Preparation and application of hydrocarbon reforming hydrogen production catalyst for direct reduction iron process

Abstract

The invention discloses preparation and application of a hydrocarbon reforming hydrogen production catalyst for a direct reduction iron process. The catalyst contains 60-80% of a carrier, 10-15% of an active component I, 5-10% of an active component II, 1-5% of an anti-carbon additive, 3-10% of a structural additive and 1-3% of an electronic additive. The prepared catalyst has the advantages of high strength, high activity, carbon deposition resistance, excellent sintering resistance and high stability, the heat transfer function of the catalyst is improved due to the abundant pore structure, the surface temperature is reduced, and carbon deposition is reduced. The prepared catalyst is suitable for a CO2-supplementing reforming hydrogen production process of natural gas with a low water-carbon ratio in gas-based direct reduction iron, can be applied to an MIDREX process and a gas reduction process of an equal hydrogen-based shaft furnace, can be used under harsh conditions such as low-carbon hydrocarbon water vapor reforming and CO2 reforming hydrogen production, and is high in methane one-way conversion rate and CO2 one-way conversion rate.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of catalyst preparation, in particular to preparation and application of a hydrocarbon reforming hydrogen catalyst for a direct reduction iron process. BACKGROUND

[0002] The gas-based direct reduction iron process is a low-carbon and environmentally friendly metallurgical technology, which has the advantages of simple process, low energy consumption and small pollution compared with the traditional blast furnace metallurgical process. The reducing gas used for direct reduction iron is derived from natural gas reforming gas, coal gasification furnace gas, coke oven gas, etc., among which natural gas reforming gas accounts for about 80%. The hydrogen-based gas-based shaft furnace smelting technology can theoretically reduce carbon dioxide emissions by more than 50%. The preparation of reducing gas is the core technology of the gas-based direct reduction iron process. The reducing gas is prepared by cracking natural gas into CO and H2. The natural gas hydrogen production technology mainly includes steam reforming, CO2 dry reforming and partial oxidation reforming. At present, steam reforming is the most mature. In order to reduce carbon emissions, the steel and metallurgical industry usually combines CO2 in natural gas with low steam reforming, achieving the goal of energy saving and low carbon emission.

[0003] The reaction process is as follows: CH4+H2O→CO +H2(1) CH4-H2O reforming CH4+CO2→CO +H2(2) CH4-CO2 reforming The existing hydrocarbon conversion catalyst has many problems in the application of the direct reduction iron process: (1) In the direct reduction iron reforming hydrogen production process, low-carbon hydrocarbons such as methane and ethane will form carbon deposition on the surface of the catalyst to cover the active sites of the catalyst, resulting in catalyst deactivation. At the same time, the low water-carbon ratio of the reaction easily leads to carbon deposition on the surface of the catalyst. (2) The poor heat dissipation performance of the catalyst leads to the migration and agglomeration of the surface active component metal ions to form larger particles. With the progress of the reaction, the specific surface area of the catalyst decreases sharply, causing the sintering or loss of the active component. (3) The reforming catalyst has large geometric size, short gas reaction contact time, low reaction pressure and low geometric surface area. The raw material gas cannot fully contact with the active component of the catalyst, which reduces the conversion efficiency of low-carbon hydrocarbons.

[0004] Patent CN105688916A discloses a high-dispersion high-load high-activity low-temperature methane reforming nickel-based catalyst. The catalyst contains nickel as the active component and adds calcium, yttrium, magnesium, cerium, zirconium and lanthanum as the synergistic components, and 5-8 nm nickel grains are prepared. The catalyst reacts under high-activity low-temperature (400-800 DEG C) conditions. The nickel content of the catalyst of the application reaches 20-25%, and in actual application, the metal nickel will migrate and agglomerate, thereby causing the sintering of the catalyst.

