CN103752319A - Anti-carbon-deposition Ni-based catalyst for hydrogen production by methane steam reforming and preparation method thereof - Google Patents

Abstract

The invention relates to an anti-carbon-deposition Ni-based catalyst for hydrogen production by methane steam reforming and a preparation method thereof. By taking lanthanum nitrate, praseodymium nitrate, samarium nitrate, yttrium nitrate, zirconium nitrate, zirconium carbonate, zirconium oxychloride, and the like as precursors and taking ammonia as a precipitant, a pyrochlore composite oxide is prepared through using a coprecipitation method; and then the pyrochlore composite oxide is mixed with alumina by using a mechanical mixing method so as to obtain a pyrochlore alumina composite carrier. Nickel nitrate, nickel chloride, nickel sulfate, nickel oxalate and the like serving as nickel sources are loaded on the pyrochlore alumina composite carrier through direct immersion. The loading capacity of nickel in the catalyst accounts for 5-30% of the weight of the catalyst, the pyrochlore content of the catalyst is 5-50%, and the alumina content of the catalyst is 20-90%. By taking the pyrochlore alumina composite oxide as a carrier, the reaction activity and anti-carbon-deposition performance of the catalyst can be greatly increased; the preparation method of the catalyst is simple; and the catalyst has excellent catalytic activity and stability to methane steam reforming in a stationary bed.

Description

Anti-carbon deposition Ni-based methane steam reforming hydrogen production catalyst and preparation method thereof

technical field

The invention belongs to the field of catalysis, and relates to a hydrogen production catalyst for steam reforming of methane.

Background technique

Hydrogen is an important industrial raw material and reducing agent. It is widely used in various fields of national economy, such as fertilizer, petrochemical, food, fine chemical, pharmaceutical, electronics, metallurgy, scientific research and other industries. At the same time, hydrogen is also an important green new energy. As an energy source, hydrogen energy will play a pivotal role on the world energy stage in the 21st century. It is an extremely superior new energy source. Its main advantages are high combustion calorific value; the only product of combustion is water, which is very clean; it can be made from water, and its resources are relatively abundant. But because hydrogen is a secondary energy source, there is no free pure hydrogen in nature and the atmosphere, its production not only needs to consume a lot of energy, but also the current large-scale reforming industrial hydrogen production efficiency is low. Therefore, seeking cheap hydrogen production technology is still a common concern of scientists all over the world.

At present, the methods for large-scale production of hydrogen mainly include: steam reforming of natural gas, steam reforming of light oil, water gas reaction, etc. Among them, steam reforming (SRM) of natural gas is the most common application. Generally, the following endothermic reaction occurs on the supported nickel-based catalyst to generate a hydrogen-rich mixed gas:

CH ₄ + H ₂ O = CO + 3H ₂ ΔH = +210 kJ/mol

CO + H ₂ O = CO ₂ + H ₂ ΔH = +43.5 kJ/mol

About 1/2 of the hydrogen in the world is produced by this method. The basic process flow is roughly the same, that is, it consists of four major units: raw material gas treatment, steam reforming, CO shifting and hydrogen purification. Studies have shown that when the precious metals Ru, Rh, Pd, etc. are loaded on a suitable carrier, they all have high reactivity and anti-carbon deposition performance. However, due to the high price of precious metals, the sources are limited, and they are widely used in automobile exhaust treatment. Among them, the preparation of noble metal-free high-performance catalysts is still an attractive research direction. Among non-noble metals, nickel catalysts have high reactivity, but have severe carbon deposition. Carbon deposits will not only cover the surface of the catalyst to cause catalyst deactivation, but also cause catalyst pulverization and blockage of the reactor, resulting in an increase in the pressure of the catalyst bed. So far, after extensive and in-depth discussions on various types of Ni-based reforming catalysts, it has been found that rare earth ions are good catalyst promoters due to their special 4f electronic structure and usually a variety of stable valence changes. Studies have shown that rare earth ions such as La, Ce, and Pr as additives can improve the strong interaction between supported metal catalysts such as Pt, Pd, Ni and other metal active catalytic center components and the support, thus improving their surface stability on the support surface. Excellent dispersion and high temperature stability, thereby effectively improving its anti-coking performance, and greatly improving the activity and life of the catalyst. At the same time, some rare earth oxides can supply oxygen to the active metal component Ni because they contain a small amount of active oxygen, so they can also improve the anti-coking performance of the catalyst and prolong its life.

