WO2019134424A1 - 用于燃料电池中甲烷蒸汽重整的催化剂 - Google Patents

用于燃料电池中甲烷蒸汽重整的催化剂 Download PDF

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WO2019134424A1
WO2019134424A1 PCT/CN2018/111870 CN2018111870W WO2019134424A1 WO 2019134424 A1 WO2019134424 A1 WO 2019134424A1 CN 2018111870 W CN2018111870 W CN 2018111870W WO 2019134424 A1 WO2019134424 A1 WO 2019134424A1
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catalyst
oxide
nickel
fuel cell
methane
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PCT/CN2018/111870
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English (en)
French (fr)
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华波
麦景红
刘阳
曾斌
谢昊
彭国建
刘卫东
杜勇
古岚
郭游博
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四川天一科技股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the technical field of catalysts, and more particularly to a catalyst for use in a fuel cell, in particular for steam reforming of methane in a molten carbonate fuel cell.
  • a molten carbonate fuel cell (“MCFC”) is a high temperature fuel cell that generates electricity through an electrochemical reaction between a cathode, an anode, and an electrolyte master between the cathode and the anode.
  • a molten eutectic for example, a molten eutectic composed of lithium carbonate and potassium carbonate
  • a carrier material for example, a membrane carrier composed of LiAlO 2 /Al 2 O 3
  • the hydrogen required for fuel cell operation can be produced directly in the cell by a methane steam reforming reaction.
  • the steam reforming reaction of methane is shown in the following example: CH4+H2O ⁇ CO+3H2(1)CO+H2O ⁇ CO2+H2(2)
  • the first reaction has strong endothermicity and can be directly consumed by electrochemical reaction.
  • the reaction is a catalytic reaction requiring the use of a reforming catalyst, and natural gas (also optionally methane, petroleum gas, naphtha, heavy oil or crude oil) can be used as a starting material for fuel cell operation.
  • the hydrogen required for fuel cell operation comes from two parts, one part is partially reformed by the pre-reformer outside the fuel cell, and part of the generated hydrogen can be used immediately after entering the battery, and another part of methane steam is reformed in the fuel cell.
  • This is called direct internal reforming (DIR).
  • DIR direct internal reforming
  • molten carbonate fuel cell at 580 ° C to 675 ° C
  • alkali metal compound such as KOH, NaOH or LiOH.
  • These alkali metal ions can be deposited on the reforming catalyst, and the catalyst is deactivated by poor poisoning.
  • Catalyst poisoning is one of the key factors affecting the life of the battery pack. Therefore, even if the initial activity of the conventional catalyst is good, there is a technical problem that the activity is degraded rapidly after poisoning, and the stability of the activity is poor, not to mention the fact that some catalysts are not active.
  • a homogeneous catalyst having a single phase perovskite oxide, wherein at least one doping element of the ABO3 perovskite type oxide site A and/or site B is substituted is disclosed in US Pat.
  • the wettability with the liquid molten carbonate electrolyte may be lowered.
  • the catalyst may have higher catalytic activity, inhibit catalyst poisoning caused by leakage and evaporation of the liquid molten carbonate electrolyte, maintain high reactivity for a long period of time, achieve high methane conversion rate, and produce a synthesis gas having a high hydrogen ratio.
  • the catalyst of the patent is prepared by a solid state mixing method.
  • the catalyst prepared by the preparation method is unstable in structure, and the strength and the specific surface decrease rapidly after the reduction. As the catalyst strength and the specific surface decrease, the activity of the catalyst rapidly decreases, thereby leading to activity stability. Poor.
  • a catalyst composition for methane steam reforming in a fuel cell, particularly for direct internal reforming of methane in a molten carbonate fuel cell, and a catalyst material made therefrom are disclosed in US 2013/0116118 Al. And a method of producing the catalyst compound.
  • the activity rate is low and the alkali metal ion has high stability.
  • the catalyst of the patent is prepared by a precipitation method, and the prepared catalyst has an unstable structure, and the strength and the specific surface decrease rapidly after the reduction. As the catalyst strength and the specific surface decrease, the activity of the catalyst rapidly decreases, resulting in poor activity stability.
  • the present invention provides a catalyst for steam reforming of methane in a molten carbonate fuel cell, which has a composition of oxides of nickel, aluminum, zirconium and hafnium (rare earth element) and has good alkali resistance.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell which has a composition of oxides of nickel, aluminum, zirconium and hafnium (rare earth element) and has good alkali resistance.
  • the ability of metal poisoning, high specific surface to enhance catalyst activity, reasonable pore structure further improve the ability of the catalyst to resist alkali metal poisoning, the catalyst has high stability; its strength, specific surface and pore structure change before and after use. Small, so that the stability of the activity prolongs the service life of the catalyst and meets the ever-increasing commercial target level.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell which is characterized in that it comprises a regular granular carrier made of an oxide of aluminum, zirconium and hafnium, and then loaded An oxide of nickel is applied to finally form a particulate catalyst formed of oxides of nickel, aluminum, zirconium and hafnium.
  • the particulate catalyst is a cylindrical particulate catalyst having a diameter of 1-3 mm and a height of 0.5-5 mm.
  • the catalyst comprises the following mass percentage components: nickel oxide 35-60%, alumina 30-50%, zirconia 1-15%, lanthanum oxide 1-15%, total mass content 100%.
  • the catalyst comprises the following mass percentage components: nickel oxide 35-55%, alumina 35-50%, zirconia 6-10%, cerium oxide 4-5%, total mass content 100%.
  • the catalyst comprises the following mass percentage components: nickel oxide 40%, alumina 46%, zirconia 9%, and cerium oxide 4.5%, with the balance being impurities.
  • the raw materials of the alumina, zirconia, cerium oxide and nickel oxide are alumina powder, zirconia powder, cerium oxide powder and nickel nitrate solution, and the mass ratio of the alumina powder, the zirconia powder and the cerium oxide powder is 7- 11:43-47:4-5.
  • Zirconium oxide is made of high-purity ultrafine zirconia powder (monoclinic phase)
  • alumina is made of high-purity ultrafine activated alumina powder
  • cerium oxide is made of high-purity ultrafine cerium oxide (rare earth) powder.
  • the purity of the three raw materials is 90-99.9%.
  • d 50 is from 0.5 to 50 ⁇ m.