[0005] Patent CN114618490 discloses a natural gas reforming hydrogen catalyst and its preparation method and application. The invention is composed of platinum supported on aluminum-manganese composite oxide and palladium supported on cerium oxide in a ratio of 1-4:1. The platinum oxide: aluminum-manganese composite oxide is 0.05-1:100, and the palladium oxide: cerium oxide is 0.02-0.5:100. The active components are loaded on the carrier by impregnation, and then mixed uniformly according to the ratio. The invention uses noble metals as active components, which has good sintering resistance, but the active site density is much smaller than that of Ni, Co and other metal active components, so the activity of the catalyst is relatively low. At the same time, noble metal has poor sulfur resistance, high production cost of noble metal catalyst, and is not conducive to industrialization.

[0006] Patent CN114931959A discloses a catalyst for hydrogen production from light hydrocarbons. The catalyst uses spherical colloidal alumina as a carrier and oxides of nickel, cadmium and platinum as composite active components. The composite active components are evenly coated on the surface of colloidal alumina. The molar ratio of nickel, cadmium and platinum is 10:6.5-8.5:0.6-1.3. The active component solution is sprayed on the surface of colloidal alumina. The catalyst can effectively improve the pore structure of the catalyst by using a porous carrier, but the active components are prone to loss and migration on the surface of the catalyst.

[0007] In summary, it is of great practical significance and economic value to develop a hydrocarbon conversion catalyst for direct reduced iron process with high activity, excellent anti-coking performance, high dispersion of active components and good thermal stability. SUMMARY

[0008] The purpose of the present invention is to solve the problems of the catalyst for direct reduced iron process. The preparation method of a hydrocarbon reforming hydrogen catalyst for direct reduced iron process is provided. The catalyst prepared by the method has high activity, high strength, strong anti-coking performance and good thermal stability, which can better solve the problems in the background technology.

[0009] To achieve the above purposes, the specific technical solutions of the present invention are as follows: A hydrogen reforming catalyst for a direct reduction iron process, the catalyst comprising a carrier, an active component one, an active component two, an anti-carbon deposition aid, an electron aid and a structure aid; wherein the carrier is an aluminum-containing material with a high stable structure, accounting for 60-80% of the weight percentage of the catalyst; the active component one is a transition metal, accounting for 10-15% of the weight percentage of the catalyst (calculated in the oxidized state); the active component two accounts for 3-8% of the weight percentage of the catalyst; the anti-carbon deposition aid is a metal oxide with oxygen storage function, accounting for 1-3% of the mass percentage of the catalyst; the electron aid accounts for 1-3% of the weight percentage of the catalyst, and the structure aid accounts for 3-8% of the weight percentage of the catalyst, and the total mass percentage is 100%.

[0010] As a better embodiment in the application, the carrier is one or a combination of Al2O3, MgO, CaO, ZrO2 and TiO2; more preferably, the carrier is one or a combination of Al2O3, MgO and ZrO2.

[0011] As a better embodiment in the application, the active component one is any one or a combination of Ni and Re metal oxides.

[0012] As a better embodiment in the application, the active component two is any one or a combination of Fe and Co metal oxides.

[0013] As a better embodiment in the application, the anti-carbon deposition aid is any one or a combination of CeO2, La2O3, Sm2O3, Pr2O3, Nd2O3, Cr2O3 and SnO2; more preferably, the anti-carbon deposition aid is any one or a combination of CeO2, La2O3, Nd2O3 and Pr2O3.

[0014] As a better embodiment in the application, the electron aid is any one or a combination of Na, K, Rb and Cs; more preferably, the electron aid is any one or a combination of K and Cs.

[0015] As a better embodiment in the application, the structure aid is any one or a combination of calcium aluminate, magnesium aluminate, potassium aluminate and sodium aluminate; more preferably, the structure aid is any one or a combination of calcium aluminate and magnesium aluminate.

[0016] Another object of the application is to provide a preparation method of the above-mentioned catalyst.

