CN108199054B - Preparation method of catalyst for methane steam reforming in fuel cell - Google Patents

Preparation method of catalyst for methane steam reforming in fuel cell Download PDF

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CN108199054B
CN108199054B CN201810007229.6A CN201810007229A CN108199054B CN 108199054 B CN108199054 B CN 108199054B CN 201810007229 A CN201810007229 A CN 201810007229A CN 108199054 B CN108199054 B CN 108199054B
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CN108199054A (en
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刘阳
华波
麦景红
曾斌
刘卫东
彭国建
谢昊
杜勇
杨娟
郭游博
杨丽芸
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Southwest Research and Desigin Institute of Chemical Industry
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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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • 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

Abstract

The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a catalyst for methane steam reforming in a fuel cell, in particular to a molten carbonate fuel cell. The invention adopts an impregnation method preparation process, firstly prepares the catalyst carrier, and then loads the active component on the carrier, so that the prepared catalyst has large average aperture and stable structure, thereby further improving the alkali metal poisoning resistance of the catalyst, improving the activity stability and prolonging the service life of the catalyst.

Description

Preparation method of catalyst for methane steam reforming in fuel cell
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a catalyst for methane steam reforming in a fuel cell, in particular to a molten carbonate fuel cell.
Background
Molten carbonate fuel cells ("MCFCs") are high-temperature fuel cells that generate electricity by an electrochemical reaction between a cathode, an anode, and an electrolyte mother plate between the cathode and the anode. In such a battery, a molten eutectic of a mixed melt of alkali metal carbonates (e.g., a molten eutectic composed of lithium carbonate and potassium carbonate) impregnated in a support material (e.g., a film support composed of LiAlO2/Al2O 3) is used as an electrolytic solution. The hydrogen required for fuel cell operation can be produced directly in the cell by the methane steam reforming reaction. The steam reforming reaction of methane is shown in the following example: the first reaction, CH4+ H2O → CO +3H2 (1) CO + H2O → CO2+ H2 (2), is strongly endothermic and directly consumes the heat released by the electrochemical reaction. The reaction is a catalytic reaction requiring the use of a reforming catalyst, and natural gas (alternatively methane, petroleum gas, naphtha, heavy oil, or crude oil) may be used as a starting material for the operation of the fuel cell.
Currently, the hydrogen required for the operation of fuel cells comes from two parts, one part is partially reformed by a pre-reformer external to the fuel cell, part of the hydrogen produced is immediately available once it enters the cell, and the other part is steam reformed in the fuel cell, known as Direct Internal Reforming (DIR). During operation of the molten carbonate fuel cell at 580 to 675 ℃, part of the electrolyte is observed to evaporate in the form of alkali metal compounds (such as KOH, NaOH or LiOH). These alkali metal ions can deposit on the reforming catalyst, deactivating the catalyst through undesirable poisoning, which is one of the key factors affecting battery life. Therefore, even though the initial activity of the traditional catalyst is good, the traditional catalyst has the technical problems of rapid activity reduction after poisoning and poor activity stability, and needless to say, the activity of some catalysts is not high.
US patent US 2016/0006040 Al discloses a homogeneous catalyst having a single phase perovskite oxide in which at least one doping element of site a and/or site B of the ABO3 perovskite type oxide is substituted so that wettability with a liquid molten carbonate electrolyte may be reduced. The catalyst has high catalytic activity, inhibits catalyst poisoning caused by leakage and evaporation of liquid molten carbonate electrolyte, maintains high reaction activity for a long time, realizes high methane conversion rate, and can produce synthetic gas with high hydrogen ratio.
The catalyst is prepared by a solid-state mixing method, the catalyst prepared by the preparation method is unstable in structure, the strength and the specific surface of the catalyst are reduced quickly after reduction, and the activity of the catalyst is reduced quickly along with the reduction of the strength and the specific surface of the catalyst, so that the activity stability is poor.
A catalyst composition and catalyst material made therefrom for steam reforming of methane in fuel cells, particularly for direct internal reforming of methane in molten carbonate fuel cells, and a method for producing the catalyst composition are disclosed in US 2013/0116118 Al. Low activity and high stability to alkali metal ions.
The catalyst is prepared by adopting a precipitation method, the catalyst prepared by the preparation method is unstable in structure, the strength and the specific surface of the catalyst are reduced quickly after reduction, and the activity of the catalyst is reduced quickly along with the reduction of the strength and the specific surface of the catalyst, so that the activity stability is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a catalyst for methane steam reforming in a molten carbonate fuel cell, which is an immersion method preparation process, can obtain a stable framework structure, and has small changes in strength, pore structure and specific surface before and after reduction, thereby ensuring the activity stability of the catalyst and prolonging the service life of the catalyst.
A method for preparing a catalyst for steam reforming of methane in a molten carbonate fuel cell according to the present invention for solving the above technical problems, is characterized in that: the method comprises the following steps:
(1) ball milling and mixing: the three oxide powders of aluminum, zirconium and lanthanum are crushed and mixed, and different materials are uniformly mixed and further crushed, which is favorable for generating stable crystalline phase during pretreatment and calcination.
