CN108134102B - Catalyst for methane steam reforming in fuel cell - Google Patents
Catalyst for methane steam reforming in fuel cell Download PDFInfo
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- CN108134102B CN108134102B CN201810007262.9A CN201810007262A CN108134102B CN 108134102 B CN108134102 B CN 108134102B CN 201810007262 A CN201810007262 A CN 201810007262A CN 108134102 B CN108134102 B CN 108134102B
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for methane steam reforming in a fuel cell, in particular to a molten carbonate fuel cell, which is characterized in that: the catalyst comprises a regular granular carrier made of oxides of aluminum, zirconium and lanthanum, and nickel oxide loaded on the regular granular carrier, and finally the regular granular catalyst formed by the oxides of nickel, aluminum, zirconium and lanthanum is formed. The catalyst 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 (rare earth element) and zirconium makes the crystal grains of the carrier dislocated, increases the active centers and improves the overall activity of the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to 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. But has low activity and high stability to alkali metal ions. The catalyst is prepared by adopting a precipitation method, the prepared catalyst 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 catalyst for methane steam reforming in a molten carbonate fuel cell, which consists of oxides of nickel, aluminum, zirconium and lanthanum (rare earth elements), has good alkali metal poisoning resistance, high specific surface area and improved catalyst activity, reasonable pore structure further improves the alkali metal poisoning resistance of the catalyst, and the catalyst has high stability; the strength, specific surface and pore structure of the catalyst are slightly changed before and after use, so that the activity stability is prolonged, the service life of the catalyst is prolonged, and the commercial target level with higher and higher requirements is reached.
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: comprises regular granular carriers made of oxides of aluminum, zirconium and lanthanum, then nickel oxides are loaded on the carriers, and finally, the granular catalyst formed by the oxides of nickel, aluminum, zirconium and lanthanum is formed.
The granular catalyst is a cylindrical granular catalyst with the diameter of 1-3mm and the height of 0.5-5 mm.
The catalyst comprises 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%.
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 in the optimized scheme, 37-42% of nickel oxide, 42-48% of aluminum oxide, 6-12% of zirconium oxide and 3.5-5% of lanthanum oxide account for 100% of the total mass content; 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%.
The catalyst 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 raw materials of the alumina, the zirconia, the lanthanum oxide and the nickel oxide are alumina powder, zirconia powder, lanthanum oxide powder and nickel nitrate solution, and the mass ratio of the alumina powder to the zirconia powder to the lanthanum oxide powder is 7-11: 43-47: 4-5.
The zirconium oxide adopts high-purity superfine zirconium oxide powder (monoclinic phase), the aluminum oxide adopts high-purity superfine active aluminum oxide powder, the lanthanum oxide adopts high-purity superfine lanthanum oxide (rare earth element) powder, the purity of the three raw materials is 90-99.9%, and the granularity d of the three raw materials500.5 to 50 μm.
The concentration of the nickel nitrate solution is 0. L-lmol/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.
The mass percentage content of the nickel oxide of the catalyst is more than or equal to 35 percent.
The average pore diameter of the catalyst is 200-500A, and the pore volume is 0.2-0.5 ml/g. The large aperture is not easy to be blocked by alkali metal of electrolyte, and abundant pores can continuously provide active channels for reforming reaction, thereby improving the activity stability of the catalyst.
The specific surface area of the catalyst is more than 45m2(g), the weight loss on ignition at 900 ℃ is less than 5 percent. The specific surface is such as to ensure that a sufficient active surface is provided.
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 method for preparing the catalyst for methane steam reforming in the fuel cell comprises the steps of ball milling and mixing, powder forming, pretreatment, carrier calcination and impregnation decomposition, and is prepared by adopting an impregnation method. That is, a catalyst carrier is prepared first, and then an active component is supported on the carrier to form the catalyst carrier.
The method for preparing the catalyst for steam reforming of methane in a molten carbonate fuel cell according to the present invention comprises the steps of:
(1) ball milling and mixing: the three oxide powders of aluminum, zirconium and lanthanum (rare earth elements) 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.