[0017] As a preferred embodiment of this application, the preparation method of a hydrocarbon reforming hydrogen production catalyst for direct reduction iron process includes the following steps: (1) Dissolve the soluble salt of the anti-carbon deposition additive in deionized water and stir until homogeneous to obtain mixed solution A. Then transfer mixed solution A to a high-pressure hydrothermal reactor. The mass concentration of salt in solution A is 1-5%. (2) Add the raw materials of the carrier to the high-pressure hydrothermal reactor, set the rotation speed and temperature, add an appropriate amount of alkali to adjust the pH value, and then add the modified synthetic dispersant; slowly start the high-pressure hydrothermal reactor, keep the rotation speed constant, set the pressure of the hydrothermal reactor, and carry out the hydrothermal reaction at a certain hydrothermal reaction temperature to obtain the slurry; (3) The slurry obtained in (2) is filtered and washed, dried and then calcined to obtain modified carrier precursor B; (4) Add the structural aid, release agent and pore-forming agent to the precursor B and ball mill them in a high-speed ball mill, then sieve them to obtain the ball-milled material C; (5) Add demineralized water to the ball-milled material C and mix and stir evenly, then prepare granulated material D by dry granulation machine; (6) Use a rotary tablet press to press the granulated material D to obtain a cylindrical arc-shaped porous or cylindrical sidewall grooved arc-shaped porous precursor E; (7) Precursor E was placed in air for natural curing, and then calcined in a calcining furnace at high temperature to obtain calcined precursor F. The water absorption rate and bulk density of calcined precursor F were measured. (8) Dissolve the salt of active component one, the salt of active component two and the salt of electronic additive in deionized water, stir evenly to obtain precursor solution G, the total salt mass concentration of solution G is 29-35%; (9) Place the calcined precursor F in a high-pressure reactor, then measure the precursor solution G, add a dispersant to the precursor solution G and stir evenly, add pH adjustment solution to adjust the pH value to between 2 and 4 and then transfer it to the high-pressure reactor. Under closed conditions, heat up, pressurize and impregnate. After impregnation, filter, then dry and calcine to obtain the precursor H. (10) Repeat the impregnation and calcination steps in (9) with the obtained precursor H to obtain catalyst I, which is the hydrocarbon reforming hydrogen production catalyst of the direct reduction iron process.

[0018] As a preferred embodiment of this application, in step (1) of the method for preparing a hydrocarbon reforming hydrogen production catalyst for a direct reduction iron process, the soluble salt of the anti-carbon deposition promoter is one or a combination of several of cerium nitrate, lanthanum nitrate, samarium nitrate, praseodymium nitrate, cerium oxalate, and lanthanum oxalate. In a preferred embodiment of this application, in step (2) of the method for preparing a hydrocarbon reforming hydrogen production catalyst for a direct reduction iron process, the support raw material is one or a combination of several of the following: alumina, aluminum nitrate, aluminum hydroxide, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium nitrate, zirconium nitrate, zirconium oxalate, and titanium dioxide; the stirring speed when the support raw material is added to the mixed solution A is 600~1500 r / min, and the temperature is 70~80℃; the alkali is one or a combination of several of the following: potassium carbonate, ammonia, ethylenediamine, triethylamine, and aniline; the pH value is adjusted to 7-10 by adding alkali; the modified synthetic dispersant is any one or a combination of several of the following: ethylene glycol, 1,2-propanediol, glycerol, and polyethylene glycol; the amount of modified synthetic dispersant added is 3~8% of the weight of the support; the pressure of the hydrothermal reactor is 0.5~3 MPa, the hydrothermal reaction temperature is 120~180℃, the reaction time is 4~24 h, and the ultrasonic frequency is 10KHz~50KHz.

[0019] As a preferred embodiment of this application, in step (3) of the preparation method of the hydrocarbon reforming hydrogen production catalyst of the direct reduction iron process, the slurry is filtered and washed 3 times; the drying conditions are 120~200℃ for 2~10h, and the calcination conditions are 500℃ for 3~8h.