(2) Powder forming: and (3) preparing the powder in the step (1) into small particles, and pressing the small particles into particles with a specified shape, so that the filling size requirement of the fuel cell device is met. The predetermined shape is determined by the fuel cell device, and the fuel cell device must satisfy the requirement of the packing size, and an excessively large or small size cannot be packed in the fuel cell device.
(3) Pretreatment: and (3) carrying out pretreatment on the particles with the specified shapes prepared in the step (2) to form a new stable pore structure and a new stable crystal phase structure.
(4) And (3) calcining the carrier: calcining the pretreated particles in the step (3) at high temperature to form a carrier;
(5) dipping and decomposing: and (3) soaking the carrier in the step (4) in a nickel nitrate solution, attaching the active component to the carrier, and then drying and decomposing at high temperature.
In the step (1), the mixing time is 1-12h, preferably 1-8h, and particularly preferably 6-8 h. The short mixing time is not beneficial to the mixing of multi-component materials, the prepared product is not uniform, the activity is unstable, the materials are hardened after the mixing time is too long, and the forming of the next procedure is not beneficial.
In the step (2), the small particle size is 10-500 meshes, preferably 60-400 meshes, and particularly preferably 120-320 meshes; the particle size mainly influences the uniformity of the formed product, and the particles with the mesh of 120 and 320 are more favorable for entering a pressing die. The product pressed by the oversized or undersized particles entering the die is not uniform.
In the step (3), the temperature is 50-700 ℃, preferably 100-. The pretreatment of 0.01-2.0MPa pressure, preferably 0.1-1.5MPa pressure, particularly preferably 1-1.5MPa pressure, and 1-24h residence time, preferably 5-12h residence time, particularly 6-8h residence time, so that three oxides of aluminum, zirconium and lanthanum are interacted to generate a new crystal phase structure, and simultaneously, a new stable pore structure is formed in the pretreatment process.
Under certain temperature, pressure and time, new stable crystal phase structure is formed between different oxides, and new pores are generated, so that larger and more pores are obtained, the large pore diameter is not easy to be blocked by alkali metal of electrolyte, rich pores can continuously provide active channels of reforming reaction, and the activity stability of the catalyst is improved.
In the step (4), the calcination temperature is 675 ℃, preferably the calcination temperature is more than or equal to 700 ℃, particularly preferably the calcination temperature is more than or equal to 750 ℃, and the calcination temperature is less than or equal to 1400 ℃, preferably the calcination temperature is less than or equal to 1350 ℃, particularly preferably the calcination temperature is less than or equal to 1300 ℃, the calcination time is more than or equal to 30min, preferably the calcination time is more than or equal to 40min, particularly preferably the calcination time is more than or equal to 50min, and the calcination time is less than or equal to 10h, preferably the calcination time is less than or equal to 8 h.
The calcination temperature mainly affects the strength and specific surface of the carrier, when the temperature is less than 700 ℃, the specific surface is high, but the strength is too low, the carrier is easy to be pulverized in the use process, and the service life is affected, and when the calcination temperature is more than 1400 ℃, the strength is high, but the specific surface is too low, and the use activity is too low. The calcination time has an effect on the formation of the pore structure.
In the step (4), the specific surface area of the carrier>70m2(ii) in terms of/g. The specific surface is such as to ensure that a sufficient active surface is provided.
In the step (5), the dipping temperature is 60-90 ℃, the dipping temperature is preferably 70-90 ℃, the dipping temperature is particularly preferably 80-90 ℃, the dipping time is more than or equal to 5 minutes, the dipping time is more than or equal to 10 minutes, the dipping time is more than or equal to 15 minutes, the dipping time is less than or equal to 2 hours, the dipping time is less than or equal to 1.6 hours, and the dipping time is less than or equal to 1.5 hours.
The impregnation temperature and time are suitable to allow the impregnation solution to completely enter the pores of the support, while ensuring the uniformity of the solution distribution.
In the step (5), the concentration of the nickel nitrate solution is 0.L-L mol/L.
The lower the concentration of the solution, the less active ingredient per pass is loaded on the carrier, and the concentration of the solution is selected according to the amount of active ingredient to be loaded.
And (3) taking out the carrier after the impregnation in the step (5), and drying at a raised temperature, wherein the drying temperature is more than or equal to 90 ℃, preferably more than or equal to 100 ℃, particularly preferably more than or equal to 110 ℃, and the drying time is 10min-10h, preferably 20min-8h, particularly preferably 30min-4 h.
The drying temperature and time are used for ensuring that free water and crystal water of the nickel nitrate solution adsorbed on the carrier are completely removed, and preparation is made for next decomposition.
In the step (5), the decomposition temperature is more than 150 ℃, the decomposition temperature is preferably more than or equal to 200 ℃, the decomposition temperature is particularly preferably more than or equal to 250 ℃, the decomposition temperature is less than or equal to 700 ℃, the decomposition temperature is preferably less than or equal to 650 ℃, the decomposition temperature is particularly preferably less than or equal to 600 ℃, the decomposition time is more than or equal to 30min, the decomposition time is preferably more than or equal to 40min, the decomposition time is particularly preferably more than or equal to 50min, the decomposition time is less than or equal to 10h, the decomposition time is preferably less than or equal to 8.