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.
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.
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.
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.
In the step (5), the concentration of the nickel nitrate solution is 0.L-L mol/L.
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.
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 invention has the following beneficial effects:
(1) the pore diameter is large, the pore structure is stable, the large pore diameter is not easily blocked by alkali metal of electrolyte, and an active channel for reforming reaction can be continuously provided;
(2) the combined action of aluminum, lanthanum (rare earth element) and zirconium makes the crystal grains of the carrier dislocated, increases the active centers and improves the overall activity of the catalyst.
Drawings
The invention will be described in further detail with reference to the following drawings and detailed description:
FIG. 1 is a graph comparing pore sizes of different catalysts in the present invention
FIG. 2 is a graph comparing the methane conversion in the present invention
FIG. 3 is a comparison of the poisoned comparative sample in the present invention before and after
FIG. 4 is a graph showing a comparison between before and after the catalyst poisoning in the present invention
Detailed Description
The invention is further described with reference to the accompanying drawings and the detailed description below:
example 1
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of the regular granular carrier made of the oxides of Al, Zr and La (rare-earth elements), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth elements), and features high average pore diameter (200-500 Å), pore volume (0.2-0.5 ml/g), and specific surface area greater than 45m2(g), the weight loss on ignition at 900 ℃ is less than 5 percent. The catalyst comprises the following components in percentage by mass: 37% of nickel oxide, 48% of aluminum oxide, 10% of zirconium oxide and 5% of lanthanum oxide (rare earth element). The granular catalyst is a cylindrical granular catalyst with the diameter of 1mm and the height of 0.5 mm.
Wherein the raw materials of the alumina, the zirconia, the lanthanum oxide and the nickel oxide are alumina powder, zirconia powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the concentration of the nickel nitrate solution lmol/L.
The preparation method of the catalyst for methane steam reforming in the fuel cell comprises the steps of ball milling and mixing, powder forming, pretreatment, carrier calcination and impregnation decomposition, and is prepared by adopting an impregnation method. That is, a catalyst carrier is prepared first, and then an active component is supported on the carrier to form the catalyst carrier.
The preparation method comprises the following specific steps:
(1) ball milling and mixing: adding three oxide powders of aluminum, zirconium and lanthanum (rare earth elements) into a ball mill according to a required proportion, further crushing the three oxide powders by ball milling, and fully mixing for 1-12 hours.
(2) Powder forming: and (2) preparing the powder prepared in the step (1) into fine granular materials with uniform granules by a granulator, selecting the fine granular materials with the granularity of 10-500 meshes, preferably 60-400 meshes, particularly preferably 120-320 meshes, adding the fine granular materials into a rotary tablet press or a hydraulic forming tablet press, and pressing into granules with specified shapes. 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.
(3) And (3) pretreatment, namely carrying out pretreatment on the particles with the specified shapes prepared in the step (2) at the temperature of 100-600 ℃ and the pressure of 0.2-1.0Mpa for 6-18 hours to ensure that three oxides of aluminum, zirconium and lanthanum interact to generate a new crystal phase structure, and simultaneously forming a new stable pore structure in the pretreatment process.
(4) And (3) calcining the carrier: calcining the particles with the specified shape prepared in the step (3) at high temperature of 675-1400 ℃ for 30 minutes-10 hours to ensure that the specific surface area and the pore size of the calcined carrier meet the requirements, and the specific surface area is more than 70m2/g。
(5) Dipping and decomposing: and (3) putting the carrier prepared in the step (4) into a nickel nitrate solution for soaking at the temperature of 60-90 ℃ for 5 minutes-2 hours, wherein the concentration of the nickel nitrate solution is 0.L-L mol/L. After impregnation, the support is removed and dried at an elevated temperature of at least 90 ℃ for a period of from 10 minutes to 10 hours. And further raising the temperature of the dried carrier, and removing nitrate through high-temperature decomposition of nitrate to leave nickel oxide, wherein the decomposition temperature is 150 ℃ and 700 ℃, and the decomposition time is 30 minutes-10 hours.