  • the nickel nitrate solution has a concentration of 0.1-lmol/L. The lower the concentration of the solution, the less active ingredient is loaded on the carrier each time, and the concentration of the solution is selected according to the amount of active component required to be loaded.
  • the catalyst has a nickel oxide content of ⁇ 35%.
  • Average pore diameter of the catalyst The pore volume is 0.2-0.5 ml/g.
  • the large pore size is not easily blocked by the alkali metal of the electrolyte, and the abundant pores can continuously provide the active channel of the reforming reaction and improve the activity stability of the catalyst.
  • the catalyst has a specific surface area greater than 45 m 2 /g and a loss on ignition at 900 ° C of less than 5%.
  • the specific surface is guaranteed to provide sufficient active surface.
  • the cerium may be replaced by other rare earth elements, and any other rare earth element is any one of cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum or cerium.
  • the method for preparing a catalyst for methane steam reforming in a fuel cell in the present invention is formed by a ball milling mixture, a powder molding, a pretreatment, a carrier calcination, and an immersion decomposition step, and then a dipping method. That is, a catalyst carrier is prepared first, and then the active component is supported on the carrier to form a catalyst carrier.
  • the preparation method of the catalyst for methane steam reforming in a molten carbonate fuel cell of the present invention comprises the following steps:
  • Ball-milling mixture crushing and mixing three kinds of oxide powders of aluminum, zirconium and hafnium (rare earth elements); uniformly mixing different materials and further crushing, which is favorable for generation in pretreatment and calcination Stable crystal phase.
  • step 2 The powder in step 1 is made into small particles, which are then pressed into pellets of a predetermined shape to meet the filling size requirements of the fuel cell device.
  • the prescribed shape is determined by the fuel cell device, and the size of the fuel cell device must be filled.
  • the oversized or undersized size cannot be incorporated into the fuel cell device.
  • Pretreatment The particles of the prescribed shape prepared in the step (2) are subjected to a new stable pore structure and a crystal phase structure during the pretreatment.
  • step (3) the particles pretreated in step (3) are calcined at a high temperature to form a carrier;
  • Impregnation decomposition The step (4) carrier is immersed in a nickel nitrate solution, and the active component is attached to the carrier, followed by drying and pyrolysis.
  • the mixing time is from 1 to 12 h, preferably from 1 to 8 h, particularly preferably from 6 to 8 h.
  • the small particle size is 10-500 mesh, preferably 60-400 mesh, particularly preferably 120-320 mesh; the particle size mainly affects the uniformity of the product after molding, and the 120-320 mesh particle is more favorable. Enter the press mold.
  • the temperature is 50 to 700 ° C, preferably 100 to 600 ° C, and particularly preferably 200 to 500 ° C.
  • the pretreatment is carried out at a pressure of from 0.01 to 2.0 MPa, preferably from 0.1 to 1.5 MPa, particularly preferably from 1 to 1.5 MPa, a residence time of from 1 to 24 h, preferably from 5 to 12 h, particularly preferably from 6 to 8 h, such that aluminum, zirconium and The three oxides of yttrium interact to form a new crystalline phase structure, while at the same time forming a new stable pore structure during the pretreatment process.
  • the calcination temperature is >675 ° C, preferably the calcination temperature is ⁇ 700 ° C, particularly preferably the calcination temperature is 750 ° C, and the calcination temperature is 1400 ° C, preferably the calcination temperature is ⁇ 1350 ° C, particularly preferably the calcination temperature ⁇ 1300 ° C, calcination time ⁇ 30 min, preferably calcination time ⁇ 40 min, particularly preferably calcination time ⁇ 50 min, and calcination time ⁇ 10 h, preferably calcination time ⁇ 8 h, particularly preferably calcination time ⁇ 6 h.
  • the carrier has a specific surface area of >70 m 2 /g.
  • the specific surface is guaranteed to provide sufficient active surface.
  • the immersion temperature is 60-90 ° C, preferably the immersion temperature is 70-90 ° C, particularly preferably the immersion temperature is 80-90 ° C, the immersion time ⁇ 5 minutes, preferably the immersion time ⁇ 10 minutes, particularly preferably The immersion time is ⁇ 15 minutes, and the immersion time is ⁇ 2 hours, preferably the immersion time ⁇ 1.6 hours, particularly preferably the immersion time ⁇ 1.5 hours.
  • the concentration of the nickel nitrate solution is 0.1-l mol/L.
  • the carrier is taken out, and the elevated temperature is dried, wherein the drying temperature is
  • drying temperature ⁇ 100 ° C preferably drying temperature ⁇ 110 ° C
  • drying time is 10 min - 10 h, preferably drying time is 20 min - 8 h, particularly preferably drying time is 30 min - 4 h.
  • the decomposition temperature in the step (5) is >150 ° C, preferably the decomposition temperature is ⁇ 200 ° C, particularly preferably the decomposition temperature
  • decomposition time is ⁇ 8 h, and particularly preferably the decomposition time is ⁇ 6 h.
  • the pore size is large and the pore structure is stable, and the large pore diameter is not easily blocked by the alkali metal of the electrolyte, and the active channel for continuously providing the reforming reaction can be continuously provided;
  • Aluminum, lanthanum (rare earth element) and zirconium work together to displace the carrier grains and increase the active center, which improves the overall activity of the catalyst.
  • Figure 1 is a comparison diagram of pore size of different catalysts in the present invention
  • Figure 2 is a comparison diagram of methane conversion rate in the present invention
  • Figure 3 is a comparison chart before and after poisoning in the present invention
  • Figure 4 is a comparison diagram of the catalyst before and after poisoning in the present invention
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements). Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is greater than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the catalyst comprises the following mass percentage components: nickel oxide 37%, alumina 48%, zirconia 10%, cerium oxide (rare earth element) 5%.
  • the particulate catalyst was a cylindrical particulate catalyst having a diameter of 1 mm and a height of 0.5 mm.
  • the raw materials of alumina, zirconia, cerium oxide and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and the concentration of nickel nitrate solution is 1 mol/L.
  • a method for preparing a catalyst for steam reforming of methane in a fuel cell is carried out by a ball milling mixture, a powder molding, a pretreatment, a carrier calcination, and an immersion decomposition step, followed by a dipping method. That is, a catalyst carrier is prepared first, and then the active component is supported on the carrier to form a catalyst carrier.