The suitable decomposition temperature and time are such that the nickel nitrate can be completely decomposed into nickel oxide.
In the invention, nickel oxide is detected by chemical analysis, and if the mass percentage content of the nickel oxide on the carrier in the step (5) is less than 40%, the step (5) is repeated. If the content of the nickel oxide is less than 40%, the active centers participating in the catalytic reaction are reduced in the using process, the activity is reduced quickly, and the service life is shortened.
The prepared catalyst can comprise the following components in percentage by mass:
35-60% of nickel oxide, 30-50% of aluminum oxide, 1-15% of zirconium oxide and 1-15% of lanthanum oxide, wherein the total mass content is 100%; or the catalyst comprises the following components in percentage by mass: 35-55% of nickel oxide, 35-50% of aluminum oxide, 6-10% of zirconium oxide and 4-5% of lanthanum oxide, wherein the total mass content is 100%.
Or 37-42% of nickel oxide, 42-48% of aluminum oxide, 6-12% of zirconium oxide and 3.5-5% of lanthanum oxide, wherein the total mass content is 100%; or also comprises the following components in percentage by mass: 40-42% of nickel oxide, 43-47% of aluminum oxide, 7-11% of zirconium oxide and 4-5% of lanthanum oxide, wherein the total mass content is 100%; or comprises the following components in percentage by mass: 40% of nickel oxide, 46% of aluminum oxide, 9% of zirconium oxide and 4.5% of lanthanum oxide, and the balance of impurities.
The lanthanum may be replaced by other rare earth elements, which are any of cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, or scandium.
The preparation method of the catalyst for methane steam reforming in the fuel cell adopts an immersion method preparation process, firstly prepares the catalyst carrier, and then loads the active component on the carrier, so that the prepared catalyst has large average pore diameter, stable structure, higher thermal stability and antitoxic property. The prepared catalyst has an average pore diameter of 200-300A, a pore volume of 0.200-0.400ml/g, a specific surface area of more than 45 m2/g, and a weight loss on ignition at 900 ℃ of less than 5%.
Drawings
The invention will be described in further detail with reference to the following drawings and detailed description:
FIGS. 1 and 2 are graphs comparing pore sizes of different catalysts in the present invention
FIG. 3 is a graph comparing methane conversion in the present invention
FIG. 4 is a comparison of the poisoned comparative sample in the present invention before and after
FIG. 5 is a comparison of the self-prepared specimens of the present invention before and after poisoning
Detailed Description
The invention is further described with reference to the accompanying drawings and the detailed description below:
the catalyst in the following examples is a regular granular carrier made of oxides of aluminum, zirconium and lanthanum, then nickel oxide is loaded on the carrier, and finally the regular granular catalyst formed by the oxides of nickel, aluminum, zirconium and lanthanum is formed, wherein the raw materials used by the catalyst are alumina powder, zirconia powder, lanthanum oxide powder and nickel nitrate solution, and the mass ratio of the alumina powder, the zirconia powder and the lanthanum oxide powder is 7-11: 43-47: 4-5, and the concentration of the nickel nitrate solution is 0. L-lmol/L. The prepared granular catalyst can be cylindrical granular catalyst with the diameter of 1-3mm and the height of 0.5-5 mm.
Example 1
The preparation method of the catalyst for methane steam reforming in the molten carbonate fuel cell specifically comprises the following steps:
(1) ball milling and mixing: adding the three oxide powders of aluminum, zirconium and lanthanum into a ball mill according to the proportion of the final required components of the catalyst, further crushing the three oxide powders by ball milling, and fully mixing for 1 hour.
(2) Powder forming: and (2) preparing the powder prepared in the step (1) into fine granular materials with uniform granules and granularity of 10 meshes through a granulator, adding the fine granular materials into a rotary tablet press or a hydraulic forming tablet press, and pressing into granules with specified shapes.
(3) Pretreatment: keeping the particles with the specified shape prepared in the step (2) at the temperature of 50 ℃ and the pressure of 0.01Mpa for 1 hour;
(4) and (3) calcining the carrier: and (4) calcining the particles with the specified shapes pretreated in the step (4) at a high temperature, wherein the calcining temperature is higher than the using temperature of 680 ℃, and the calcining time is 30 minutes. The specific surface area and the pore size of the calcined carrier are controlled by adjusting the calcination time and the calcination temperature, and the specific surface area is more than 72 m2/g。
(5) Dipping and decomposing: and (4) putting the carrier prepared in the step (4) into a nickel nitrate solution for impregnation, wherein the impregnation temperature is 60 ℃, the impregnation time is 5 minutes, and the concentration of the nickel nitrate solution is 0.l mol/L. After impregnation, the support is taken out and dried at elevated temperature, wherein the temperature is 90 ℃ for 10 minutes. And further raising the temperature of the dried carrier, and removing nitrate through high-temperature decomposition of nitrate to leave nickel oxide. The decomposition temperature was 155 ℃ and the time was 30 minutes. And (5) detecting nickel oxide through chemical analysis, and if the content of the nickel oxide is less than 40% (mass percentage content), repeating the step (5).
