，即得到所述的烧结紫铜金属纤维载体负载的氧化镍-氧化铝催化剂。
经等离子电感耦合原子发射光谱测定得知，本实施例所制备的催化剂中，NiO的重量含量为9.6％，Al2O3的重量含量为5.3％；本实施例所制备的催化剂表示为10NiO-5Al2O3/8-Cu-SMF-300。
经宏观测量得知：本实施制备的整体式催化剂10NiO-5Al2O3/8-Cu-SMF-300中，烧结金属Cu纤维结构化催化剂骨架所占的体积百分比为38％，孔隙率为62％。
本实施例第①步中紫铜金属纤维的直径可以为30微米，其余条件不变，所得催化剂表示为10NiO-5Al2O3/30-Cu-SMF-300。
实施例3
本实施例提供一种紫铜纤维载体负载氧化铁-氧化铝催化剂的制备。
①称取直径为30微米、长度为5～10毫米的紫铜金属纤维(表示为Cu-fiber)15克，在室温下，移取含粒径为1～3微米的0.075克铝粉的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后，在高纯保护气氛中于600℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应2小时，得到表层合金化的金属相载体；
②将步骤①制得的产品，在室温至60℃下用浓度为5％的盐酸水溶液进行抽铝处理1小时，经蒸馏水冲洗、空气中烘干后，得到表层多孔化的金属相载体；
③称取步骤②制得的载体3克，用等体积的含1.489克和0.614克的Fe(NO3)3·9H2O和Al(NO3)3·9H2O的水溶液，在室温下等体积浸渍载体，100℃烘干后于空气中300℃焙烧2小时，即得到所述的紫铜金属纤维载体负载的氧化铁-氧化铝催化剂。
经等离子电感耦合原子发射光谱测定得知，本实施例所制备的催化剂中，Fe2O3的重量含量为10.6％，Al2O3的重量含量为4.8％；本实施例所制备的催化剂表示为10Fe2O3-5Al2O3/30-Cu-fiber-300(此处尾数“300”表示步骤③中催化剂的焙烧温度为300℃， 下同)。
10Fe2O3-5Al2O3/30-Cu-fiber-300的光学照片见图4，扫描电镜(SEM)照片见图5。
本实施例第①步中紫铜金属纤维的直径可以为150微米(表示为150-Cu-fiber)，其余条件不变，所得催化剂表示为10Fe2O3-5Al2O3/150-Cu-fiber-300。
实施例4
本实施例提供一种铁金属纤维载体负载氧化镍-氧化铝催化剂的制备。
①称取直径为80微米、长度为5～10毫米的铁金属纤维(表示为80-Fe-fiber)5克，在室温下，移取含粒径为1～3微米的0.2克铝粉的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后，在高纯保护气氛中于600℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应2小时，得到表层合金化的金属相载体；
②将步骤①制得的产品，在室温至60℃下用浓度为5％的氢氧化钠水溶液进行抽铝处理1小时，经蒸馏水冲洗、空气中烘干后，得到表层多孔化的金属相载体；
③称取步骤②制得的载体3克，用等体积的含0.745克和0.614克的Ni(NO3)2·6H2O和Al(NO3)3·9H2O的水溶液，在室温下等体积浸渍载体，100℃烘干后于空气中400℃焙烧2小时，即得到所述的金属铁纤维载体负载的氧化镍-氧化铝催化剂。
经等离子电感耦合原子发射光谱测定得知，本实施例所制备的催化剂中，NiO的重量含量为5.2％，Al2O3的重量含量为5.3％；本实施例所制备的催化剂表示为5NiO-5Al2O3/80-Fe-fiber-400。
本实施例中所用金属纤维可以是80微米的白铜纤维(表示为80-BT-fiber)，其余条件不变，所得催化剂分别表示为5NiO-5Al2O3/80-BT-fiber-400。
实施例5
本实施例提供一种烧结镍金属纤维载体负载氧化镍-氧化铝-稀土氧化物催化剂的制备。