  • Ball-milling mixture three kinds of oxide powders of aluminum, zirconium and hafnium (rare earth elements) are added to the ball mill according to the required ratio, and the three kinds of oxide powders are further broken and fully mixed by ball milling, and the mixing time is 1- 12 hours.
  • Powder molding the powder prepared in the step (1) is passed through a granulator to form a fine particle material having a uniform particle size, and the particle size is selected to have a particle size of 10 to 500 mesh, preferably 60 to 400 mesh, particularly preferably 120.
  • the -320 mesh fine particulate material is added to a rotary tablet press or a hydroformed tablet press to be pressed into pellets of a prescribed shape.
  • the particle size mainly affects the uniformity of the product after molding, and the 120-320 mesh particles are more favorable for entering the pressing mold. Products that are too large or too small to enter the mold are not uniform.
  • the predetermined shape of the particles prepared in the step (2) is pretreated at a temperature of 100-600 ° C and a pressure of 0.2-1.0 MPa for 6-18 hours to make aluminum, zirconium and hafnium.
  • the three oxides interact to form a new crystalline phase structure while simultaneously forming a new stable pore structure during the pretreatment process.
  • Carrier calcination the particles of the specified shape prepared in the step (3) are calcined at a high temperature, calcined at a temperature of 675 ° C to 1400 ° C, and calcined for 30 minutes to 10 hours, so that the specific surface area and pore size of the carrier after calcination are required.
  • the specific surface area is greater than 70 m 2 /g.
  • Impregnation decomposition the carrier prepared in the step (4) is immersed in a nickel nitrate solution, the immersion temperature is 60-90 ° C, the immersion time is 5 minutes - 2 hours, and the concentration of the nickel nitrate solution is 0.11 mol/L. .
  • the support is taken out and the elevated temperature is dried, wherein the temperature is at least 90 ° C and the time is from 10 minutes to 10 hours.
  • the carrier after drying is further elevated in temperature, and the nitrate is decomposed by high temperature to remove nitrate, leaving an oxide of nickel, a decomposition temperature of 150-700 ° C, and a decomposition time of 30 minutes to 10 hours.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and the concentration of nickel nitrate solution is 0.1 mol/L.
  • the preparation method is as in Example 1, wherein the catalyst comprises the following mass percentage components: nickel oxide 42%, alumina 42%, zirconia 12%, cerium oxide (rare earth element) 4%.
  • the particulate catalyst was a cylindrical particulate catalyst having a diameter of 3 mm and a height of 5 mm.
  • the nickel oxide is detected by chemical analysis, and if the nickel oxide content is less than 40% (mass percentage), the step (5) in the preparation method is repeated.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is greater than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and the concentration of nickel nitrate solution is 0.5 mol/L.
  • the preparation method is as in Example 1, wherein the catalyst comprises the following mass percentage components: nickel oxide 40%, alumina 46%, zirconia 9%, and cerium oxide (rare earth element) 4.5%, the balance being impurities.
  • the particulate catalyst was a cylindrical particulate catalyst having a diameter of 2 mm and a height of 3 mm.
  • the nickel oxide is detected by chemical analysis, and if the nickel oxide content is less than 35% (mass percentage), the step (5) in the preparation method is repeated.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium.
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and the concentration of nickel nitrate solution is 0.6 mol/L.
  • the preparation method is as in Example 1, wherein the catalyst comprises the following mass percentage components: nickel oxide 38%, alumina 47%, zirconia 11%, cerium oxide (rare earth element) 4%.
  • the particulate catalyst was a cylindrical particulate catalyst having a diameter of 3 mm and a height of 0.5 mm.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and the concentration of nickel nitrate solution is 0.4 mol/L.
  • the preparation method is as in Example 1, wherein the catalyst comprises the following mass percentage components: nickel oxide 41%, alumina 43%, zirconia 11%, cerium oxide (rare earth element) 5%.
  • the particulate catalyst was a cylindrical particulate catalyst having a diameter of 1 mm and a height of 5 mm.
  • the nickel oxide is detected by chemical analysis, and if the nickel oxide content is less than 40% (mass percentage), the step (5) in the preparation method is repeated.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and the concentration of nickel nitrate solution is 0.8 mol/L.
  • the preparation method is as in Example 1, wherein the catalyst comprises the following mass percentage components: nickel oxide 41.5%, alumina 48%, zirconia 7%, cerium oxide (rare earth element) 3.5%.
  • the nickel oxide is detected by chemical analysis, and if the nickel oxide content is less than 40% (mass percentage), the step (5) in the preparation method is repeated.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia and cerium oxide (rare earth) nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and the concentration of nickel nitrate solution is 0.9 mol/L.
  • the preparation method is as in Example 1, wherein the catalyst comprises the following mass percentage components: nickel oxide 41%, alumina 48%, zirconia 6%, cerium oxide (rare earth element) 5%.
  • the nickel oxide is detected by chemical analysis, and if the nickel oxide content is less than 40% (mass percentage), the step (5) in the preparation method is repeated.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and alumina powder, zirconia powder and cerium oxide.
  • the mass ratio of the (rare earth element) powder was 7:43:4, and the nickel nitrate solution concentration of nickel oxide was 0.2 mol/L.
  • Zirconium oxide is made of high-purity ultrafine zirconia powder (monoclinic phase)
  • alumina is made of high-purity ultrafine activated alumina powder
  • cerium oxide is made of high-purity ultrafine cerium oxide (rare earth) powder.
  • the preparation method is as in Example 1.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and alumina powder, zirconia powder and cerium oxide.
  • the mass ratio of the (rare earth element) powder was 11:47:5, and the nickel nitrate solution concentration of nickel oxide was 0.7 mol/L.
  • Zirconium oxide is made of high-purity ultrafine zirconia powder (monoclinic phase)
  • alumina is made of high-purity ultrafine activated alumina powder
  • cerium oxide is made of high-purity ultrafine cerium oxide (rare earth) powder.
  • the preparation method is as in Example 1.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium.
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and alumina powder, zirconia powder and cerium oxide.
  • the mass ratio of the (rare earth element) powder is 7-11:43-47:4-5, and the nickel nitrate solution concentration of nickel oxide is 0.7 mol/L.
  • Zirconium oxide is made of high-purity ultrafine zirconia powder (monoclinic phase)
  • alumina is made of high-purity ultrafine activated alumina powder
  • cerium oxide is made of high-purity ultrafine cerium oxide powder.