The catalyst prepared by the method has large aperture and stable pore structure, the large aperture is not easy to be blocked by alkali metal of electrolyte, and an active channel of reforming reaction can be continuously provided; the combined action of aluminum, lanthanum and zirconium leads the crystal grains of the carrier to be dislocated, increases the active centers and improves the overall activity of the catalyst.
Example 2
The preparation method of the catalyst for methane steam reforming in the molten carbonate fuel cell specifically comprises the following steps:
(1) ball milling and mixing: adding the three oxides of aluminum, zirconium and lanthanum into a ball mill according to the proportion of the final required components of the catalyst, further crushing the three oxides by ball milling, and fully mixing for 12 hours.
(2) Powder forming: and (2) preparing the powder prepared in the step (1) into fine granular materials with uniform granules through a granulator, wherein the granularity is 500 meshes, and then adding the fine granular materials into a rotary tablet press or a hydraulic forming tablet press to press the fine granular materials into granules with specified shapes.
(3) Pretreatment: the particles with the specified shape prepared in the step (2) are kept for 24 hours at the temperature of 700 ℃ and the pressure of 2.0 Mpa;
(4) and (3) calcining the carrier: and (4) calcining the particles with the specified shapes pretreated in the step (3) at a high temperature of 700 ℃ for 40 minutes. The specific surface area and the pore size of the calcined carrier are controlled by adjusting the calcination time and the calcination temperature, and the specific surface area is generally required to be more than 75 m2/g。
(5) Dipping and decomposing: and (4) putting the carrier prepared in the step (4) into a nickel nitrate solution for impregnation, wherein the impregnation temperature is 70 ℃, the impregnation time is 10 minutes, and the concentration of the nickel nitrate solution is 0.6 mol/L. After impregnation, the support is taken out and dried at elevated temperature, wherein the temperature is 100 ℃ for 20 minutes. The dried support is further raised in temperature to remove nitrate by pyrolysis of the nitrate, leaving the nickel oxide. The decomposition temperature was 200 ℃ and the time was 40 minutes. And (5) detecting nickel oxide through chemical analysis, and if the content of the nickel oxide is less than 40% (mass percentage content), repeating the step (5).
Example 3
The preparation method of the catalyst for methane steam reforming in the molten carbonate fuel cell specifically comprises the following steps:
(1) ball milling and mixing: adding the three oxides of aluminum, zirconium and lanthanum into a ball mill according to the proportion of the final required components of the catalyst, further crushing the three oxides by ball milling, and fully mixing for 6 hours.
(2) Powder forming: and (3) preparing the powder prepared in the step (1) into fine granular materials with uniform granules and granularity of 60 meshes by a granulator, adding the fine granular materials into a rotary tablet press or a hydraulic forming tablet press, and pressing into granules with specified shapes.
(3) Pretreatment: the particles with the specified shape prepared in the step (2) are subjected to temperature of 100 ℃, pressure of 0.1Mpa and retention time of 5 hours;
(4) and (3) calcining the carrier: and (3) calcining the particles with the specified shapes pretreated in the step (3) at a high temperature of 750 ℃ for 10 hours. The specific surface area and the pore size of the calcined carrier are controlled by adjusting the calcination time and the calcination temperature, and the specific surface area is generally required to be more than 80 m2/g。
(5) Dipping and decomposing: and (4) putting the carrier prepared in the step (4) into a nickel nitrate solution for impregnation, wherein the impregnation temperature is 80 ℃, the impregnation time is 1.6 hours, and the concentration of the nickel nitrate solution lmol/L. After impregnation, the support is taken out and dried at elevated temperature, wherein the temperature is 110 ℃ for 2 hours. The dried support is further raised in temperature to remove nitrate by pyrolysis of the nitrate, leaving the nickel oxide. The decomposition temperature was 250 ℃ and the time was 50 minutes.
And (5) detecting nickel oxide through chemical analysis, and if the content of the nickel oxide is less than 40% (mass percentage content), repeating the step (5).
The catalyst prepared by the method has large aperture and stable pore structure, the large aperture is not easy to be blocked by alkali metal of electrolyte, and an active channel of reforming reaction can be continuously provided; the combined action of aluminum, lanthanum and zirconium leads the crystal grains of the carrier to be dislocated, increases the active centers and improves the overall activity of the catalyst.
Example 4
The preparation method of the catalyst for methane steam reforming in the molten carbonate fuel cell specifically comprises the following steps:
(1) ball milling and mixing: adding the three oxides of aluminum, zirconium and lanthanum into a ball mill according to the proportion of the final required components of the catalyst, further crushing the three oxides by ball milling, and fully mixing for 8 hours.
(2) Powder forming: and (2) preparing the powder prepared in the step (1) into fine granular materials with uniform granules by a granulator, wherein the granularity is 400 meshes, adding the fine granular materials into a rotary tablet press or a hydraulic forming tablet press, and pressing into granules with specified shapes.