①称取直径为8微米、长度为2～5毫米的镍金属纤维15克和长度为0.1～1毫米纤维素纤维2.5克及1.5升水加入到搅拌机中，充分搅拌成均匀分散的纤维浆后转移到造纸机内，将水加到8.5升，搅拌、排水后成型；待干燥后在空气氛中于500℃焙烧1小时；再在氢气中于950℃烧结1小时，将产品的厚度通过压制控制在1毫米，得到烧结金属镍纤维载体，表示为8-Ni-SMF；
②将步骤①制得的烧结金属镍纤维载体裁剪成直径为16毫米圆片并称取5克置于50毫升烧杯中。在室温下，移取含粒径为1～3微米的0.1克铝粉(铝粉/金属相载体的质量比为2/100)的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后， 在高纯保护气氛中于650℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应2小时，得到表层合金化的金属相载体；
③将步骤②制得的产品，在室温至60℃下用浓度为5％的氢氧化钠水溶液进行抽铝处理6小时，经蒸馏水冲洗、空气中烘干后，得到表层多孔化的金属相载体；
④称取步骤③制得的载体3克，用等体积的含0.596克、0.698克和0.211克的Ni(NO3)2·6H2O、Al(NO3)3·9H2O和Ce(NO3)3·6H2O的水溶液，在室温下等体积浸渍载体，100℃烘干燥后于空气中500℃焙烧2小时，即得到所述的镍金属纤维载体负载的氧化镍-氧化铝-氧化铈催化剂，其中NiO、Al2O3和CeO2在催化剂中的重量含量分别为5％、5％和2.5％，催化剂表示为5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500。
经宏观测量得知：本实施制备的整体式催化剂5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500中，金属镍纤维结构化催化剂骨架所占的体积百分比为22％，孔隙率为78％。
本实施例第④步中，用于等体积浸渍3克载体的水溶液中Ni(NO3)2·6H2O、Al(NO3)3·9H2O和Ce(NO3)3·6H2O的含量可以是0.719克、0.614克和0.500克，或1.528克、0.652克和0.510克，其余条件不变，，制得的催化剂表示为5NiO-5Al2O3-5CeO2/8-Ni-SMF-500，10NiO-5Al2O3-5CeO2/8-Ni-SMF-500。
本实施例第④步中，用于等体积浸渍3克载体的水溶液中稀土元素的盐可以是La(NO3)3·6H2O，其含量可以是0.120克或0.230克，其余条件不变，制得的催化剂表示为5NiO-5Al2O3-2.5La2O3/8-Ni-SMF-500，5NiO-5Al2O3-5La2O3/8-Ni-SMF-500。
实施例6
本实施例提供一种镍金属纤维载体负载不同含量氧化镍-氧化铝-碱土金属氧化物化剂的制备。
①称取直径为8微米、长度为2～5毫米的镍金属纤维15克和长度为0.1～1毫米纤维素纤维2.5克及1.5升水加入到搅拌机中，充分搅拌成均匀分散的纤维浆后转移到造纸机内，将水加到8.5升，搅拌、排水后成型；待干燥后在空气氛中于500℃焙烧1小时；再在氢气中于950℃烧结1小时，将产品的厚度通过压制控制在1毫米，得到烧结金属镍纤维载体，表示为8-Ni-SMF；
②将步骤①制得的烧结金属镍纤维载体裁剪成直径为16毫米圆片并称取5克置于50毫升烧杯中。在室温下，移取含粒径为1～3微米的0.025克铝粉(铝粉/金属相载体的质量比为0.5/100)的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后，在高纯保护气氛中于500℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应2小时，得到表层合金化的金属相载体；
③将步骤②制得的产品，在室温至60℃下用浓度为5％的氢氧化钠水溶液进行抽铝处理1小时，经蒸馏水冲洗、空气中烘干后，得到表层多孔化的金属相载体；