[0020] As a preferred embodiment of this application, in step (4) of the method for preparing a hydrocarbon reforming hydrogen production catalyst for a direct reduction iron process, the release agent is one or more of graphite, calcium stearate, magnesium stearate and sodium stearate, and the amount added is 1-3% of the weight of precursor B; the pore-forming agent is one or more of guar gum powder, starch, polyethyl cellulose, polyvinyl alcohol and polycaprolactone, and the amount added is 1-3% of the weight of precursor B; the ball milling time in the high-speed ball mill is 2-10 hours, and the ball milled product is passed through a 200-mesh sieve.

[0021] As a preferred embodiment of this application, in step (5) of the method for preparing a hydrocarbon reforming hydrogen production catalyst for a direct reduction iron process, the amount of demineralized water added is 10-20% of the weight of the ball milled material C; the particle size of the granulated material D is sieved through a 20-100 mesh sieve.

[0022] In a preferred embodiment of this application, in step (6) of the method for preparing a hydrocarbon reforming hydrogen production catalyst using a direct reduction iron process, the specific dimensions of the cylindrical arc-shaped porous structure are: outer diameter of the cylinder 10-25 mm, length of the cylinder itself 10-15 mm, total length of the two arc surfaces of the cylinder 10-30 mm, number of intermediate holes 4-6, and hole diameter 1-4 mm; the specific dimensions of the cylindrical sidewall grooved arc-shaped porous structure are: outer diameter of the cylinder 20-40 mm, length of the cylinder itself 10-15 mm, total length of the two arc surfaces of the cylinder 10-30 mm, number of intermediate holes 4-6, and hole diameter 1-4 mm; number of outer wall grooves 3-6, and diameter 2-5 mm.

[0023] As a preferred embodiment of this application, in step (7) of the method for preparing a hydrocarbon reforming hydrogen production catalyst by direct reduction iron process, the natural curing time is 24~120h; the high-temperature calcination temperature in the calcining furnace is 1000~1500℃, and the time is 3~10h.

[0024] In a preferred embodiment of this application, in step (8) of the method for preparing a hydrocarbon reforming hydrogen production catalyst for a direct reduction iron process, the salt of active component one is one or a combination of nickel nitrate, nickel oxalate, ferric nitrate, and ferric oxalate; the salt of active component two is one or a combination of cobalt nitrate, perrhenic acid, and cobalt oxalate; and the salt of the electronic additive is one or a combination of sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, and potassium oxalate.

[0025] In a preferred embodiment of this application, in step (9) of the method for preparing a hydrocarbon reforming hydrogen production catalyst for a direct reduction iron process, the volume ratio of calcined precursor F to precursor solution G is 1-2; the pH adjusting solution is an acid or a base, wherein the acid is one or a combination of nitric acid, formic acid, acetic acid, oxalic acid, hydrochloric acid, and phosphoric acid; the base is one or a combination of ammonia, ethylenediamine, and phenylethylamine; the dispersant is one or a combination of citric acid, tartaric acid, polyethylene glycol, ethylene glycol, and polypyrrolidone; the amount of dispersant is 1-3% of the carrier weight; the catalyst is sealed in an autoclave, heated to 100-150°C, pressurized to 1-3 MPa and impregnated for 1-5 hours, filtered after impregnation, dried at 100-200°C for 2-8 hours, and then calcined at 400-600°C for 3-10 hours.

[0026] In a preferred embodiment of this application, in step (10) of the method for preparing a hydrocarbon reforming hydrogen production catalyst by direct reduction iron process, the impregnation and calcination step in step (9) is repeated 1 to 3 times with the obtained precursor H.

[0027] This invention protects the catalysts prepared using the above methods.

[0028] The third objective of this invention is to provide the application of the catalyst described above, namely, its application in the direct reduction of iron process for hydrogen production from hydrocarbon reforming.