(3) Pretreatment: the particles with the specified shape prepared in the step (2) are kept for 12 hours at the temperature of 600 ℃ and the pressure of 1.5 Mpa;
(4) and (3) calcining the carrier: and (3) calcining the particles with the specified shapes pretreated in the step (3) at the high temperature of 1400 ℃ for 1 hour. The specific surface area and the pore size of the calcined carrier are controlled by adjusting the calcination time and the calcination temperature, and the specific surface area is generally required to be 76 m2/g。
(5) Dipping and decomposing: and (3) putting the carrier prepared in the step (3) into a nickel nitrate solution for impregnation, wherein the impregnation temperature is 90 ℃, the impregnation time is 1 hour, and the concentration of the nickel nitrate solution is 0.5 mol/L. After impregnation, the support is taken out and dried at elevated temperature, wherein the temperature is 130 ℃ for 4 hours. The dried support is further raised in temperature to remove nitrate by pyrolysis of the nitrate, leaving the nickel oxide. The decomposition temperature is 700 ℃ and the time is 6 hours.
And (5) detecting nickel oxide through chemical analysis, and if the content of the nickel oxide is less than 40% (mass percentage content), repeating the step (5).
Example 5
The preparation method of the catalyst for methane steam reforming in the molten carbonate fuel cell specifically comprises the following steps:
(1) ball milling and mixing: adding the three oxides of aluminum, zirconium and lanthanum into a ball mill according to the proportion of the final required components of the catalyst, further crushing the three oxides by ball milling, and fully mixing for 7 hours.
(2) Powder forming: and (2) preparing the powder prepared in the step (1) into fine granular materials with uniform granules by a granulator, wherein the granularity is 120 meshes, and then adding the fine granular materials into a rotary tablet press or a hydraulic forming tablet press to press the fine granular materials into granules with specified shapes.
(3) Pretreatment: keeping the particles with the specified shape prepared in the step (2) at the temperature of 200 ℃, the pressure of 1Mpa and the retention time of 6 h;
(4) and (3) calcining the carrier: and (3) calcining the particles with the specified shapes pretreated in the step (3) at high temperature of 900 ℃ for 4 hours. The specific surface area and the pore size of the calcined carrier are controlled by adjusting the calcination time and the calcination temperature, and the specific surface area is generally required to be more than 85 m2/g。
(5) Dipping and decomposing: and (4) putting the carrier prepared in the step (4) into a nickel nitrate solution for impregnation, wherein the impregnation temperature is 85 ℃, the impregnation time is 1 hour, and the concentration of the nickel nitrate solution is 0.6 mol/L. After impregnation, the support is taken out and dried at elevated temperature, wherein the temperature is 120 ℃ for 3 hours. The dried support is further raised in temperature to remove nitrate by pyrolysis of the nitrate, leaving the nickel oxide. The decomposition temperature is 500 ℃ and the time is 3 hours.
And (5) detecting nickel oxide through chemical analysis, and if the content of the nickel oxide is less than 40% (mass percentage content), repeating the step (5).
The catalyst prepared by the method has large aperture and stable pore structure, the large aperture is not easy to be blocked by alkali metal of electrolyte, and an active channel of reforming reaction can be continuously provided; the combined action of aluminum, lanthanum and zirconium leads the crystal grains of the carrier to be dislocated, increases the active centers and improves the overall activity of the catalyst.
Example 6
The preparation method of the catalyst for methane steam reforming in the molten carbonate fuel cell specifically comprises the following steps:
(1) ball milling and mixing: adding three oxides of aluminum, zirconium and lanthanum into a ball mill according to the proportion of the final required components of the catalyst, further crushing the three oxides by ball milling, and fully mixing for 4 hours.
(2) Powder forming: and (2) preparing the powder prepared in the step (1) into fine granular materials with uniform granules through a granulator, wherein the granularity is 320 meshes, adding the fine granular materials into a rotary tablet press or a hydraulic forming tablet press, and pressing into granules with specified shapes.
(3) Pretreatment: keeping the particles with the specified shape prepared in the step (2) at the temperature of 500 ℃, the pressure of 1.5Mpa and the retention time of 8 h;
(4) and (3) calcining the carrier: and (3) calcining the particles with the specified shapes prepared in the step (3) at high temperature of 1100 ℃ for 2 hours. The specific surface area and the pore size of the calcined carrier are controlled by adjusting the calcination time and the calcination temperature, and the specific surface area is 83 m2/g。
(5) Dipping and decomposing: and (4) putting the carrier prepared in the step (4) into a nickel nitrate solution for impregnation, wherein the impregnation temperature is 75 ℃, the impregnation time is 1.5 hours, and the concentration of the nickel nitrate solution is 0.4 mol/L. After impregnation, the support is taken out and dried at elevated temperature, wherein the temperature is 95 ℃ for 8 hours. The dried support is further raised in temperature to remove nitrate by pyrolysis of the nitrate, leaving the nickel oxide. The decomposition temperature is 400 ℃ and the time is 2 hours.