④称取步骤③制得的载体3克，用等体积的含1.222克、1.043克和0.510克的 Ni(NO3)2·6H2O、Al(NO3)3·9H2O和Mg(NO3)2·6H2O的水溶液，在室温下等体积浸渍载体，100℃烘干燥后于空气中600℃焙烧2小时，即得到所述的镍金属纤维载体负载的氧化镍-氧化铝-氧化镁催化剂，其中NiO、Al2O3和MgO在催化剂中的重量含量分别为8％、8％和2％，催化剂表示为8NiO-8Al2O3-2MgO/8-Ni-SMF-600。
经宏观测量得知：本实施制备的整体式催化剂8NiO-8Al2O3-2MgO/8-Ni-SMF-600中，金属镍纤维结构化催化剂骨架所占的体积百分比为28％，孔隙率为72％。
本实施例第④步中，用于等体积浸渍5克载体的水溶液中碱土金属元素的盐可以是Ca(NO3)2·4H2O，其含量是0.519克，其余条件不变，制得的催化剂表示为8NiO-8Al2O3-2CaO/8-Ni-SMF-600。
实施例7
本实施例提供一种烧结镍金属纤维载体负载氧化镍-氧化铝-碱金属氧化物催化剂的制备。
①称取直径为8微米、长度为2～5毫米的镍金属纤维15克和长度为0.1～1毫米纤维素纤维2.5克及1.5升水加入到搅拌机中，充分搅拌成均匀分散的纤维浆后转移到造纸机内，将水加到8.5升，搅拌、排水后成型；待干燥后在空气氛中于500℃焙烧1小时；再在氢气中于950℃烧结1小时，将产品的厚度通过压制控制在1毫米，得到烧结金属镍纤维载体，表示为8-Ni-SMF；
②将步骤①制得的烧结金属镍纤维载体裁剪成直径为16毫米圆片并称取5克置于50毫升烧杯中。在室温下，移取含粒径为1～3微米的0.025克铝粉(铝粉/金属相载体的质量比为0.5/100)的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后，在高纯保护气氛中于550℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应2小时，得到表层合金化的金属相载体；
③将步骤②制得的产品，在室温至60℃下用浓度为5％的氢氧化钠水溶液进行抽铝处理1小时，经蒸馏水冲洗、空气中烘干后，得到表层多孔化的金属相载体；
④称取步骤③制得的载体3克，用等体积的含1.222克、1.043克和0.110克的Ni(NO3)2·6H2O、Al(NO3)3·9H2O和NaNO3的水溶液，在室温下等体积浸渍载体，100℃烘干燥后于空气中600℃焙烧2小时，即得到所述的镍金属纤维载体负载的氧化镍-氧化铝-氧化钠催化剂，其中NiO、Al2O3和Na2O在催化剂中的重量含量分别为8％、8％和2％，催化剂表示为8NiO-8Al2O3-2Na2O/8-Ni-SMF-600。
经宏观测量得知：本实施制备的整体式催化剂8NiO-8Al2O3-2Na2O/8-Ni-SMF-600中，金属镍纤维结构化催化剂骨架所占的体积百分比为28％，孔隙率为72％。
本实施例第④步中，用于等体积浸渍3克载体的水溶液中碱土金属元素的盐可以是KNO3，其含量是0.090克，其余条件不变，制得的催化剂表示为 8NiO-8Al2O3-2K2O/8-Ni-SMF-600。
实施例8
本实施例提供一种金属泡沫镍载体负载氧化镍-氧化铝-氧化铈催化剂的制备。
①称取镍泡沫金属(表示为Ni-foam)5克，在室温下，移取含粒径为1～10微米的0.3克铝粉的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后，在高纯保护气氛中于600℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应2小时，得到表层合金化的金属相载体；
②将步骤①制得的产品，在室温至60℃下用浓度为15％的氢氧化钠水溶液进行抽铝处理1小时，经蒸馏水冲洗、空气中烘干后，得到表层多孔化的金属镍泡沫载体；
③称取步骤②制得的载体3克，用等体积的含1.528克、0.652克和0.450克的Ni(NO3)2·6H2O、Al(NO3)3·9H2O和Ce(NO3)3·6H2O的水溶液，室温下等体积浸渍载体，100℃烘干后于空气中600℃焙烧2小时，即得到所述的镍泡沫载体负载的氧化镍-氧化铝-氧化铈催化剂，其中NiO、Al2O3和CeO2在催化剂中的重量含量分别为10％、5％和5％，该催化剂表示为10NiO-5Al2O3-5CeO2/Ni-foam-600。