  • the preparation method is as in Example 1.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and alumina powder, zirconia powder and cerium oxide.
  • the mass ratio of the (rare earth element) powder was 9:45:4.5, and the nickel nitrate solution concentration of nickel oxide was 0.7 mol/L.
  • Zirconium oxide is made of high-purity ultrafine zirconia powder (monoclinic phase)
  • alumina is made of high-purity ultrafine activated alumina powder
  • cerium oxide is made of high-purity ultrafine cerium oxide (rare earth) powder.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the raw materials of alumina, zirconia, cerium oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, cerium oxide (rare earth element) powder and nickel nitrate solution, and alumina powder, zirconia powder and cerium oxide.
  • the mass ratio of the (rare earth element) powder was 10:44:5, and the nickel nitrate solution concentration of nickel oxide was 0.7 mol/L.
  • Zirconium oxide is made of high-purity ultrafine zirconia powder (monoclinic phase)
  • alumina is made of high-purity ultrafine activated alumina powder
  • cerium oxide is made of high-purity ultrafine cerium oxide (rare earth) powder.
  • the preparation method is as in Example 1.
  • a catalyst for steam reforming of methane in a molten carbonate fuel cell comprising a structured particulate support made of an oxide of aluminum, zirconium and hafnium (rare earth element), further loaded with an oxide of nickel, and finally formed with nickel, A regular particulate catalyst formed from oxides of aluminum, zirconium and hafnium (rare earth elements).
  • Average pore diameter of catalyst The pore volume is 0.2-0.5 ml/g, the specific surface area is more than 45 m 2 /g, and the loss on ignition at 900 ° C is less than 5%.
  • the preparation method is as in Example 1.
  • Example 1 shows that the catalyst comprises the following mass percent components: nickel oxide 55%, alumina 35%, zirconia 6%, cerium oxide 4%.
  • Example 1 shows that the catalyst comprises the following mass percent components: nickel oxide 60%, alumina 30%, zirconia 3%, yttria 7%.
  • Example 1 wherein the catalyst comprises the following mass percent components: nickel oxide 36%, alumina 42%, zirconia 12%, yttrium oxide 10%.
  • Example 1 wherein the catalyst comprises the following mass percent components: nickel oxide 36%, alumina 45%, zirconia 4%, yttrium oxide 15%.
  • the pore size distribution of the comparative sample and the catalyst of the present invention was measured by mercury intrusion method according to ASTM UOP 578-02, using a contact angle of 140 ° and a pressure ranging from 0.6 to 60,000 psig, as shown in Fig. 1.
  • the present invention has a larger pore diameter than the comparative sample, and provides an active channel for the reforming reaction.
  • the alkali metal of the electrolyte is less likely to cause clogging of the pore diameter, so that the catalyst activity is not lowered.
  • the comparative sample and the catalyst of the present invention were taken for poisoning test, wherein the comparative sample was the comparative sample in Test 1.
  • Test process under normal pressure, the catalyst bed is heated by N2. When the bed temperature rises to 550 °C, H2 is introduced for reduction; after the reduction is completed, water is pumped through the advection pump to drive into the water catalyst bed. After the layer was stabilized at 550 ° C, CO 2 was introduced , and the temperature of the catalyst bed layer continued to rise to 650 ° C. After stabilization, N 2 was turned off, and CH 4 was passed to conduct initial activity measurement of the catalyst.
  • the reactor was cooled to room temperature, and the test gas was re-introduced through the electrolyte layer under an inert gas (N 2 ), and the time was started after the temperature of the electrolyte layer was raised to 650 ° C, and analyzed once every 4 hours during the poisoning test.
  • N 2 inert gas
  • the catalyst of the present invention has a relatively stable methane conversion activity throughout the test period.
  • the initial methane conversion of the comparative catalyst is slightly higher than the initial methane conversion of the catalyst of the present invention, but after initial poisoning by alkali metal hydroxide or alkali metal carbonate vapor, the initial methane conversion decreases, after about 100 hours, The initial methane conversion is lower than the methane conversion of the catalyst of the present invention.
  • the structure of the catalyst in the present invention is stable, and the pore diameter changes little before, after, and after poisoning, and particularly after reduction and after poisoning, the pore size and pore distribution are substantially unchanged.
  • the comparative samples changed significantly before, after, and after the toxic pore size and pore distribution, indicating that the catalyst structure was unstable and was greatly affected by temperature and alkali metal.
  • the stable structure of the catalyst of the invention can provide stable pore size and pore distribution for a long time, is more favorable for stability of activity, and improves the service life of the catalyst.
  • the catalyst has a large pore size and a stable pore structure, and the large pore diameter is not easily blocked by the alkali metal of the electrolyte, and can continuously provide an active channel for the reforming reaction; aluminum, lanthanum and zirconium act together to displace the carrier crystal grains and increase the active center. Increases the overall activity of the catalyst.