Currently, the commonly used supports for steam methane reforming catalysts are alumina, zirconia, ceria, magnesia, lanthanum oxide, niobium oxide, zeolite, perovskite, silica clay, yttrium oxide, cobalt oxide, iron oxide and a mixture or one thereof. However, its catalytic activity and stability cannot meet the needs of industrial hydrogen production by steam reforming of methane. Composite oxides with fixed composition such as perovskite, spinel and hexaaluminate with different chemical compositions are used as Ni supports, or Ni is introduced into these composite oxide species as lattice ions to prepare reforming catalysts. This type of catalyst usually has high activity, anti-coking performance, reaction stability and thermal stability, and is suitable for the high-temperature environment of natural gas steam or dry gas reforming.

Pyrochlore is a new type of inorganic non-metallic material that has received widespread attention in the past ten years. It has the advantages of high melting point, good thermal stability, and low sintering speed. The results of XRD phase analysis show that, except for Ce, other rare earth elements react with SnO ₂ in the solid phase during the roasting process to form a pyrochlore crystal phase with the structure of Sn ₂ Ln ₂ O ₇ , so the thermal stability is improved. And it is beneficial to maintain a high specific surface at high temperature.

Contents of the invention

A methane steam reforming catalyst for hydrogen production and a preparation method thereof provided by the invention have the characteristics of simple preparation method, high reactivity, strong anti-coking ability, good stability, and can reduce costs. It is used in methane water When hydrogen is produced by steam reforming, it can meet the requirements of industrialization for catalyst activity and service life.

In order to solve the problems of the technologies described above, the technical solution of the present invention is as follows:

Anti-coking Ni-based methane steam reforming hydrogen production catalyst, the content of nickel in the catalyst is 5-30% of the catalyst weight, the content of rare earth pyrochlore is 5-50% of the catalyst mass, and the content of alumina is 5-50% of the catalyst weight. 20% to 90% of the mass; the rare earth is one or more of La, Y, Pr, and Sm;

The pyrochlore is rare earth zirconium or rare earth tin base pyrochlore.

The alumina carrier is roasted and ground after high-temperature pretreatment, and the selected particle diameter is 1-3 mm, preferably 0.125-0.250 mm.

The preparation method of the described anti-carbon deposition Ni-based methane steam reforming hydrogen production catalyst comprises the steps:

(1) Dissolve rare earth soluble salts and zirconium soluble salts in water, preferably in deionized water, use ammonia water as a precipitant, control pH = 9-11, stir until precipitation is complete, age, wash, and dry at 600-1000 Roasting at ℃ for 2-6 hours to prepare rare earth zirconium composite oxides;

(2) Mix the rare earth zirconium composite oxide and alumina obtained in step (1) evenly, grind it with an agate mortar for 1 hour, and then roast it at 600-1000°C, preferably 800°C, for 2-6 hours to obtain pyrochlore Alumina composite oxide carrier;

(3) Dissolve the soluble nickel salt in deionized water according to the composition ratio of the catalyst, and after stirring evenly, impregnate the greenstone-alumina composite oxide carrier obtained in step (2) in the solution, and ultrasonically disperse for 10-60 minutes while stirring , after drying, calcining at 600-1000°C for 2-6 hours to obtain catalyst powder.

In step (1), the rare earth is one or more of La, Y, Pr, and Sm, and the soluble salt is nitrate.

The drying in step (2) is oven drying or vacuum drying.