本实施例所制备的10NiO-5Al2O3-5CeO2/Ni-foam-600催化剂的光学照片及扫描电镜(SEM)照片分别见图6、图7。
经宏观测量得知：本实施制备的整体式催化剂10NiO-5Al2O3-5CeO2/Ni-foam-600中，金属镍泡沫骨架所占的体积百分比为20％，孔隙率为80％。
本实施例中金属泡沫材料可以是泡沫白铜(表示为BT-foam)、泡沫铜(表示为Cu-foam)、泡沫铁(表示为Fe-foam)，其余条件不变，所制得的催化剂分别表示为10NiO-5Al2O3-5CeO2/BT-foam-600、10NiO-5Al2O3-5CeO2/Cu-foam-600、10NiO-5Al2O3-5CeO2/Fe-foam-600。
实施例9
本实施例提供一种金属泡沫镍载体负载氧化镍-氧化铝-氧化锰催化剂的制备。
①称取镍泡沫(表示为Ni-foam)金属5克，在室温下，移取含粒径为1～10微米的0.3克铝粉的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后，在高纯保护气氛中于600℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应2小时，得到表层合金化的金属相载体；
②将步骤①制得的产品，在室温至60℃下用浓度为15％的氢氧化钠水溶液进行抽铝处理1小时，经蒸馏水冲洗、空气中烘干后，得到表层多孔化的金属镍泡沫载体；
③称取步骤②制得的载体3克，用等体积的含1.528克、0.652克和0.250克的Ni(NO3)2·6H2O、Al(NO3)3·9H2O和Mn(NO3)2·4H2O的水溶液，室温下等体积浸渍载体， 100℃烘干后于空气中600℃焙烧2小时，即得到所述的镍泡沫载体负载的氧化镍-氧化铝-氧化锰催化剂，其中NiO、Al2O3和MnO2在催化剂中的重量含量分别为10％、5％和5％，该催化剂表示为10NiO-5Al2O3-5MnO2/Ni-foam-600。
本实施例第③步中，用于等体积浸渍3克载体的水溶液可以是含1.528克、0.652克和0.250克的Ni(NO3)2·6H2O、Al(NO3)3·9H2O和Mo(NO3)3.5H2O的水溶液，室温下等体积浸渍载体，100℃烘干后于空气中600℃焙烧2小时，其余条件不变，即得到所述的镍泡沫载体负载的氧化镍-氧化铝-氧化钼催化剂，其中NiO、Al2O3和MoO3在催化剂中的重量含量分别为10％、5％和5％，该催化剂表示为10NiO-5Al2O3-5MoO3/Ni-foam-600。
本实施例第③步中，首先用等体积的含1.528克和0.652克的Ni(NO3)2·6H2O和Al(NO3)3·9H2O的水溶液，室温下等体积浸渍3克载体，100℃烘干后，用等体积的含0.230克Na2WO4·2H2O的水溶液再次等体积浸渍后，于100℃烘干和空气中600℃焙烧2小时，其余条件不变，即得到所述的镍泡沫载体负载的氧化镍-氧化铝-氧化钨-氧化钠催化剂，其中NiO、Al2O3、WO3和Na2O在催化剂中的重量含量分别为10％、5％、4％和1％，该催化剂表示为10NiO-5Al2O3-4WO3-1Na2O/Ni-foam-600。
本申请的发明人发现，本发明以多孔金属相载体负载NiO等所得催化剂在催化性能和导热性能上都明显优于Al2O3等氧化物载体负载的NiO基催化剂。下面是本申请的发明人所做的用于对比实验的催化剂。
对比例1
称取1.438g的Ni(NO3)2·6H2O和1.198g的Mg(NO3)2·6H2O溶于4毫升水中配成水溶液，在室温下将3.0g干燥γ-Al2O3以等体积浸渍法浸渍于配制的硝酸镍和硝酸镁混合水溶液中12小时后，在120℃干燥后，在空气氛中于550℃焙烧2小时，即得到MgO改性的氧化铝负载的氧化镍催化剂，其中NiO和MgO在催化剂中的重量含量分别为10％和5％，表示为10NiO-5MgO/γ-Al2O3。