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Abstract

本发明属于催化剂技术领域，尤其涉及一种用于燃料电池中，特别是用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂,其特征在于：包括铝、锆和镧的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧的氧化物形成的规整颗粒状催化剂。本发明中催化剂孔径大且孔结构稳定，大孔径不容易被电解液的碱金属堵塞，能持续提供重整反应的活性通道；铝、镧(稀土元素)和锆共同作用，使载体晶粒错位，活性中心增多，提高了催化剂的整体活性。

Description

[根据细则26改正11.01.2019]　一种用于燃料电池中甲烷蒸汽重整的催化剂 技术领域
本发明属于催化剂技术领域，尤其涉及一种用于燃料电池中，特别是用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂。
背景技术
熔融碳酸盐燃料电池(“MCFC”)是通过阴极、阳极以及阴极和阳极之间的电解液母板之间的电化学反应产生电力的高温燃料电池。在这类电池中，以载体材料(例如由LiAlO2/Al2O3构成的膜载体)中浸满的碱金属碳酸盐混合熔融物的熔融共晶(例如碳酸锂和碳酸钾组成的熔融共晶)作为电解液。燃料电池工作所需的氢气可通过甲烷蒸汽重整反应在电池中直接产生。甲烷的蒸汽重整反应如下例所示：CH4+H2O→CO+3H2(1)CO+H2O→CO2+H2(2)第一个反应具有强吸热性，并能直接消耗由电化学反应释放的热量。该反应为需要使用重整催化剂的催化反应，可以利用天然气(也可选择甲烷、石油气、石脑油、重油或原油)作为燃料电池工作的起始物料。
目前，燃料电池工作所需氢气来自两个部分，一部分为燃料电池外部的预重整器进行部分重整，产生的部分氢气一旦进入电池即可立即使用，另一部分甲烷蒸汽重整在燃料电池中进行，被称为直接内部重整(DIR)。熔融碳酸盐燃料电池在580℃至675℃下工作期间，观察到部分电解液以碱金属化合物(如KOH、NaOH或LiOH)的形式蒸发。这些碱金属离子可以沉积在重整催化剂上，经不良的毒化使催化剂去活，催化剂中毒是影响电池组寿命的关键因素之一。所以传统催化剂即使初始活性好，但存在着中毒后活性下降较快，活性的稳定性差的技术问题，更不用说存着有些催化剂在活性上不高的情况。
美国专利US 2016/0006040 Al中公开了一种具有单相钙钛矿氧化物的均相催化剂，其中至少取代ABO3钙钛矿型氧化物位点A和/或位点B的一个掺杂元素，使得与液态熔融碳酸盐电解质的润湿性可能降低。所述催化剂可具有较高催化活性，抑制液态熔融碳酸盐电解质漏泄和蒸发引起的催化剂中毒，长时间保持高反应活性，实现高甲烷转化率，并可生产出具有高氢气比例的合成气体。
该专利的催化剂采用固态混合法制备，该制备法制备的催化剂结构不稳定，在还原后强度和比表面下降较快，随着催化剂强度和比表面下降，催化剂活性迅速下降，从而导致活性稳定性较差。
美国专利US 2013/0116118 Al中公开了一种用于燃料电池中甲烷蒸汽重整，特别是用于熔融碳酸盐燃料电池中甲烷直接内部重整的催化剂组合物和由其制成的催化剂材料，以及生产该催化剂化合物的方法。但活率低，同时对碱金属离子具有高稳定性。该专利的催化剂采用沉淀法制备，所制备的催化剂结构不稳定，在还原后强度和比表面下降较快，随着催化剂强度和比表面下降，催化剂活性迅速下降，从而导致活性稳定性较差。
发明内容
为了解决以上技术问题，本发明提供一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，以镍、铝、锆和镧(稀土元素)的氧化物的组成，具有良好的抗碱金属中毒的能力，高的比表面提高催化剂活性，合理的孔结构进一步提高催化剂的抗碱金属中毒的能力，催化剂具有较高的稳定性；其强度、比表面和孔结构，在使用前后变化较小，使活性稳定性延长催化剂使用寿命，达到要求越来越高的商业目标水平。
解决以上技术问题的本发明中的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：包括铝、锆和镧的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后从而形成以镍、铝、锆和镧的氧化物形成的颗粒状催化剂。
所述颗粒状催化剂为直径1-3mm，高度0.5-5mm的圆柱体颗粒状催化剂。
所述催化剂包括以下质量百分比的组分：氧化镍35-60％、氧化铝30-50％、氧化锆1-15％、氧化镧1-15％，总质量含量为100％。
所述催化剂包括以下质量百分比的组分：氧化镍35-55％、氧化铝35-50％、氧化锆6-10％、氧化镧4-5％，总质量含量为100％。
或优化方案中氧化镍37-42％、氧化铝42-48％、氧化锆6-12％、氧化镧3.5-5％，总质量含量为100％；或也可包括以下质量百分比的组分：氧化镍40-42％、氧化铝43-47％、氧化锆7-11％、氧化镧4-5％，总质量含量为100％。
所述催化剂包括以下质量百分比的组分：氧化镍40％、氧化铝46％、氧化锆9％和氧化镧4.5％，其余为杂质。
所述氧化铝、氧化锆、氧化镧和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧粉和硝酸镍溶液，其氧化铝粉、氧化锆粉和氧化镧粉的质量比例为7-11：43-47：4-5。
氧化锆采用高纯超细氧化锆粉(单斜晶相)，氧化铝采用高纯超细活性氧化铝粉，氧化镧采用高纯超细氧化镧(稀土元素)粉，三种原料的纯度为90-99.9％，粒度d 50为0.5～50μm。
所述硝酸镍溶液浓度0.l-lmol/L。溶液浓度越低每次负载在载体上的活性组分越少，根据需要负载的活性组分量选择溶液浓度。
所述催化剂氧化镍质量百分含量≥35％。
所述催化剂平均孔径
Figure PCTCN2018111870-appb-000001
孔容0.2-0.5ml/g。大孔径不容易被电解液的碱金属堵塞，丰富的孔隙能持续提供重整反应的活性通道，提高催化剂的活性稳定性。
所述催化剂比表面积大于45m 2/g，900℃烧失重低于5％。比表面是保证提供足够的活性表面。
所述镧可由其它稀土元素替代，其它稀土元素为铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钇或钪中的任何一种。
本发明中制备用于燃料电池中甲烷蒸汽重整的催化剂的方法，经球磨混料、粉料成型、预处理、载体煅烧和浸渍分解步骤，再采用浸渍法制备工艺而成。即先制备催化剂载体，再在载体上负载活性组分而形成催化剂载体。
本发明中可用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂的制备方法包括以下步骤：
(1)球磨混料：将配比好的铝、锆和镧(稀土元素)的三种氧化物粉末破碎、混合；将不同物料均匀混合，并进一步破碎，有利于在预处理和煅烧时生成稳定的晶相。
(2)粉料成型：将步骤1中粉料制成小颗粒，再压制成规定形状的颗粒，符合燃料电池装置装填尺寸要求。规定形状由燃料电池装置所决定，必须满足燃料电池装置装填尺寸的要求，过大或过小的尺寸都无法装入燃料电池装置中。