[0029] As a preferred embodiment of this application, the catalyst (product) is used under the following conditions: the inlet temperature of the reaction gas is 500~800℃, and the volume hourly space velocity (VHSV) is 1000~3000 h⁻¹. -1 The reaction pressure is 0.1~0.5MPa, and the water-to-carbon ratio is 0.2~0.8. The inlet methane volume concentration is ≤30%, and the inlet carbon dioxide volume concentration is ≤20%.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) In this invention, the anti-carbon deposition agent is dispersed and embedded in the carrier lattice through ultrasonic high-pressure hydrothermal synthesis, which improves the catalyst's anti-carbon deposition ability. After adding the structural additive, high-temperature steam curing is performed to achieve structural solidification. Then, calcination at a high temperature above 1000℃ results in a catalyst strength ≥700N / particle, while forming a stable crystal orientation and reducing side reactions. The pore-forming agent provides the carrier with a richer pore structure and a larger specific surface area, providing richer and more convenient "channels" for the internal diffusion of reactants, thus improving the reaction efficiency.

[0031] (2) The high temperature and high pressure impregnation method of this invention can make the active metal more uniformly dispersed on its inner and outer surfaces. At the same time, the synergistic effect of the two active metals reduces the migration rate of the same metal particles on the catalyst surface at high temperature, effectively reducing the agglomeration of active metal particles on the catalyst surface and causing sintering deactivation.

[0032] (3) In this invention, bimetallic synergistic catalysis, the catalyst’s excellent anti-sintering and hydrocarbon conversion performance and its strong interaction with the support extend the catalyst’s service life.

[0033] (4) The electronic additives added in this invention can improve electron transfer for the valence state cycle of active variable valence metals, and can also transfer electrons to surface active metals to improve the adsorption and desorption rate of hydrocarbon gases, thereby increasing the reaction rate.

[0034] (v) The finished catalyst obtained in this invention has a cylindrical arc-shaped porous surface or a cylindrical arc-shaped porous surface with grooves on the outer wall. Compared with traditional cylindrical or cylindrical planar porous surfaces, it has lower bed resistance, a larger geometric surface area in actual use, and better surface heat dissipation performance. At the same time, the catalyst is more uniformly dispersed during impregnation, and the larger geometric surface area can greatly increase the density of active sites and improve the reaction rate of the catalyst. Attached Figure Description

[0035] Figure 1 This is a schematic diagram of the structure of an evaluation device for a dechlorinating agent for deep removal of organic chlorine from raw gas at room temperature, as described in this invention. Figure labels: 1: Nitrogen cylinder, 2: 20% vol hydrogen + nitrogen cylinder, 3: Raw material gas cylinder, 4, 7, 10, 15, 16, 23, 25, 26, 30: Shut-off valve, 5, 8, 11: Gas pressure reducing valve, 6, 9, 12: Gas mass flow meter, 13: Gas mixer, 14: Three-way ball valve, 17: Horizontal flow pump, 18: Deionized water storage bottle, 19: Balance, 20: Deionized water vaporizer, 21: Reactor, 22: Tubular heater, 24: Condenser, 27, 31, 33: Needle valve, 32: Wet flow meter, 34: Gas chromatograph. Detailed Implementation

[0036] A direct reduction iron process hydrocarbon reforming hydrogen production catalyst, comprising a support, an active component one, an active component two, an anti-coking agent, an electronic aid, and a structural aid; wherein the support is an aluminum-containing material with a highly stable structure, accounting for 60-80% by weight of the catalyst; the active component one is a transition metal, accounting for 10-15% by weight of the catalyst (based on oxidation state); the active component two accounts for 3-8% by weight of the catalyst; the anti-coking agent is a metal oxide with oxygen storage function, accounting for 1-3% by weight of the catalyst; the electronic aid accounts for 1-3% by weight of the catalyst; and the structural aid accounts for 3-8% by weight of the catalyst; the total mass percentage is 100%.