Example 2
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth element), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth element). The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
Wherein the raw materials of the alumina, the zirconia, the lanthanum oxide (rare earth element) and the nickel oxide are alumina powder, zirconia powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the concentration of the nickel nitrate solution is 0.lmol/L.
The preparation method is as in example 1, wherein the catalyst comprises the following components in percentage by mass: 42% of nickel oxide, 42% of aluminum oxide, 12% of zirconium oxide and 4% of lanthanum oxide (rare earth element). The granular catalyst is a cylindrical granular catalyst with the diameter of 3mm and the height of 5 mm.
And (5) detecting nickel oxide through chemical analysis, and repeating the step (5) in the preparation method if the content of the nickel oxide is less than 40% (mass percentage content).
Example 3
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of the regular granular carrier made of the oxides of Al, Zr and La (rare-earth elements), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth elements), and features high average pore diameter (200-500 Å), pore volume (0.2-0.5 ml/g), and specific surface area greater than 45m2(g), the weight loss on ignition at 900 ℃ is less than 5 percent.
Wherein the raw materials of the alumina, the zirconia, the lanthanum oxide (rare earth element) and the nickel oxide are alumina powder, zirconia powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the concentration of the nickel nitrate solution is 0.5 mol/L.
The preparation method is as in example 1, wherein the catalyst 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 (rare earth element), and the balance of impurities. The granular catalyst is a cylindrical granular catalyst with the diameter of 2mm and the height of 3 mm.
And (5) detecting nickel oxide through chemical analysis, and repeating the step (5) in the preparation method if the content of the nickel oxide is less than 35% (mass percentage content).
Example 4
A catalyst for steam reforming of methane in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth elements), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La. The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
Wherein the raw materials of the alumina, the zirconia, the lanthanum oxide (rare earth element) and the nickel oxide are alumina powder, zirconia powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the concentration of the nickel nitrate solution is 0.6 mol/L.
The preparation method is as in example 1, wherein the catalyst comprises the following components in percentage by mass: 38% of nickel oxide, 47% of aluminum oxide, 11% of zirconium oxide and 4% of lanthanum oxide (rare earth element). The granular catalyst is a cylindrical granular catalyst with the diameter of 3mm and the height of 0.5 mm.
Example 5
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth element), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth element). The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
Wherein the raw materials of the alumina, the zirconia, the lanthanum oxide (rare earth element) and the nickel oxide are alumina powder, zirconia powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the concentration of the nickel nitrate solution is 0.4 mol/L.
The preparation method is as in example 1, wherein the catalyst comprises the following components in percentage by mass: 41% of nickel oxide, 43% of aluminum oxide, 11% of zirconium oxide and 5% of lanthanum oxide (rare earth element). The granular catalyst is a cylindrical granular catalyst with the diameter of 1mm and the height of 5 mm.
And (5) detecting nickel oxide through chemical analysis, and repeating the step (5) in the preparation method if the content of the nickel oxide is less than 40% (mass percentage content).
Example 6
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth element), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth element). The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
Wherein the raw materials of the alumina, the zirconia, the lanthanum oxide (rare earth element) and the nickel oxide are alumina powder, zirconia powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the concentration of the nickel nitrate solution is 0.8 mol/L.
The preparation method is as in example 1, wherein the catalyst comprises the following components in percentage by mass: 41.5% of nickel oxide, 48% of aluminum oxide, 7% of zirconium oxide and 3.5% of lanthanum oxide (rare earth element).
And (5) detecting nickel oxide through chemical analysis, and repeating the step (5) in the preparation method if the content of the nickel oxide is less than 40% (mass percentage content).