(3)预处理：将步骤(2)制备的规定形状的颗粒，经预处理过程中形成新的稳定的孔隙结构及晶相结构。
(4)载体煅烧：将步骤(3)预处理的颗粒高温煅烧形成载体；
(5)浸渍分解：将步骤(4)载体放入硝酸镍溶液中浸渍，将活性组分附着在载体上，再干燥和高温分解即可。
所述步骤(1)中，混合时间为1-12h，优选为1-8h，特别优选为6-8h。
所述步骤(2)中，小颗粒大小为10-500目，优选为60-400目，特别优选120-320目；颗粒大小主要影响成型后产品的均匀性，120-320目的颗粒更有利于进入压制模具中。
所述步骤(3)中，在温度50-700℃，优选为100-600℃，特别优选为200-500℃。压力在0.01-2.0Mpa下，优选为0.1-1.5Mpa，特别优选为1-1.5Mpa，停留时间1-24h，优选为5-12h，特别优选为6-8h的预处理，使铝、锆和镧的三种氧化物相互作用，生成新的晶相结构，同时，在预处理过程中形成新的稳定的孔隙结构。
所述步骤(4)中，煅烧温度>675℃，优选为煅烧温度≥700℃，特别优选为煅烧温度≥750℃，且煅烧温度≤1400℃，优选煅烧温度≤1350℃，特别优选煅烧温度≤1300℃，煅烧时间≥30min，优选煅烧时间≥40min，特别优选煅烧时间≥50min，并且煅烧时间≤10h，优选煅烧时间≤8h，特别优选煅烧时间≤6h。
所述步骤(4)中，载体比表面积>70m 2/g。比表面是保证提供足够的活性表面。
所述步骤(5)中，浸渍温度为60-90℃，优选浸渍温度为70-90℃，特别优选浸渍温度为80-90℃,浸渍时间≥5分钟，优选浸渍时间≥10分钟，特别优选浸渍时间≥15分钟，并且浸渍时间≤2小时，优选浸渍时间≤1.6小时，特别优选浸渍时间≤1.5个小时。
所述步骤(5)中，硝酸镍溶液浓度为0.l-l mol/L。
所述步骤(5)中浸渍完后将载体取出，升高的温度进行干燥处理，其中干燥温度
≥90℃，优选干燥温度≥100℃，特别优选干燥温度≥110℃，干燥时间为10min-10h，优选干燥时间为20min-8h，特别优选干燥时间为30min-4h。
所述步骤(5)中分解温度>150℃，优选分解温度≥200℃，特别优选分解温度
≥250℃，且分解温度≤700℃，优选分解温度≤650℃，特别优选分解温度≤600℃，分解时间≥30min，优选分解时间≥40min，特别优选分解时间≥50min，并且分解时间≤10h，优选分解时间≤8h，特别优选分解时间≤6h。
本发明中有益效果：
(1)孔径大且孔结构稳定，大孔径不容易被电解液的碱金属堵塞，能持续提供重整反应的活性通道；
(2)铝、镧(稀土元素)和锆共同作用，使载体晶粒错位，活性中心增多，提高了催化剂的整体活性。
附图说明
下面结合附图及具体实施方式对本发明做更进一步详细说明：
图1为本发明中不同催化剂孔径大小对比图
图2为本发明中甲烷转化率对比图
图3为本发明中对比样中毒前后对比图
图4为本发明中催化剂中毒前后对比图
具体实施方式
下面结合说明书附图和具体实施方式对本实用新型进行进一步说明：
实施例1
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000002
孔容0.2-0.5ml/g，比表面积大于45m 2/g，900℃烧失重低于5％。催化剂包括以下质量百分比的组分：氧化镍37％、氧化铝48％、氧化锆10％、氧化镧(稀土元素)5％。颗粒状催化剂为直径1mm，高度0.5mm的圆柱体颗粒状催化剂。
其中氧化铝、氧化锆、氧化镧和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，硝酸镍溶液浓度lmol/L。
制备用于燃料电池中甲烷蒸汽重整的催化剂的方法，经球磨混料、粉料成型、预处理、载体煅烧和浸渍分解步骤，再采用浸渍法制备工艺而成。即先制备催化剂载体，再在载体上负载活性组分而形成催化剂载体。
具体制备步骤如下：
(1)球磨混料：将铝、锆和镧(稀土元素)的三种氧化物粉根据要求比例，加入球磨机中，通过球磨将三种氧化物粉进一步破碎并充分混合，混合时间为1-12小时。
(2)粉料成型：将步骤(1)制备的粉料通过制粒机制成颗粒均匀的细小颗粒物料，并选取粒度为颗粒大小为10-500目，优选为60-400目，特别优选120-320目的细小颗粒物料加入到旋转式压片机或液压成型压片机中，压制成规定形状的颗粒。颗粒大小主要影响成型后产品的均匀性，120-320目的颗粒更有利于进入压制模具中。过大或过小的颗粒进入模具所压制的产品都不均匀。
(3)预处理:将步骤(2)制备的规定形状的颗粒，在温度100-600℃，压力在0.2-1.0Mpa下，经过6-18小时停留的预处理，使铝、锆和镧的三种氧化物相互作用，生成新的晶相结构，同时，在预处理过程中形成新的稳定的孔隙结构。
(4)载体煅烧：将步骤(3)制备的规定形状的颗粒，经高温煅烧，煅烧温度675℃-1400℃，煅烧时间30分钟-10小时，使煅烧后载体的比表面积、孔径大小达到要求，比表面积大于70m 2/g。
(5)浸渍分解：将步骤(4)制备的载体，放入到硝酸镍溶液中浸渍，浸渍温度为60-90℃,浸渍时间5分钟-2小时,硝酸镍溶液浓度0.l-l mol/L。浸渍完后将载体取出，升高的温度进行干燥处理，其中温度为至少90℃，时间为10分钟-10小时。对干燥完成后的载体进一步升高温度，将硝酸盐通过高温分解，去除硝酸根，留下镍的氧化物，分解温度150-700℃，分解时间30分钟-10小时。
实施例2
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000003
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，硝酸镍溶液浓度0.lmol/L。
制备方法如实施例1中内容，其中催化剂包括以下质量百分比的组分：氧化镍42％、氧化铝42％、氧化锆12％、氧化镧(稀土元素)4％。颗粒状催化剂为直径3mm，高度5mm的圆柱体颗粒状催化剂。
通过化学分析对氧化镍检测，若氧化镍含量小于40％(质量百分含量)，重复制备方法中(5)步骤。
实施例3
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000004
孔容0.2-0.5ml/g，比表面积大于45m 2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，硝酸镍溶液浓度0.5mol/L。
制备方法如实施例1中内容，其中催化剂包括以下质量百分比的组分：氧化镍40％、氧化铝46％、氧化锆9％和氧化镧(稀土元素)4.5％，其余为杂质。颗粒状催化剂为直径2mm，高度3mm的圆柱体颗粒状催化剂。
通过化学分析对氧化镍检测，若氧化镍含量小于35％(质量百分含量)，重复制备方法中(5)步骤。
实施例4
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000005
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，硝酸镍溶液浓度0.6mol/L。
制备方法如实施例1中内容，其中催化剂包括以下质量百分比的组分：氧化镍38％、氧化铝47％、氧化锆11％、氧化镧(稀土元素)4％。颗粒状催化剂为直径3mm，高度0.5mm的圆柱体颗粒状催化剂。