应用例1
在固定床反应器上考察了本发明催化剂在不同反应条件下对一氧化碳甲烷化反应的催化性能，反应原料是一氧化碳和氢气，一氧化碳和氢气的摩尔比为1∶3。固定床反应器是一个内径为16毫米的石英管，一氧化碳和氢气在进入反应管之前进行混合，混合均匀后进入催化剂床层进行反应。反应产物经冷阱冷凝后气相产物进入色谱，利用热导池检测器(TCD)进行分析。
本应用例在实施例1制得的10NiO-10Al2O3/8-Ni-SMF-450催化剂上进行，催化剂用量为0.482克，体积约为1.25毫升，所采用的反应条件及转化率和选择性分别列于表1。
表1反应温度、气时空速对实施例1制得催化剂10NiO-10Al2O3/8-Ni-SMF-450催化CO甲烷化性能的影响
反应温度(℃) 原料气空速(h-1) CO转化率(％) CH4选择性(％)
250 2500 85.9 91.5
250 5000 91.9 86.8
250 10000 96.7 84.3
400 2500 99.3 92.8
400 5000 99.1 90.7
400 10000 98.2 86.8
550 2500 84.1 80.8
550 5000 83.6 82.5
550 10000 75.3 78.4
应用例2
在固定床反应器上考察了本发明催化剂在不同反应条件下对二氧化碳甲烷化反应的催化性能，反应原料是二氧化碳和氢气，二氧化碳和氢气的摩尔比为1∶4。固定床反应器是一个内径为16毫米的石英管，二氧化碳和氢气在进入反应管之前进行混合，混合均匀后进入催化剂床层进行反应。反应产物经冷阱冷凝后气相产物进入色谱，利用热导池检测器(TCD)进行分析。
本应用例在实施例1制得的10NiO-10Al2O3/8-Ni-SMF-450催化剂上进行，催化剂用量为0.482克，体积约为1.25毫升，所采用的反应条件及转化率和选择性分别列于表2。
表2反应温度、气时空速对实施例1制得催化剂10NiO-10Al2O3/8-Ni-SMF-450催化CO2甲烷化性能的影响
反应温度(℃) 原料气空速(h-1) CO2转化率(％) CH4选择性(％)
250 2500 52.7 99.65
250 5000 46.2 99.85
250 10000 35.5 99.92
400 2500 91.3 99.6
400 5000 81.8 99.0
400 10000 76.5 97.4
550 2500 72.6 82.1
550 5000 67.2 75.6
550 10000 64.6 69.5
应用例3
反应装置、反应原料、催化剂用量同应用例1。
本应用例在气时空速5000h-1和反应温度350℃条件下，考察了实施例催化剂的一氧化碳甲烷化催化反应性能，结果列于表3。
表3各实施例和对比例催化剂的一氧化碳甲烷化催化性能
Figure PCTCN2015000020-appb-000001
应用例4
在固定床反应器上考察了本发明的催化剂在不同条件下对一氧化碳和二氧化碳共甲 烷化反应的催化性能，反应原料是一氧化碳、二氧化碳、甲烷和氢气的混合气，一氧化碳、二氧化碳、甲烷和氢气的摩尔比为17∶20∶10∶53。固定床反应器是一个内径为16毫米的石英管，一氧化碳、二氧化碳、甲烷和氢气在进入反应管之前进行混合，混合均匀后进入催化剂床层进行反应。反应产物经冷阱冷凝后气相产物进入色谱，利用热导池检测器(TCD)进行分析。
本应用例在实施例2制得的10NiO-5Al2O3/8-Cu-SMF-300催化剂上进行，催化剂用量为1.053克，体积约为1.61毫升，所采用的反应条件及转化率分别列于表4。二氧化碳的转化率为负值表示二氧化碳没有转化，新生成部分二氧化碳。
表4反应温度、气时空速对实施例2制得催化剂10NiO-5Al2O3/8-Cu-SMF-300催化性能的影响
反应温度(℃) 原料气空速(h-1) CO转化率(％) CO2转化率(％)
350 5000 95.4 -8.9
350 10000 91.8 -7.8
350 15000 87.4 -6.0