The soluble nickel salt in step (3) is nickel nitrate, nickel oxalate or nickel acetate.

The catalyst powder is pressed and molded to obtain a molded catalyst, and the molded catalyst can be made into a granular catalyst after being crushed.

Put the prepared 8-12 mesh granular catalyst into a fixed-bed quartz reactor to evaluate the activity and stability of the catalyst. The reactor is a quartz tube reactor with an inner diameter of φ12mm and a length of 300mm, and the catalyst dosage is 2-10ml. The catalyst is first reduced with hydrogen at a certain temperature for 2-4 hours, and then the catalyst is evaluated for activity and stability at a temperature of 600-1000°C.

The methane steam reforming hydrogen production catalyst provided by the invention has the following advantages:

(1) Pyrochlore alumina composite oxide is used as the carrier in the catalyst, which is a novel carrier used in the field of methane steam reforming to produce hydrogen. The pyrochlore composite oxide is prepared by coprecipitation method, and the process is simple. The cost is low, and the repeatability of the preparation process is good. After 250 hours of continuous reaction, the conversion rate still reached over 85%, and the activity of the catalyst did not decrease and showed a slight upward trend. After the reaction, no obvious carbon deposition can be seen in the thermogravimetric analysis of the sample.

(2) The catalyst of the present invention adopts the direct impregnation method, the preparation method is simple, the conditions are easy to control, and the repeatability of the catalyst is good.

Description of drawings

Fig. 1 is the X-ray diffraction (XRD) figure of the Ni/Ln ₂ Zr ₂ O ₇ catalyst of the present invention.

Fig. 2 is the X-ray diffraction (XRD) diagram of the Ni/La ₂ Zr ₂ O ₇ -Al ₂ O ₃ catalyst of the present invention.

Detailed ways

The following examples and accompanying drawings will help to understand the present invention, but do not limit the content of the present invention.

The alumina carrier is spherical alumina produced by Shandong Zibo Chalco. The particle diameter of the alumina carrier is 1-3mm.

Example 1

Ni/La ₂ Zr ₂ O ₇ particle catalyst, the preparation method is as follows:

(1) Dissolve La(NO ₃ ) ₃ ·6H ₂ O and Zr(NO ₃ ) ₃ ·3H ₂ O with a La:Zr (molar ratio) of 1:1 in deionized water measured to a concentration of 0.5 mol /L solution;

(2) Dilute the industrial ammonia water with a concentration of 25% to 1 times as a precipitating agent. Under continuous stirring, add the salt solution obtained in (1) dropwise to the above precipitating agent, control the pH=10, and after the precipitation is complete, let it stand at room temperature. After drying for 12 hours, wash with deionized water until the TDS of the filtrate is <<20, dry in a blast oven at 90°C for 12 hours, and bake at 800°C for 4 hours to obtain a La ₂ Zr ₂ O ₇ composite oxide support, which is characterized by XRD, as shown in the figure As shown in 1, the characteristic diffraction peak of the pyrochlore structure appeared on the support; the X-ray diffraction results showed that the catalysts with the pyrochlore structure containing different rare earths were synthesized.

(3) Ni(NO ₃ ) ₃ 6H ₂ O with a nickel content of 12% by mass of the catalyst was dissolved in metered deionized water, and the prepared carrier was impregnated in metered nickel salt solution by an equal volume impregnation method, The above-mentioned precursor impregnated with nickel ions was left at room temperature for 12 hours, evaporated to dryness in a water bath at 80°C, dried at 90°C, and calcined at 800°C for 4 hours to prepare a Ni/La ₂ Zr ₂ O ₇ methane steam reforming hydrogen production catalyst powder;

(4) The above-mentioned prepared catalyst powder is pressed into tablets under a certain pressure, and crushed and sieved to 60-80 mesh, prepared into a granular catalyst, and packed in a fixed-bed quartz reactor for catalyst activity and Stability evaluation, the methane conversion rate reached 84.6% after 259 hours of reaction at 800 °C.