And (5) detecting nickel oxide through chemical analysis, and if the content of the nickel oxide is less than 40% (mass percentage content), repeating the step (5).
Example 7
The preparation method of the catalyst for methane steam reforming in the molten carbonate fuel cell specifically comprises the following steps:
(1) ball milling and mixing: adding the three oxides of aluminum, zirconium and lanthanum into a ball mill according to the proportion of the final required components of the catalyst, further crushing the three oxides by ball milling, and fully mixing for 10 hours.
(2) Powder forming: and (2) preparing the powder prepared in the step (1) into fine granular materials with uniform granules through a granulator, wherein the granularity is 200 meshes, adding the fine granular materials into a rotary tablet press or a hydraulic forming tablet press, and pressing into granules with specified shapes.
(3) Pretreatment: the granules of the prescribed shape prepared in step (2) were heated at a temperature of 300 ℃. The pressure is 1.2Mpa, and the retention time is 7 h;
(4) and (3) calcining the carrier: and (3) calcining the particles with the specified shapes pretreated in the step (3) at a high temperature of 800 ℃ for 6 hours. The specific surface area and the pore size of the calcined carrier are controlled by adjusting the calcination time and the calcination temperature, and the specific surface area is 71 m2/g。
(5) Dipping and decomposing: and (3) putting the carrier prepared in the step (3) into a nickel nitrate solution for impregnation, wherein the impregnation temperature is 65 ℃, the impregnation time is 50 minutes, and the concentration of the nickel nitrate solution is 0.2 mol/L. After impregnation, the support is taken out and dried at elevated temperature, wherein the temperature is 105 ℃ for 10 hours. The dried support is further raised in temperature to remove nitrate by pyrolysis of the nitrate, leaving the nickel oxide. The decomposition temperature is 300 ℃ and the time is 10 hours.
And (5) detecting nickel oxide through chemical analysis, and if the content of the nickel oxide is less than 40% (mass percentage content), repeating the step (5).
Example 8
The preparation method of the catalyst for methane steam reforming in the molten carbonate fuel cell specifically comprises the following steps:
(1) ball milling and mixing: adding the three oxides of aluminum, zirconium and lanthanum into a ball mill according to the proportion of the final required components of the catalyst, further crushing the three oxides by ball milling, and fully mixing for 7 hours.
(2) Powder forming: and (2) preparing the powder prepared in the step (1) into fine granular materials with uniform granules through a granulator, wherein the granularity is 260 meshes, adding the fine granular materials into a rotary tablet press or a hydraulic forming tablet press, and pressing into granules with specified shapes.
(3) Pretreatment: the granules of the prescribed shape prepared in step (2) were heated at 400 ℃. The pressure is 1.3Mpa, and the retention time is 8 h;
(4) and (3) calcining the carrier: and (3) calcining the particles with the specified shapes pretreated in the step (3) at a high temperature of 1300 ℃ for 1.5 hours. Controlling the calcined carrier by adjusting the calcination time and the calcination temperatureSpecific surface area, pore size, specific surface area 84 m2/g。
(5) Dipping and decomposing: and (3) putting the carrier prepared in the step (3) into a nickel nitrate solution for impregnation, wherein the impregnation temperature is 85 ℃, the impregnation time is 30 minutes, and the concentration of the nickel nitrate solution is 0.7 mol/L. After impregnation the support is taken out and dried at elevated temperature, wherein the temperature is 140 ℃ for 30 minutes. The dried support is further raised in temperature to remove nitrate by pyrolysis of the nitrate, leaving the nickel oxide. The decomposition temperature is 200 ℃ and the time is 8 hours.
And (5) detecting nickel oxide through chemical analysis, and if the content of the nickel oxide is less than 40% (mass percentage content), repeating the step (5).
Test No.)
Let us assume the experimental example (pretreated sample) which is the catalyst of the present invention prepared by the method of example 1 and the control (non-pretreated sample) which is otherwise the same as that of example 1, but without step (3) and without the pretreatment step.
The pore size distribution of the control and the catalyst of the invention (a self-made catalyst sample, the same applies hereinafter) was determined according to ASTM UOP578-02 using mercury intrusion methods using a contact angle of 140 ℃ and a pressure in the range of 0.6 to 60,000psig, as shown in FIG. 1.
As can be seen from fig. 1, the pore size and pore distribution of the pretreated product are higher than those of the non-pretreated product.
Test No. two
The pore size distribution of the control and the catalyst produced by the preparation method of the present invention (self-made catalyst samples, the same below) was determined according to ASTM UOP578-02 method using mercury intrusion methods using contact angles of 140 ℃ and pressures ranging from 0.6 to 60,000psig as shown in FIG. 2.