[0037] Furthermore, the carrier is one or more of Al2O3, MgO, CaO, ZrO2, and TiO2, more preferably one or more of Al2O3, MgO, and ZrO2.

[0038] Furthermore, the active component is any one or a combination of two of Ni and Re metal oxides; Furthermore, the second active component is any one or a combination of several of Co and Fe metal oxides.

[0039] Furthermore, the anti-carbon deposition agent is any one or a combination of several of CeO2, La2O3, Sm2O3, Pr2O3, Nd2O3, Cr2O3, and SnO2; more preferably, it is any one or a combination of several of CeO2, La2O3, Nd2O3, and Pr2O3.

[0040] Furthermore, the electronic additive is any one or a combination of Na, K, Rb, and Cs, more preferably any one or a combination of K and Cs.

[0041] Furthermore, the structural additive is any one or a combination of several of calcium aluminate, magnesium aluminate, potassium aluminate, and sodium aluminate, more preferably, the structural additive is any one or a combination of two of calcium aluminate and magnesium aluminate.

[0042] Furthermore, the preparation method of the hydrocarbon reforming hydrogen production catalyst for the direct reduction iron process includes the following steps: (1) Weigh a certain amount of the anti-carbon deposition additive soluble salt and dissolve it in an appropriate amount of deionized water and stir evenly. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasound) to obtain mixed solution A.

[0043] (2) Weigh an appropriate amount of carrier raw material and add it to mixed solution A. Set the rotation speed to 800~1200 r / min, raise the temperature to 70~80℃, add a certain concentration of alkali solution at a certain rate to adjust the pH value to 8-10, and then add 2~5% of the carrier weight of modified synthetic dispersant. Slowly start the high-pressure hydrothermal reactor, keep the rotation speed constant, set the pressure of the hydrothermal reactor to 1~3 MPa, the hydrothermal reaction temperature to 120~150℃, the reaction time to 12~24 h, and the ultrasonic frequency to 20KHz~50KHz.

[0044] (3) The slurry obtained in (2) is filtered and washed 3 times, then dried at 120~180℃ for 4~8h, and then calcined at 500℃ for 3~6h to obtain modified carrier precursor B.

[0045] (4) Weigh an appropriate amount of structural additive, 2-5% of the weight of precursor B of release agent and 1-3% of the weight of precursor B of pore-forming agent and add them to a high-speed ball mill for ball milling for 4-8 hours. Then pass the mixture through a 200-mesh sieve to obtain ball milled material C.

[0046] (5) Add 10-20% of desalinated water by weight of C, mix and stir evenly, and then sieve through a dry granulator to obtain granulated material D with a mesh size of 20-100.

[0047] (6) Use a rotary tablet press to press the granulated material into a cylindrical arc-shaped porous or cylindrical arc-shaped porous precursor with grooved sidewalls.

[0048] (7) Precursor E is placed in air and naturally cured for 24-120 hours, and then calcined in a calcining furnace at 1000-1500℃ for 3-10 hours to obtain calcined precursor F. The water absorption rate and bulk density of F are measured.

[0049] (8) Prepare a certain concentration of active component one salt, active component two salt and electronic auxiliary salt, dissolve them in a certain amount of deionized water, and stir evenly to obtain precursor solution G.

[0050] (9) Take a certain volume of calcined precursor F and place it in a high-pressure reactor. Then, take precursor solution G according to the liquid-solid volume ratio of 1-2. Then, add 1-3% of the carrier weight of dispersant and stir evenly. Add an appropriate amount of pH adjustment solution to adjust the pH value to between 2 and 4 and then transfer it to a high-pressure reactor. Seal and heat to 100-150℃ and pressurize to 1-3MPa for 1-5 hours. After immersion, filter and dry at 100-200℃ for 2-8 hours. Then, calcine at 400-600℃ for 3-10 hours to obtain precursor H.