实施例5
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000006
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，硝酸镍溶液浓度0.4mol/L。
制备方法如实施例1中内容，其中催化剂包括以下质量百分比的组分：氧化镍41％、氧化铝43％、氧化锆11％、氧化镧(稀土元素)5％。颗粒状催化剂为直径1mm，高度5mm的圆柱体颗粒状催化剂。
通过化学分析对氧化镍检测，若氧化镍含量小于40％(质量百分含量)，重复制备方法中(5)步骤。
实施例6
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000007
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，硝酸镍溶液浓度0.8mol/L。
制备方法如实施例1中内容，其中催化剂包括以下质量百分比的组分：氧化镍41.5％、氧化铝48％、氧化锆7％、氧化镧(稀土元素)3.5％。
通过化学分析对氧化镍检测，若氧化镍含量小于40％(质量百分含量)，重复制备方法中(5)步骤。
实施例7
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000008
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，硝酸镍溶液浓度0.9mol/L。
制备方法如实施例1中内容，其中催化剂包括以下质量百分比的组分：氧化镍41％、氧化铝48％、氧化锆6％、氧化镧(稀土元素)5％。
通过化学分析对氧化镍检测，若氧化镍含量小于40％(质量百分含量)，重复制备方法中(5)步骤。
实施例8
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元 素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000009
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，其氧化铝粉、氧化锆粉和氧化镧(稀土元素)粉的质量比例为7：43：4，氧化镍的硝酸镍溶液浓度0.2mol/L。
氧化锆采用高纯超细氧化锆粉(单斜晶相)，氧化铝采用高纯超细活性氧化铝粉，氧化镧采用高纯超细氧化镧(稀土元素)粉。
制备方法如实施例1中内容。
实施例9
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径 孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，其氧化铝粉、氧化锆粉和氧化镧(稀土元素)粉的质量比例为11：47：5，氧化镍的硝酸镍溶液浓度0.7mol/L。
氧化锆采用高纯超细氧化锆粉(单斜晶相)，氧化铝采用高纯超细活性氧化铝粉，氧化镧采用高纯超细氧化镧(稀土元素)粉。
制备方法如实施例1中内容。
实施例10
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000011
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，其氧化铝粉、氧化锆粉和氧化镧(稀土元素)粉的质量比例为7-11：43-47：4-5，氧化镍的硝酸镍溶液浓度0.7mol/L。
氧化锆采用高纯超细氧化锆粉(单斜晶相)，氧化铝采用高纯超细活性氧化铝粉，氧化镧采用高纯超细氧化镧粉。
制备方法如实施例1中内容。
实施例11
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000012
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，其氧化铝粉、氧化锆粉和氧化镧(稀土元素)粉的质量比例为9：45：4.5，氧化镍的硝酸镍溶液浓度0.7mol/L。
氧化锆采用高纯超细氧化锆粉(单斜晶相)，氧化铝采用高纯超细活性氧化铝粉，氧化镧采用高纯超细氧化镧(稀土元素)粉。
制备方法如实施例1中内容。
实施例12
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000013
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，其氧化铝粉、氧化锆粉和氧化镧(稀土元素)粉的质量比例为10：44：5，氧化镍的硝酸镍溶液浓度0.7mol/L。
氧化锆采用高纯超细氧化锆粉(单斜晶相)，氧化铝采用高纯超细活性氧化铝粉，氧化镧采用高纯超细氧化镧(稀土元素)粉。
制备方法如实施例1中内容。
实施例13
用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，包括铝、锆和镧(稀土元素)的氧化物制成的规整颗粒状载体，再负载上镍的氧化物，最后形成以镍、铝、锆和镧(稀土元素)的氧化物形成的规整颗粒状催化剂。催化剂平均孔径
Figure PCTCN2018111870-appb-000014
孔容0.2-0.5ml/g，比表面积大于45m2/g，900℃烧失重低于5％。
其中氧化铝、氧化锆、氧化镧(稀土元素)和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧(稀土元素)粉和硝酸镍溶液，其氧化铝粉、氧化锆粉和氧化镧(稀土元素)粉的质量比例为8：46：4.5，氧化镍的硝酸镍溶液浓度0.7mol/L。
氧化锆采用高纯超细氧化锆粉(单斜晶相)，氧化铝采用高纯超细活性氧化铝粉，氧化镧采用高纯超细氧化镧(稀土元素)粉。
制备方法如实施例1中内容。
实施例14
其它内容如实施例1，其中：催化剂包括以下质量百分比的组分：氧化镍35％、氧化铝50％、氧化锆10％、氧化铈(稀土元素)5％。
实施例15
其它内容如实施例1，其中：催化剂包括以下质量百分比的组分：氧化镍55％、氧化铝35％、氧化锆6％、氧化镨4％。
实施例16
其它内容如实施例1，其中：催化剂包括以下质量百分比的组分：氧化镍60％、氧化铝30％、氧化锆3％、氧化钇7％。
实施例17
其它内容如实施例1，其中：催化剂包括以下质量百分比的组分：氧化镍48％、氧化铝32％、氧化锆15％、氧化钆1％。
实施例18
其它内容如实施例1，其中：催化剂包括以下质量百分比的组分：氧化镍36％、氧化铝42％、氧化锆12％、氧化钬10％。
实施例19
其它内容如实施例1，其中：催化剂包括以下质量百分比的组分：氧化镍58％、氧化铝38％、氧化锆1％、氧化钆3％。
实施例20
其它内容如实施例1，其中：催化剂包括以下质量百分比的组分：氧化镍36％、氧化铝45％、氧化锆4％、氧化镧15％。
试验一
按照ASTM UOP578-02法，使用压汞法测定对比样和本发明中催化剂(自制催化剂样品，以下相同)的孔径分布，使用140°的接触角及压力范围在0.6至60,000psig，如图1。