The control is a catalyst prepared according to the preparation method in US 2013/0116118 Al: 420g of a homogeneous mixture comprising nickel, aluminum and zirconium oxide (BET surface area =160 m)2/g；NiO=72wt.%，Al2O3=19wt.%，ZrO2=9wt.%，d50=137 μm) as active reforming phase (component a)). 180g of gamma-Al are added2O3、 δ-A/2 O3And theta-Al2O3Alumina powder (BET = 126 m)2/g，d50=116 μm; ). The powder mixture was then mixed with 3wt.% graphite and thoroughly mixed by a barrel mixer. The resulting mixture was compacted on a compactor and subsequently treated on a hydraulic eccentric press to give solid pellets (diameter =2.5 mm; height =2.5 mm) (total composition of oxide-based catalyst: 50.4 wt.% NiO, 43.65wt.% a12O3And 5.95 wt.% ZrO2）。
As can be seen from the examination in FIG. 2, the present invention has larger pore size compared with the comparative sample, provides an active channel for the reforming reaction, and the alkali metal of the electrolyte is not easy to block the pore size, so that the catalyst activity is reduced.
Test two catalyst poisoning test
Taking a comparative sample and the catalyst prepared by the method of the invention for a poisoning test, wherein the comparative sample is a comparative sample in the first test, and the test is as follows: .
Reaction tube: phi 25 x 3 mm; catalyst size: Φ 2 × 4mm test particle size: primary granularity; catalyst loading volume: 3 ml; catalyst loading height: about 1 cm; electrolyte weight: 31g of a basic amine; electrolyte particle size:<5 mm; reduction pressure: normal pressure; reduction temperature: 550 ℃ at the inlet, 550 ℃ at the middle part and 550 ℃ at the outlet; flow rate of reducing gas: n2: 1.25NL/min, 75 NL/h; h2: 0.505NL/min, 30.3 NL/h; reduction time: 4 h;
and (3) testing pressure: normal pressure; and (3) testing temperature: the inlet is downward 1cm650 ℃, the inlet is 650 ℃ and the outlet is 650 ℃ (based on the actual temperature); testing the gas flow: h2：1.01NL/min，60.6NL/h；H2O：8ml/min，480ml/h；CO2:0.25NL/min，15NL/h；CH4:2.5NL/min，150NL/h；N2：0.3NL/min，18NL/h；
Testing inlet gas composition:
Figure 1
and (3) testing the water-carbon ratio: 3.98 of; testing the water-hydrogen ratio: 9.86 of the total weight of the steel; testing the carbon space velocity: 10000 h-1;
the testing process comprises the following steps: heating a catalyst bed layer by using N2 under the normal pressure state, and introducing H2 for reduction when the temperature of the bed layer is increased to 550 ℃; and after the reduction is finished, pumping water through a constant flow pump, pumping the water into a water catalyst bed layer, introducing CO2 after the water catalyst bed layer is stabilized at 550 ℃, continuously heating the temperature of the catalyst bed layer to 650 ℃, closing N2 after the water catalyst bed layer is stabilized, and introducing CH4 to measure the initial activity of the catalyst. For the poisoning study, the reactor was cooled to room temperature and the test gas was re-admitted through the electrolyte layer under inert gas (N2), the inlet and outlet composition was analyzed once 4 hours at the time of the poisoning test when the electrolyte layer temperature was raised to 650 ℃, and the methane conversion was measured periodically throughout the test period (about 800 hours), the results are shown in fig. 3.
As can be seen in fig. 3, the catalyst of the present invention has a relatively stable methane conversion activity throughout the duration of the test. The initial methane conversion of the comparative catalyst was slightly higher than that of the catalyst of the present invention, but after steam poisoning by alkali metal hydroxide or alkali metal carbonate, the initial methane conversion decreased, and after about 100 hours, the initial methane conversion was lower than that of the catalyst of the present invention.
Experiment three
The pore size and pore volume of the comparative sample and the catalyst prepared by the method of the invention were measured and analyzed before use, after reduction and after poisoning, according to ASTM UOP578-02, using mercury intrusion, using a contact angle of 140 ° and a pressure ranging from 0.6 to 60,000psig, the results for the comparative sample are shown in fig. 4, and the results for the catalyst of the invention are shown in fig. 5.
Wherein the control sample is the control in test one.
As can be seen from fig. 5, the catalyst of the present invention has a stable structure, and the pore diameter has small changes before use, after reduction and after neutralization, and particularly, the pore diameter and the pore distribution have substantially no changes after reduction and neutralization. It can be seen from fig. 4 that the comparative samples varied significantly before use, after reduction and after the toxic pore size and pore distribution, indicating that the catalyst structure was unstable and was greatly affected by temperature and alkali metals. The stable structure of the catalyst can provide stable aperture and pore distribution for a long time, is more beneficial to the stability of activity and prolongs the service life of the catalyst.
The catalyst prepared by the preparation method has large aperture and stable pore structure, the large aperture is not easy to be blocked by alkali metal of electrolyte, and an active channel of reforming reaction can be continuously provided; the combined action of aluminum, lanthanum and zirconium leads the crystal grains of the carrier to be dislocated, increases the active centers and improves the overall activity of the catalyst.