Example 2

Ni/Y ₂ Zr ₂ O ₇ particle catalyst, the preparation method is as follows:

(1) Dissolve Y(NO ₃ ) ₃ ·6H ₂ O and Zr(NO ₃ ) ₃ ·3H ₂ O in metered deionized water with a Y:Zr (molar ratio) of 1:1, and make the concentration 0.5mol /L solution;

(2) Dilute the industrial ammonia water with a concentration of 25% to 1 times as a precipitating agent. Under continuous stirring, add the salt solution obtained in (1) dropwise to the above precipitating agent, control the pH=10, and after the precipitation is complete, let it stand at room temperature. After drying for 12 hours, wash with deionized water until the TDS of the filtrate<<20, dry in a blast drying oven at 90°C for 12h, and bake at 800°C for 4h to obtain a Y ₂ Zr ₂ O ₇ composite oxide support, which is characterized by XRD, as shown in the figure As shown in 1, the carrier has pyrochlore-type structural characteristic diffraction peaks;

(3) Ni(NO ₃ ) ₃ 6H ₂ O with a nickel content of 12% by mass of the catalyst was dissolved in metered deionized water, and the prepared carrier was impregnated in metered nickel salt solution by an equal volume impregnation method, The above-mentioned precursor impregnated with nickel ions was left at room temperature for 12 hours, evaporated to dryness in a water bath at 80°C, dried at 90°C, and calcined at 800°C for 4 hours to prepare a Ni/Y ₂ Zr ₂ O ₇ methane steam reforming hydrogen production catalyst powder;

(4) The above-mentioned prepared catalyst powder is pressed into tablets under a certain pressure, and crushed and sieved to 60-80 mesh, prepared into a granular catalyst, and packed in a fixed-bed quartz reactor for catalyst activity and Stability evaluation. The methane conversion rate reached 78.5% after reacting at 800 °C for 81 hours.

Example 3

Ni/Pr ₂ Zr ₂ O ₇ particle catalyst, the preparation method is as follows:

(1) Dissolve Pr(NO ₃ ) ₃ 6H ₂ O and Zr(NO ₃ ) ₃ 3H ₂ O in metered deionized water with a Pr:Zr (molar ratio) of 1:1 to a concentration of 0.5 mol /L solution;

(2) Dilute the industrial ammonia water with a concentration of 25% to 1 times as a precipitating agent. Under continuous stirring, add the salt solution obtained in (1) dropwise to the above precipitating agent, control the pH=10, and after the precipitation is complete, let it stand at room temperature. After drying for 12 hours, wash with deionized water until the TDS of the filtrate is <<20, dry in a forced air oven at 90°C for 12 hours, and calcinate at 800°C for 4 hours to obtain a Pr ₂ Zr ₂ O ₇ composite oxide carrier, which is characterized by XRD, as shown in the figure As shown in 1, the carrier has pyrochlore-type structural characteristic diffraction peaks;

(3) Ni(NO ₃ ) ₃ 6H ₂ O with a nickel content of 12% by mass of the catalyst was dissolved in metered deionized water, and the prepared carrier was impregnated in metered nickel salt solution by an equal volume impregnation method, The above-mentioned precursor impregnated with nickel ions was left at room temperature for 12 hours, evaporated to dryness in a water bath at 80°C, dried at 90°C, and calcined at 800°C for 4 hours to prepare a Ni/Pr ₂ Zr ₂ O ₇ methane steam reforming hydrogen production catalyst powder;

(4) The above-mentioned prepared catalyst powder is pressed into tablets under a certain pressure, and crushed and sieved to 60-80 mesh, prepared into a granular catalyst, and packed in a fixed-bed quartz reactor for catalyst activity and Stability evaluation. The methane conversion rate reached 54.6% after reacting at 800 °C for 122 hours.