450 5000 82.8 -4.0
450 10000 75.2 -2.0
450 15000 66.5 1.7
550 5000 33.5 9.0
550 10000 24.3 14.1
550 15000 17.0 18.4
应用例5
在固定床反应器上考察了本发明的催化剂在不同条件下对甲烷和二氧化碳重整反应的催化性能，反应原料是二氧化碳和甲烷的混合气，甲烷、二氧化碳的摩尔比为1∶1。固定床反应器是一个内径为16毫米的石英管，甲烷和二氧化碳在进入反应管之前进行混合，混合均匀后进入催化剂床层进行反应。反应产物经冷阱冷凝后气相产物进入色谱，利用热导池检测器(TCD)进行分析。
本应用例在实施例5制得的5NiO-5Al203-2.5CeO2/8-Ni-SMF-500催化剂上进行，催化剂用量为1.216克，体积约为1.92毫升，所采用的反应条件及转化率分别列于表5。
表5反应温度、气时空速对实施例5催化剂5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500催化性能的影响
反应温度(℃) 原料气空速(h-1) CH4转化率(％) CO2转化率(％)
750 3000 72.0 74.3
750 6000 59.9 72.6
750 9000 42.8 62.2
800 3000 87.0 91.8
800 6000 84.8 86.7
800 9000 68.9 80.7
850 3000 93.6 95.4
850 6000 93.2 94.4
850 9000 88.5 92.1
应用例6
在固定床反应器上考察了本发明的催化剂在不同条件下对甲烷自热重整反应的催化性能，反应原料是甲烷、水蒸气和氧气的混合气，甲烷、水蒸气和氧气的摩尔比为3∶10∶2。固定床反应器是一个内径为16毫米的石英管，甲烷、水蒸气和氧气在进入反应管之前进行混合，混合均匀后进入催化剂床层进行反应。反应产物经冷阱冷凝后气相产物进入色谱，利用热导池检测器(TCD)进行分析。
本应用例在实施例6制得的8NiO-8Al2O3-2MgO/8-Ni-fiber-600催化剂上进行，催化剂用量为1.139克，体积约为1.76毫升，所采用的反应条件及转化率和选择性分别列于表6。
表6反应温度、气时空速对实施例6催化剂8NiO-8Al2O3-2MgO/8-Ni-fiber-600催化性能的影响
反应温度(℃) 原料气空速(h-1) CH4转化率(％) CO选择性(％)
650 3000 74.3 93.6
650 6000 70.6 92.9
650 9000 64.8 92.4
750 3000 88.2 95.2
750 6000 85.3 94.9
750 9000 81.9 95.1
850 3000 96.8 97.8
850 6000 94.3 97.2
850 9000 92.4 96.4
应用例7
本实施例是通过CFD模拟对比说明本发明的催化剂的高导热性对强化反应移热、消除高温热点的优异效果。
反应装置、反应原料、催化剂用量同应用例1。
本应用例在实施例6制得的8NiO-8Al2O3-2MgO/8-Ni-fiber-600催化剂上进行，反应温度350℃、气时空速10000h-1、一氧化碳和氢气的摩尔比为1∶3，一氧化碳转化率为95％、甲烷选择性为91％。在相同反应条件下，对比例1所制催化剂10NiO-5MgO/γ-Al2O3上，一氧化碳转化率为98％、甲烷选择性为85％。利用CFD软件fluent对反应器内的温度分布进行数值模拟，颗粒床(10NiO-5MgO/γ-Al2O3)和金属纤维结构化催化剂(8NiO-8Al2O3-2MgO/8-Ni-fiber-600)反应器内的温度分布见图8。由图8可见，本发明催化剂由于具有良好的导热性，催化剂床层中心的热点温度仅为110℃；然而，传统的氧化物载体催化剂床层中心的热点温度高达400℃。
应用例8
反应装置、反应原料、催化剂用量同应用例1。