Example 7
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth element), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth element). The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
Wherein the raw materials of the alumina, the zirconia and the lanthana (rare earth element) nickel oxide are alumina powder, zirconia powder, lanthana (rare earth element) powder and nickel nitrate solution, and the concentration of the nickel nitrate solution is 0.9 mol/L.
The preparation method is as in example 1, wherein the catalyst comprises the following components in percentage by mass: 41% of nickel oxide, 48% of aluminum oxide, 6% of zirconium oxide and 5% of lanthanum oxide (rare earth element).
And (5) detecting nickel oxide through chemical analysis, and repeating the step (5) in the preparation method if the content of the nickel oxide is less than 40% (mass percentage content).
Example 8
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth element), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth element). The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
The raw materials of the aluminum oxide, the zirconium oxide, the lanthanum oxide (rare earth element) and the nickel oxide are aluminum oxide powder, zirconium oxide powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the mass ratio of the aluminum oxide powder to the zirconium oxide powder to the lanthanum oxide (rare earth element) powder is 7: 43: 4, the concentration of the nickel nitrate solution of the nickel oxide is 0.2 mol/L.
The zirconia adopts high-purity superfine zirconia powder (monoclinic phase), the alumina adopts high-purity superfine active alumina powder, and the lanthanum oxide adopts high-purity superfine lanthanum oxide (rare earth element) powder.
The preparation was as described in example 1.
Example 9
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth element), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth element). The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
The raw materials of the aluminum oxide, the zirconium oxide, the lanthanum oxide (rare earth element) and the nickel oxide are aluminum oxide powder, zirconium oxide powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the mass ratio of the aluminum oxide powder to the zirconium oxide powder to the lanthanum oxide (rare earth element) powder is 11: 47: 5, the concentration of the nickel nitrate solution of the nickel oxide is 0.7 mol/L.
The zirconia adopts high-purity superfine zirconia powder (monoclinic phase), the alumina adopts high-purity superfine active alumina powder, and the lanthanum oxide adopts high-purity superfine lanthanum oxide (rare earth element) powder.
The preparation was as described in example 1.
Example 10
A catalyst for steam reforming of methane in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth elements), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La. The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
Wherein the raw materials of alumina, zirconia, lanthanum oxide (rare earth element) and nickel oxide are alumina powder, zirconia powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the mass ratio of the alumina powder, the zirconia powder and the lanthanum oxide (rare earth element) powder is 7-11: 43-47: 4-5, and the concentration of the nickel nitrate solution of the nickel oxide is 0.7 mol/L.
The zirconia adopts high-purity superfine zirconia powder (monoclinic phase), the alumina adopts high-purity superfine active alumina powder, and the lanthanum oxide adopts high-purity superfine lanthanum oxide powder.
The preparation was as described in example 1.
Example 11
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth element), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth element). The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
The raw materials of the aluminum oxide, the zirconium oxide, the lanthanum oxide (rare earth element) and the nickel oxide are aluminum oxide powder, zirconium oxide powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the mass ratio of the aluminum oxide powder to the zirconium oxide powder to the lanthanum oxide (rare earth element) powder is 9: 45: 4.5, the concentration of the nickel nitrate solution of the nickel oxide is 0.7 mol/L.
The zirconia adopts high-purity superfine zirconia powder (monoclinic phase), the alumina adopts high-purity superfine active alumina powder, and the lanthanum oxide adopts high-purity superfine lanthanum oxide (rare earth element) powder.
The preparation was as described in example 1.
Example 12
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth element), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth element). The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
The raw materials of the aluminum oxide, the zirconium oxide, the lanthanum oxide (rare earth element) and the nickel oxide are aluminum oxide powder, zirconium oxide powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the mass ratio of the aluminum oxide powder to the zirconium oxide powder to the lanthanum oxide (rare earth element) powder is 10: 44: 5, the concentration of the nickel nitrate solution of the nickel oxide is 0.7 mol/L.
The zirconia adopts high-purity superfine zirconia powder (monoclinic phase), the alumina adopts high-purity superfine active alumina powder, and the lanthanum oxide adopts high-purity superfine lanthanum oxide (rare earth element) powder.