Example 4

Ni/Sm ₂ Zr ₂ O ₇ particle catalyst, the preparation method is as follows:

(1) Dissolve Sm(NO ₃ ) ₃ 6H ₂ O and Zr(NO ₃ ) ₃ 3H ₂ O in metered deionized water with a Sm:Zr (molar ratio) of 1:1, and prepare a concentration of 0.5 mol /L solution;

(2) Dilute the industrial ammonia water with a concentration of 25% to 1 times as a precipitating agent. Under continuous stirring, add the salt solution obtained in (1) dropwise to the above precipitating agent, control the pH=10, and after the precipitation is complete, let it stand at room temperature. After 12 hours, wash with deionized water until the TDS of the filtrate is < 20, dry in a blast oven at 90°C for 12h, and roast at 800°C for 4h to obtain a Sm ₂ Zr ₂ O ₇ composite oxide carrier, which is characterized by XRD, as shown in Figure 1 As shown, the carrier has pyrochlore-type structure characteristic diffraction peaks;

(3) Ni(NO ₃ ) ₃ 6H ₂ O with a nickel content of 12% by mass of the catalyst was dissolved in metered deionized water, and the prepared carrier was impregnated in metered nickel salt solution by an equal volume impregnation method, The above-mentioned precursor impregnated with nickel ions was left at room temperature for 12 hours, evaporated to dryness in a water bath at 80°C, dried at 90°C, and calcined at 800°C for 4 hours to prepare a Ni/Sm ₂ Zr ₂ O ₇ methane steam reforming hydrogen production catalyst powder;

(4) The above-mentioned prepared catalyst powder is pressed into tablets under a certain pressure, and crushed and sieved to 60-80 mesh, prepared into a granular catalyst, and packed in a fixed-bed quartz reactor for catalyst activity and Stability evaluation. The methane conversion rate reached 84.5% after reacting at 800 °C for 105 hours.

Example 5

Ni/5%La ₂ Zr ₂ O ₇ -Al ₂ O ₃ particle catalyst, the preparation method is as follows:

Step (1), (2) are with embodiment 1;

(3) Mix the pyrochlore carrier prepared in (2) with 5% of the mass of the catalyst and 95% of the 80-100 mesh alumina powder, grind it with an agate mortar for 1 hour, and then roast it at 800°C for 4 hours to obtain Pyrochlore-alumina composite oxide carrier;

(4) Ni(NO ₃ ) ₃ 6H ₂ O with a nickel content of 12% by mass of the catalyst was dissolved in metered deionized water, and the prepared carrier was impregnated in metered nickel salt solution by an equal-volume impregnation method, The above-mentioned precursor impregnated with nickel ions was left at room temperature for 12 hours, evaporated to dryness in a water bath at 80°C, dried at 90°C, and calcined at 800°C for 4 hours to prepare a Ni/La ₂ Zr ₂ O ₇ methane steam reforming hydrogen production catalyst powder;

(5) The above-mentioned prepared catalyst powder is pressed into tablets under a certain pressure, and crushed and sieved to 60-80 mesh, prepared into a granular catalyst, and packed in a fixed-bed quartz reactor for catalyst activity and Stability evaluation. The methane conversion rate reached 96.4% after reacting at 800 °C for 103 hours. Figure 2, the results of the X-ray diffraction pattern of the catalyst show that a catalyst with a pyrochlore structure was synthesized, and a nickel metaaluminate crystal phase was formed.

Example 6

Ni/10%La ₂ Zr ₂ O ₇ -Al ₂ O ₃ particle catalyst, the preparation method is as follows:

Step (1), (2) are with embodiment 1;

(3) Mix the pyrochlore carrier prepared in (2) with 10% of the mass of the catalyst and 90% of the 80-100 mesh alumina powder, grind it with an agate mortar for 1 hour, and then roast it at 800°C for 4 hours to obtain Pyrochlore-alumina composite oxide carrier;