本应用例在实施例5制得的5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500催化剂上，以一氧化碳和氢气的摩尔比为1∶3的混合气为原料，考察了催化一氧化碳甲烷化反应的1000小时稳定性，结果见图9。
应用例9
反应装置、反应原料同应用例1，催化剂用量10.4毫升。
本应用例在实施例5制得的5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500催化剂上，以一氧化碳和氢气的摩尔比为1∶3的混合气为原料，在330℃反应温度和5000h-1气时空速下，考察了催化一氧化碳甲烷化反应的3000小时稳定性，结果见图10。由图10可见，本发明催化剂对一氧化碳甲烷化具有优异的反应稳定性以及活性和选择性。
应用例10
反应装置、反应原料同应用例1，催化剂用量10.2毫升。
本应用例在实施例5制得的5NiO-5Al2O3-2.5CeO2/8-Ni-SMF-500催化剂上进行，以二氧化碳和氢气的摩尔比为1∶4的混合气为原料，在320℃反应温度和5000h-1气时空速下，考察了催化二氧化碳甲烷化的1000小时稳定性，结果见图11。由图11可见，本发明催化 剂对二氧化碳甲烷化具有优异的反应稳定性以及活性和选择性。
工业实用性
本发明所涉及的催化剂能够被应用于化工领域。

Claims (12)

  1. 一种金属相载体负载型催化剂，包括负载于金属相载体的活性组分金属氧化物和助剂金属氧化物并具有通式xM1O-yM2O/ZT，其中M1O表示活性组分金属氧化物，M2O表示助剂金属氧化物，ZT表示金属相载体，x表示活性组分金属氧化物所占催化剂的质量百分数，y表示助剂金属氧化物占催化剂的质量百分数。
  2. 根据权利要求1所述的催化剂，其特征在于：所述质量百分数x为1～15％，所述质量百分数y为1～15％，所述催化剂的其余成分为所述金属相载体。
  3. 根据权利要求1所述的催化剂，其特征在于：所述金属相载体ZT为金属镍、金属铜、金属铁或金属白铜。
  4. 根据权利要求1所述的催化剂，其特征在于：所述金属相载体是直径为4～150微米、长度为2～10毫米的纤维、或由该纤维烧结而成的三维多孔结构整体式金属纤维载体或三维多孔结构整体式金属泡沫载体。
  5. 根据权利要求4所述的催化剂，其特征在于：所述金属相载体的金属骨架占所述金属相载体的体积百分比为5～40％，余下的为孔隙率。
  6. 根据权利要求1所述的催化剂，其特征在于：活性组分金属氧化物M1O为镍和铁的氧化物中的至少一种。
  7. 根据权利要求1所述的催化剂，其特征在于：助剂金属氧化物M2O为铝、铈、镧、钼、锰、钨、镁、钙、钠、钾的氧化物中的至少一种。
  8. 一种用于制备金属相载体负载型催化剂的方法，包括如下步骤：
    ①用含铝粉的悬浊液等体积浸渍金属相载体并干燥使铝粉颗粒分散在金属相载体表面后，于550～650℃下使铝粉颗粒与金属相载体表层进行固-固合金化反应，得到表层合金化的金属相载体；
    ②将步骤①制得的表层合金化的金属相载体，在60℃以下的温度下用浓度为5～20％的盐酸或氢氧化钠水溶液进行抽铝处理，经冲洗、烘干，得到表层多孔化的金属相载体；
    ③将步骤②制得的表层多孔化的金属相载体，等体积浸渍于含活性组分M1金属元素的盐和助剂组分M2金属元素的盐的水溶液，经烘干后在300～600℃下焙烧，即得到所述的金属相载体负载型催化剂。
  9. 根据权利要求8所述的催化剂方法，其特征在于，在所述金属相载体表层合金化过程中，所述铝粉的粒径为1～10微米，铝粉/金属相载体的质量比为0.5～10/100。
  10. 将权利要求1所述的或根据权利要求8制备的金属相载体负载型催化剂用作为一氧化碳或(和)二氧化碳加氢合成甲烷的反应的催化剂的用途。
  11. 将权利要求1所述或根据权利要求8制备的金属相载体负载型催化剂的用作为甲烷制备合成气的反应的催化剂的用途。
  12. 根据权利要求11所述的用途，其特征在于：所述甲烷制备合成气的反应是甲烷-二氧化碳重整或甲烷自热重整制备合成气的反应。
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