[0051] (10) Repeat the impregnation and calcination steps (8) 1 to 3 times with the obtained precursor H to obtain catalyst I.

[0052] Furthermore, the soluble salt of the anti-carbon deposit additive mentioned in step (1) is one or a combination of several of cerium nitrate, lanthanum nitrate, neodymium nitrate, praseodymium nitrate, etc.

[0053] Furthermore, the carrier material mentioned in step (2) is one or a combination of several of alumina, aluminum nitrate, aluminum hydroxide, magnesium hydroxide, magnesium nitrate, and zirconium nitrate. The alkali is one or a combination of several of ammonia and ethylenediamine. The modified synthetic dispersant is any one or a combination of two of ethylene glycol and polyethylene glycol.

[0054] Furthermore, the release agent mentioned in step (4) is one or a combination of two of graphite and magnesium stearate. The pore-forming agent is one or a combination of two of guar gum powder and polyvinyl alcohol.

[0055] Furthermore, the specific dimensions of the cylindrical arc-shaped porous shape in step (6) are as follows: outer diameter of cylinder 10~25mm, length of cylinder 10~15mm, total length of the two arc surfaces of cylinder 10~30mm, number of intermediate holes 4~6, diameter of holes 1~4mm; the specific dimensions of the cylindrical sidewall grooved arc-shaped porous shape are as follows: outer diameter of cylinder 20~40mm, length of cylinder 10~15mm, total length of the two arc surfaces of cylinder 10~30mm, number of intermediate holes 4~6, diameter of holes 1~4mm; number of outer wall grooves 3~6, ​​diameter of grooves 2~5mm.

[0056] Furthermore, in step (8), the soluble salt of active component one is one or a combination of two of nickel nitrate and ferric nitrate. The soluble salt of active component two is one or a combination of two of cobalt nitrate and perrhenic acid. The soluble salt of the electronic additive is one or a combination of two of potassium nitrate and cesium nitrate. The acid is nitric acid or oxalic acid, and the alkali solution is ammonia or ethylenediamine. The dispersant is one or a combination of two of citric acid and ethylene glycol.

[0057] Furthermore, the operating conditions for catalyst product G are as follows: reaction gas inlet temperature of 500~800℃, and reaction volume hourly space velocity of 1000~3000 h⁻¹. -1 The reaction pressure is 0.1~0.5MPa, and the water-to-carbon ratio is 0.2~0.8. The inlet methane volume concentration is ≤30%, and the inlet carbon dioxide volume concentration is ≤20%.

[0058] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0059] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0060] It should be noted that the terminology used herein is for the purpose of describing particular implementations only and is not intended to limit the exemplary implementations according to this application. As used herein, the singular form includes the plural form unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this description, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0061] In this invention, some conventional operating equipment, devices and components have been omitted or only briefly described.

[0062] Unless otherwise specified in the examples, the conditions shall be performed according to the standard conditions or the conditions recommended by the manufacturer.

[0063] In this application, any percentage not marked indicates its weight percentage content.

[0064] Example 1: A direct reduction iron process hydrocarbon reforming hydrogen production catalyst, comprising a support, an active component one, an active component two, an anti-coking agent, an electronic aid, and a structural aid; wherein... Carrier: Al2O3 53%, ZrO2 20%, totaling 73%; Active component 1: NiO 10%; Active component 2: Fe2O35%; Structural additives: 8% pure magnesium aluminate; Electronic additive: K2O 2%; Anti-carbon deposit additive: CeO22%, with a total mass percentage of 100%.

[0065] The preparation method of the above catalyst includes the following steps: (1) Weigh 50.46 g of cerium nitrate hexahydrate and dissolve it in 1200 g of deionized water and stir until homogeneous. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasound) to obtain mixed solution A1.