(4) Ni(NO ₃ ) ₃ 6H ₂ O with a nickel content of 12% by mass of the catalyst was dissolved in metered deionized water, and the prepared carrier was impregnated in metered nickel salt solution by an equal-volume impregnation method, The above-mentioned precursor impregnated with nickel ions was left at room temperature for 12 hours, evaporated to dryness in a water bath at 80°C, dried at 90°C, and calcined at 800°C for 4 hours to prepare a Ni/La ₂ Zr ₂ O ₇ methane steam reforming hydrogen production catalyst powder;

(5) The above-mentioned prepared catalyst powder is pressed into tablets under a certain pressure, and crushed and sieved to 60-80 mesh, prepared into a granular catalyst, and packed in a fixed-bed quartz reactor for catalyst activity and Stability evaluation. The methane conversion rate reached 98.8% after reacting at 800 °C for 100 hours. Figure 2, the results of the X-ray diffraction pattern of the catalyst show that a catalyst with a pyrochlore structure was synthesized, and a nickel metaaluminate crystal phase was formed.

Example 7

Ni/15%La ₂ Zr ₂ O ₇ -Al ₂ O ₃ particle catalyst, the preparation method is as follows:

Step (1), (2) are with embodiment 1;

(3) Mix the pyrochlore carrier prepared in (2) with 15% of the mass of the catalyst and 85% of the 80-100 mesh alumina powder, grind it with an agate mortar for 1 hour, and then roast it at 800°C for 4 hours to obtain Pyrochlore-alumina composite oxide carrier;

(4) Ni(NO ₃ ) ₃ 6H ₂ O with a nickel content of 12% by mass of the catalyst was dissolved in metered deionized water, and the prepared carrier was impregnated in metered nickel salt solution by an equal-volume impregnation method, The above-mentioned precursor impregnated with nickel ions was left at room temperature for 12 hours, evaporated to dryness in a water bath at 80°C, dried at 90°C, and calcined at 800°C for 4 hours to prepare a Ni/La ₂ Zr ₂ O ₇ methane steam reforming hydrogen production catalyst powder;

(5) The above-mentioned prepared catalyst powder is pressed into tablets under a certain pressure, and crushed and sieved to 60-80 mesh, prepared into a granular catalyst, and packed in a fixed-bed quartz reactor for catalyst activity and Stability evaluation. The conversion rate of methane reached 96.5% after reacting at 800°C for 100 hours. Figure 2, the results of the X-ray diffraction pattern of the catalyst show that a catalyst with a pyrochlore structure was synthesized, and a nickel metaaluminate crystal phase was formed.

Example 8

Ni/20%La ₂ Zr ₂ O ₇ -Al ₂ O ₃ granular catalyst, the preparation method is as follows:

Step (1), (2) are with embodiment 1;

(3) Mix the pyrochlore carrier prepared in (2) with 20% of the mass of the catalyst and 80% of the 80-100 mesh alumina powder, grind it with an agate mortar for 1 hour, and then roast it at 800°C for 4 hours to obtain Pyrochlore-alumina composite oxide carrier;

(4) Ni(NO ₃ ) ₃ 6H ₂ O with a nickel content of 12% by mass of the catalyst was dissolved in metered deionized water, and the prepared carrier was impregnated in metered nickel salt solution by an equal-volume impregnation method, The above-mentioned precursor impregnated with nickel ions was left at room temperature for 12 hours, evaporated to dryness in a water bath at 80°C, dried at 90°C, and calcined at 800°C for 4 hours to prepare a Ni/La ₂ Zr ₂ O ₇ methane steam reforming hydrogen production catalyst powder;

(5) The above-mentioned prepared catalyst powder is pressed into tablets under a certain pressure, and crushed and sieved to 60-80 mesh, prepared into a granular catalyst, and packed in a fixed-bed quartz reactor for catalyst activity and Stability evaluation. The conversion rate of methane reached 96.9% after reacting at 800°C for 100 hours. Figure 2, the results of the X-ray diffraction pattern of the catalyst show that a catalyst with a pyrochlore structure was synthesized, and a nickel metaaluminate crystal phase was formed.