其中，对比样是根据美国专利US 2013/0116118 Al中的制备方法制作出的催化剂：将420g包含镍、铝和锆氧化物的均匀混合物(BET表面积＝160m 2/g；NiO＝72wt.％， Al 2O 3＝19wt.％，ZrO 2＝9wt.％，d 50＝137μm)用作活性重整相(成分a)，加入180g包含γ-Al 2O 3、 δ-A/2O 3和θ-Al 2O 3的氧化铝粉末(BET＝126m 2/g，d 50＝116μm；)；随后将粉末混合物与3wt.％的石墨混合，并通过筒箍混合机充分混合。在压实机上压实获得的混合物，随后在液压偏心压机上处理，得到固体球粒(直径＝2.5mm；高度＝2.5mm)(基于氧化物的催化剂的总组成：50.4wt.％的NiO，43.65wt.％的A1 2O 3和5.95wt.％的ZrO 2)。
从图1可知，本发明比对比样具有更大的孔径，提供重整反应的活性通道，电解液的碱金属不易对孔径造成堵塞，使催化剂活性不降低。
试验二 催化剂中毒测试
取对比样品和本发明中催化剂作中毒测试，其中对比样品为试验一中的对比样。
测试具体如下：
反应管：Φ25×3mm；催化剂尺寸：Φ2×4mm测试粒度：原粒度；催化剂装填体积：3ml；催化剂装填高度：约1cm；电解质重量：31g；电解质粒度：<5mm；还原压力：常压；还原温度：入口550℃、中部550℃、出口550℃；还原气体流量：N2：1.25NL/min，75NL/h；H 2：0.505NL/min，30.3NL/h；还原时间：4h；
测试压力：常压；测试温度：入口往下1cm650℃、入口650℃、出口650℃(以实际温度为准)；测试气体流量：H 2：1.01NL/min，60.6NL/h；H 2O：8ml/min，480ml/h；CO 2:0.25NL/min，15NL/h；CH 4:2.5NL/min，150NL/h；N2：0.3NL/min，18NL/h；
测试入口气组成：
组成 N2(％) CH4(％) CO2(％) H2(％) H2O(％)
干基 7.39 61.57 6.16 24.88 ——
湿基 2.14 17.84 1.78 7.21 71.03
测试水碳比：3.98；测试水氢比：9.86；测试碳空速：10000h -1；
测试过程：在常压状态下，以N2对催化剂床层进行升温，当床层温度升至550℃时，通入H2进行还原；还原完成后，通过平流泵打入水，打入水催化剂床层在550℃稳定后通入CO 2，后催化剂床层温度继续升温至650℃，稳定后关闭N2，通入CH4进行催化剂的初始活性测定。为了进行中毒研究，将反应器冷却至室温，并在惰性气体(N 2)下，将测试气体通过电解质层再进入，当电解质层温度升至650℃后开始计时，中毒测试时4小时分析一次进出口组成，在整个测试期间(约800小时)，定期测量甲烷转化率，结果如图2。
从图2中可以看出，本发明所述催化剂在整个测试期间具有较稳定甲烷转化活性。对比样催化剂的初始甲烷转化率略高于本发明所述催化剂的初始甲烷转化率，但是通过碱金属氢 氧化物或碱金属碳酸盐蒸气中毒后，初始甲烷转化率下降，大约100小时之后，初始甲烷转化率低于本发明所述催化剂的甲烷转化率。
试验三
将对比样品和发明中催化剂作使用前、还原后和中毒后的孔径和孔容测试并分析，按照ASTM UOP578-02法，使用压汞法测定孔径分布，使用140°的接触角及压力范围在0.6至60,000psig，对比样品结果如图3，发明中催化剂结果如图4。
其中对比样品为试验一中的对比样。
从图4中可知，本发明中催化剂的结构稳定，孔径在使用前、还原后和中毒后变化较小，特别在还原后和中毒后，孔径和孔分布基本无变化。而从图3中可以看出，对比样品在使用前、还原后和中毒孔径和孔分布后变化明显，说明该催化剂结构不稳定，受温度和碱金属的影响较大。本发明的催化剂稳定的结构，能长时间提供稳定的孔径和孔分布，更有利于活性的稳定性，提高催化剂的使用寿命。
本发明中催化剂孔径大且孔结构稳定，大孔径不容易被电解液的碱金属堵塞，能持续提供重整反应的活性通道；铝、镧和锆共同作用，使载体晶粒错位，活性中心增多，提高了催化剂的整体活性。
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点，上述实施例和说明书所描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都将落入要求保护的本发明范围内。本发明要求保护的范围由所附的权利要求书及其等效物界定。

Claims (10)

  1. 一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：包括铝、锆和镧的氧化物制成的颗粒状载体，再负载上镍的氧化物，形成以镍、铝、锆和镧的氧化物形成颗粒状催化剂。
  2. 根据权利要求1所述的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：所述催化剂包括以下质量百分比的组分：氧化镍35-60％、氧化铝30-50％、氧化锆1-15％、氧化镧1-15％，总质量含量为100％。
  3. 根据权利要求1所述的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：所述催化剂包括以下质量百分比的组分：氧化镍35-55％、氧化铝35-50％、氧化锆6-10％、氧化镧4-5％，总质量含量为100％。
  4. 根据权利要求1所述的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：所述催化剂包括以下质量百分比的组分：氧化镍40％、氧化铝46％、氧化锆9％和氧化镧4.5％，其余为杂质。
  5. 根据权利要求1-4中任一项所述的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：所述氧化铝、氧化锆、氧化镧和氧化镍的原料为氧化铝粉、氧化锆粉、氧化镧粉和硝酸镍溶液，其氧化铝粉、氧化锆粉和氧化镧粉的质量比例为7-11：43-47：4-5。
  6. 根据权利要求5所述的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：所述硝酸镍溶液浓度0.l-lmol/L。
  7. 根据权利要求1所述的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：所述催化剂中氧化镍质量百分含量≥35％；所述催化剂为直径1-3mm，高度0.5-5mm的圆柱体颗粒状催化剂。
  8. 根据权利要求1所述的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：所述催化剂平均孔径
    Figure PCTCN2018111870-appb-100001
    孔容0.2-0.5ml/g。
  9. 根据权利要求1所述的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：所述催化剂比表面积大于45m 2/g，900℃烧失重低于5％。
  10. 根据权利要求1-9中任一项所述的一种用于熔融碳酸盐燃料电池中甲烷蒸汽重整的催化剂，其特征在于：所述镧可由其它稀土元素替代，其它稀土元素为铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钇或钪中的任何一种。
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