The preparation was as described in example 1.
Example 13
A catalyst for reforming methane steam in molten carbonate fuel cell is composed of regular granular carrier made of the oxides of Al, Zr and La (rare-earth element), Ni oxide, and the regular granular catalyst made of the oxides of Ni, Al, Zr and La (rare-earth element). The average pore diameter of the catalyst is 200-500 anga, the pore volume is 0.2-0.5ml/g, the specific surface area is more than 45m2/g, and the ignition weight loss at 900 ℃ is less than 5%.
The raw materials of the aluminum oxide, the zirconium oxide, the lanthanum oxide (rare earth element) and the nickel oxide are aluminum oxide powder, zirconium oxide powder, lanthanum oxide (rare earth element) powder and nickel nitrate solution, and the mass ratio of the aluminum oxide powder to the zirconium oxide powder to the lanthanum oxide (rare earth element) powder is 8: 46: 4.5, the concentration of the nickel nitrate solution of the nickel oxide is 0.7 mol/L.
The zirconia adopts high-purity superfine zirconia powder (monoclinic phase), the alumina adopts high-purity superfine active alumina powder, and the lanthanum oxide adopts high-purity superfine lanthanum oxide (rare earth element) powder.
The preparation was as described in example 1.
Example 14
The rest is as in example 1, wherein: the catalyst comprises the following components in percentage by mass: 35% of nickel oxide, 50% of aluminum oxide, 10% of zirconium oxide and 5% of cerium oxide (rare earth element).
Example 15
The rest is as in example 1, wherein: the catalyst comprises the following components in percentage by mass: 55% of nickel oxide, 35% of aluminum oxide, 6% of zirconium oxide and 4% of praseodymium oxide.
Example 16
The rest is as in example 1, wherein: the catalyst comprises the following components in percentage by mass: 60% of nickel oxide, 30% of aluminum oxide, 3% of zirconium oxide and 7% of yttrium oxide.
Example 17
The rest is as in example 1, wherein: the catalyst comprises the following components in percentage by mass: 48% of nickel oxide, 32% of aluminum oxide, 15% of zirconium oxide and 1% of gadolinium oxide.
Example 18
The rest is as in example 1, wherein: the catalyst comprises the following components in percentage by mass: 36% of nickel oxide, 42% of aluminum oxide, 12% of zirconium oxide and 10% of holmium oxide.
Example 19
The rest is as in example 1, wherein: the catalyst comprises the following components in percentage by mass: 58% of nickel oxide, 38% of aluminum oxide, 1% of zirconium oxide and 3% of gadolinium oxide.
Example 20
The rest is as in example 1, wherein: the catalyst comprises the following components in percentage by mass: 36% of nickel oxide, 45% of aluminum oxide, 4% of zirconium oxide and 15% of lanthanum oxide.
Test No.)
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 60,000 psig, as shown in FIG. 1.
The comparative sample was a catalyst prepared according to the preparation method of US patent 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) was used as active reforming phase (component a), 180g of a catalyst containing γ -Al were added2O3、 δ-A/2 O3And theta-Al2O3Alumina powder (BET = 126 m)2/g，d50=116 μm; ) (ii) a 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 FIG. 1, the present invention has larger pore diameter than the comparative sample, provides an active channel for reforming reaction, and the alkali metal of the electrolyte is not easy to block the pore diameter, so that the catalyst activity is not reduced.
Test two catalyst poisoning test
A comparative sample and the catalyst of the present invention were taken for the poisoning test, wherein the comparative sample was the comparative sample in test one.