Example 9

Ni/30%La ₂ Zr ₂ O ₇ -Al ₂ O ₃ granular catalyst, the preparation method is as follows:

Step (1), (2) are with embodiment 1;

(3) Mix the pyrochlore carrier prepared in (2) with 30% of the mass of the catalyst and 70% of the 80-100 mesh alumina powder, grind it with an agate mortar for 1 hour, and then roast it at 800°C for 4 hours to obtain Pyrochlore-alumina composite oxide carrier;

(4) Ni(NO ₃ ) ₃ 6H ₂ O with a nickel content of 12% by mass of the catalyst was dissolved in metered deionized water, and the prepared carrier was impregnated in metered nickel salt solution by an equal-volume impregnation method, The above-mentioned precursor impregnated with nickel ions was left at room temperature for 12 hours, evaporated to dryness in a water bath at 80°C, dried at 90°C, and calcined at 800°C for 4 hours to prepare a Ni/La ₂ Zr ₂ O ₇ methane steam reforming hydrogen production catalyst powder;

(5) The above-mentioned prepared catalyst powder is pressed into tablets under a certain pressure, and crushed and sieved to 60-80 mesh, prepared into a granular catalyst, and packed in a fixed-bed quartz reactor for catalyst activity and Stability evaluation. The methane conversion rate reached 95.7% after reacting at 800 °C for 50 hours. Figure 2, the results of the X-ray diffraction pattern of the catalyst show that a catalyst with a pyrochlore structure was synthesized, and a nickel metaaluminate crystal phase was formed.

Claims (7)

1. Anti-coking Ni-based methane steam reforming hydrogen production catalyst, characterized in that the content of nickel in the catalyst is 5-30% of the weight of the catalyst, and the content of rare earth pyrochlore is 5-50% of the weight of the catalyst. The content of aluminum is 20-90% of the mass of the catalyst; the rare earth is one or more of La, Y, Pr and Sm. 2. The anti-carbon deposition Ni-based methane steam reforming hydrogen production catalyst as claimed in claim 1, characterized in that the pyrochlore is a rare earth zirconium-based or a rare-earth tin-based pyrochlore. 3. The anti-carbon deposition Ni-based methane steam reforming hydrogen production catalyst as claimed in claim 1, characterized in that the alumina carrier is roasted and ground through high-temperature pretreatment, and the selected particle diameter is 1-3mm, preferably 0.125-0.250 mm. 4. the preparation method of the anti-carbon deposition Ni-base methane steam reforming hydrogen production catalyst described in claim 1 comprises the steps: (1) dissolving rare earth soluble salts and zirconium soluble salts in water is preferably dissolved in deionized water, with Ammonia water is used as a precipitating agent, control pH=9-11, stir until the precipitation is complete, age, wash, dry, and roast at 600-1000°C for 2-6 hours to obtain a rare earth zirconium composite oxide; (2) the step (1 ) mixing the obtained rare earth zirconium composite oxide and alumina evenly, grinding with an agate mortar for 1 hour, and then calcining at 600-1000°C, preferably 800°C, for 2-6 hours to obtain a pyrochlore-alumina composite oxide carrier; (3) Dissolve the soluble nickel salt in deionized water according to the composition ratio of the catalyst, and after stirring evenly, impregnate the greenstone-alumina composite oxide carrier obtained in step (2) in the solution, and ultrasonically disperse for 10-60 minutes while stirring , after drying, calcining at 600-1000°C for 2-6 hours to obtain catalyst powder. 5. The method according to claim 4, wherein the rare earth in step (1) is one or more of La, Y, Pr, Sm, and the soluble salt is nitrate. 6. The method according to claim 4, characterized in that the drying in step (2) is oven drying or vacuum drying. 7. The method according to claim 4, characterized in that the soluble nickel salt in step (3) is nickel nitrate, nickel oxalate or nickel acetate.

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