While the foregoing shows and describes the fundamental principles and principal features of the invention, together with the advantages thereof, the foregoing embodiments and description are illustrative only of the principles of the invention, and various changes and modifications can be made therein without departing from the spirit and scope of the invention, which will fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (20)

1. A method of preparing a catalyst for steam reforming of methane in a molten carbonate fuel cell, comprising: the method comprises the following steps:
(1) ball milling and mixing: crushing and mixing the proportioned three oxides of aluminum, zirconium and lanthanum for 1-12 h;
(2) powder forming: preparing the powder in the step 1 into particles, and pressing the particles into particles with a specified shape;
(3) pretreatment: forming a new stable pore structure in the pretreatment process of the particles with the specified shape prepared in the step (2); the pretreatment temperature is 100 ℃ and 700 ℃, the pressure is 1-2.0Mpa, and the retention time is 1-24 h;
(4) and (3) calcining the carrier: calcining the particles with the specified shape pretreated in the step 3 at high temperature to form a carrier; wherein the calcination temperature is 675 ℃ and is less than or equal to 1400 ℃, and the calcination time is 30min and is less than or equal to 10 h;
(5) dipping and decomposing: putting the carrier into a nickel nitrate solution for dipping, drying and high-temperature decomposition; if the mass percentage content of the nickel oxide on the carrier is less than 40 percent, repeatedly dipping; the prepared catalyst has a pore diameter of 200-300A and a pore volume of 0.200-0.400 ml/g.
2. The method of claim 1, wherein the catalyst is prepared by a method comprising: the mixing time in the step (1) is 1-8 h.
3. The method of claim 2, wherein the catalyst is selected from the group consisting of: the mixing time in the step (1) is 6-8 h.
4. The method of claim 1, wherein the catalyst is prepared by a method comprising: in the step (2), the particle size is 10-500 meshes.
5. The method of claim 4, wherein the catalyst is selected from the group consisting of: in the step (2), the particle size is 60-400 meshes.
6. The method of claim 5, wherein the catalyst is selected from the group consisting of: in the step (2), the particle size is 120-320 meshes.
7. The method of claim 1, wherein the catalyst is prepared by a method comprising: in the step (3), the temperature is 100-.
8. The method of claim 7, wherein the catalyst is selected from the group consisting of: in the step (3), the temperature is 200 ℃ and 500 ℃, and the retention time is 6-8 h.
9. The method of claim 1 or 7, wherein the catalyst for steam reforming of methane in a molten carbonate fuel cell is prepared by: in the step (4), the calcination temperature is more than or equal to 700 ℃ and less than or equal to 1350 ℃, and the calcination time is more than or equal to 40min and less than or equal to 8 h.
10. The method of claim 9, wherein the catalyst is selected from the group consisting of: in the step (4), the calcination temperature is more than or equal to 750 ℃ and less than or equal to 1300 ℃, and the calcination time is more than or equal to 50min and less than or equal to 6 h.
11. The method of claim 10, wherein the catalyst is prepared by a method comprising: in the step (4), the specific surface area of the carrier>70m2(ii)/g; in the step (5), the concentration of the nickel nitrate solution is 0.L-L mol/L.
12. The method of claim 1, wherein the catalyst is prepared by a method comprising: in the step (5), the dipping temperature is 60-90 ℃, the dipping time is more than or equal to 5 minutes, and the dipping time is less than or equal to 2 hours.
13. The method of claim 12, wherein the catalyst is selected from the group consisting of: in the step (5), the dipping temperature is 70-90 ℃, the dipping time is more than or equal to 10 minutes, and the dipping time is less than or equal to 1.6 hours.
14. The method of claim 13, wherein the catalyst is selected from the group consisting of: in the step (5), the dipping temperature is 80-90 ℃, the dipping time is more than or equal to 15 minutes, and the dipping time is less than or equal to 1.5 hours.
15. The method of claim 1, wherein the catalyst is prepared by a method comprising: and (5) taking out the carrier after the impregnation is finished, and drying at a raised temperature, wherein the drying temperature is more than or equal to 90 ℃, and the drying time is 10min-10 h.
16. The method of claim 15, wherein the catalyst is selected from the group consisting of: and (5) taking out the carrier after the impregnation is finished, and drying at a raised temperature, wherein the drying temperature is more than or equal to 100 ℃, and the drying time is 20min-8 h.
17. The method of claim 16, wherein the catalyst is selected from the group consisting of: and (5) taking out the carrier after the impregnation is finished, and drying at a raised temperature, wherein the drying temperature is more than or equal to 110 ℃, and the drying time is 30min-4 h.
18. The method of claim 1, wherein the catalyst is prepared by a method comprising: in the step (5), the decomposition temperature is more than 150 ℃, the decomposition temperature is less than or equal to 700 ℃, the decomposition time is more than or equal to 30min, and the decomposition time is less than or equal to 10 h.
19. The method of claim 18, wherein the catalyst is selected from the group consisting of: in the step (5), the decomposition temperature is more than or equal to 200 ℃, the decomposition temperature is less than or equal to 650 ℃, the decomposition time is more than or equal to 40min, and the decomposition time is less than or equal to 8 h.
20. The method of claim 19, wherein the catalyst is selected from the group consisting of: in the step (5), the decomposition temperature is more than or equal to 250 ℃, the decomposition temperature is less than or equal to 600 ℃, the decomposition time is more than or equal to 50min, and the decomposition time is less than or equal to 6 h.
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