The test is as follows:
reaction tube diameter of 25 mm 25 × 3mm, catalyst size of 2mm 2 × 4mm, test particle size of original particle size, catalyst loading volume of 3ml, catalyst loading height of about 1cm, electrolyte weight of 31g, 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:
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: 10000h-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 ℃; after reduction is finished, pumping water through a constant flow pump, pumping the water into a water catalyst bed layer, introducing CO after the water catalyst bed layer is stabilized at 550 DEG C2And continuously raising the temperature of the catalyst bed layer to 650 ℃, closing the N2 after the temperature is stabilized, and introducing CH4 to carry out initial activity determination on the catalyst. For poisoning studies, the reactor was cooled to room temperature and placed under an inert gas (N)2) Next, the test gas was re-introduced through the electrolyte layer, and when the time was started after the temperature of the electrolyte layer was increased to 650 ℃, the inlet and outlet composition was analyzed once in 4 hours at the time of the poisoning test, and the methane conversion was periodically measured throughout the test period (about 800 hours), and the results are shown in fig. 2.
As can be seen from fig. 2, 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 comparative sample and inventive catalyst were tested and analyzed for pore size and pore volume before use, after reduction and after poisoning, and the pore size distribution was determined according to ASTM UOP578-02 using mercury intrusion methods using contact angles of 140 ° and pressures ranging from 0.6 to 60,000 psig, the comparative sample results are shown in fig. 3, and the inventive catalyst results are shown in fig. 4.
Wherein the control sample is the control in test one.
As can be seen from fig. 4, 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 the pore diameter and pore distribution have substantially no changes particularly after reduction and neutralization. It can be seen from fig. 3 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 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 (8)
1. A catalyst for steam reforming of methane in a molten carbonate fuel cell, characterized by: the catalyst comprises a granular carrier made of oxides of aluminum, zirconium and lanthanum, and nickel oxide is loaded on the granular carrier to form a granular catalyst formed by the oxides of nickel, aluminum, zirconium and lanthanum; the catalyst comprises 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%; average pore diameter of catalyst
Pore volume is 0.2-0.5ml/g, specific surface area of catalyst is greater than 45m2/g。
2. The catalyst for steam reforming of methane in a molten carbonate fuel cell according to claim 1, wherein: 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%.
3. The catalyst for steam reforming of methane in a molten carbonate fuel cell according to claim 1, wherein: the catalyst 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.
4. A catalyst for steam reforming of methane in a molten carbonate fuel cell according to any one of claims 1-3, wherein: the raw materials of the alumina, the zirconia, the lanthanum oxide and the nickel oxide are alumina powder, zirconia powder, lanthanum oxide powder and nickel nitrate solution, and the mass ratio of the alumina powder to the zirconia powder to the lanthanum oxide powder is 7-11: 43-47: 4-5.
5. The catalyst for steam reforming of methane in a molten carbonate fuel cell according to claim 4, wherein: the concentration of the nickel nitrate solution is 0. L-lmol/L.
6. The catalyst for steam reforming of methane in a molten carbonate fuel cell according to claim 1, wherein: the mass percentage content of nickel oxide in the catalyst is more than or equal to 35 percent; the catalyst is a cylindrical granular catalyst with the diameter of 1-3mm and the height of 0.5-5 mm.
7. The catalyst for steam reforming of methane in a molten carbonate fuel cell according to claim 1, wherein: the weight loss on ignition of the catalyst at 900 ℃ is lower than 5%.
8. The catalyst for steam reforming of methane in a molten carbonate fuel cell according to claim 1, wherein: 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.
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| PCT/CN2018/111870 WO2019134424A1 (en) | 2018-01-04 | 2018-10-25 | Catalyst for steam reforming of methane in fuel cell |
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| CN108134102B (en) * | 2018-01-04 | 2020-10-09 | 西南化工研究设计院有限公司 | Catalyst for methane steam reforming in fuel cell |
| CN110947391B (en) * | 2019-11-28 | 2021-05-07 | 南昌大学 | Lanthanum oxide supported nickel-based catalyst and preparation method and application thereof |
| CN111313031B (en) * | 2020-02-26 | 2021-03-26 | 深圳氢时代新能源科技有限公司 | Composite catalyst particles, and preparation method and application thereof |
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