[0066] (2) Weigh 530 g of alumina that has passed through a 200-mesh sieve and 696.32 g of zirconium nitrate pentahydrate and add them to mixed solution A1. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, and add 1 mol / L potassium carbonate solution at a rate of 10 ml / min to adjust the pH value to 8.5. Then add 35 g of ethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 1 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 16 h, and the ultrasonic frequency to 40 kHz.

[0067] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 6 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B1.

[0068] (4) Weigh 80 g of magnesium aluminate, 21.6 g of graphite, 7.2 g of magnesium stearate and 14.4 g of guar gum powder and ball mill them with precursor B1 in a high-speed ball mill for 5 h, and pass them through a 200 mesh sieve to obtain ball milled material C1.

[0069] (5) Add 15% of deionized water by weight of C1, mix and stir evenly, and then sieve through a dry granulator to obtain granulated material D1 with a mesh size of 20~100.

[0070] (6) Use a low-speed tablet press to press the granulated material into a precursor E1 with an outer diameter of 25mm, 5 holes in the middle (hole diameter of 3mm), a column height of 12mm, and a total height of 25mm with arc surfaces at both ends.

[0071] (7) Precursor E1 was naturally cured in air for 48 hours, and then calcined at 1300℃ in a calcining furnace for 6 hours to obtain calcined precursor F1. The water absorption rate of F1 was 31% and the bulk density was 0.9 kg / L.

[0072] (8) Weigh 418g of nickel nitrate hexahydrate, 271.5g of ferric nitrate nonahydrate and 46.2g of potassium nitrate and dissolve them in 736g of deionized water and stir well to obtain impregnation solution G1.

[0073] (9) Take 200 ml of calcined precursor F1 and place it in a high-pressure reaction vessel. Take 300 ml of G1 solution, add 3.6 g of citric acid and stir well. Add an appropriate amount of ethylenediamine to adjust the pH value to 2.5, then transfer it to a high-pressure reactor. Seal the reactor and pressurize it to 2 MPa. Heat it to 100 °C and impregnate it for 2 h. After impregnation, filter it, then dry it at 130 °C for 5 h, and then calcine it at 450 °C for 5 h to obtain the first impregnation precursor H1.

[0074] (10) The precursor H1 obtained is impregnated and calcined twice in step (9) to obtain catalyst I1.

[0075] Example 2: A direct reduction iron process hydrocarbon reforming hydrogen production catalyst, comprising a support, an active component one, an active component two, an anti-coking agent, an electronic aid, and a structural aid; wherein... Carrier: Al2O3 40%, MgO 15%, ZrO2 15%, totaling 70%; Active component 1: NiO 10%, ReO 25%; Active component 2: Co2O 35%; Structural aid: 6% calcium aluminate; Electronic additive: K2O 1%; Anti-carbon deposit additive: 2% La2O3, with a total mass percentage of 100%.

[0076] The preparation method of the above catalyst includes the following steps: (1) Weigh 79.69 g of lanthanum nitrate hexahydrate and dissolve it in 1200 g of deionized water and stir until homogeneous. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasound) to obtain mixed solution A2.

[0077] (2) Weigh 400 g of alumina that has passed through a 200-mesh sieve, 961.54 g of magnesium nitrate hexahydrate, and 523.17 g of lanthanum nitrate pentahydrate and add them to mixed solution A2. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, add 1 mol / L potassium carbonate solution at a rate of 10 ml / min to adjust the pH value to 8.5, and then add 21 g of ethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12 h, and the ultrasonic frequency to 40 kHz.

[0078] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 6 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B2.

[0079] (4) Weigh 60g of calcium aluminate, 21.6g of graphite, 7.2g of calcium stearate and 21.6g of polyvinyl alcohol and ball mill them with precursor B2 in a high-speed ball mill for 5h, and pass them through a 200-mesh sieve to obtain ball milled material C2.

[0080] (5) Add 10% of desalinated water by weight of C2 and mix evenly. Then, sieve the mixture through a dry granulator to obtain granulated material D2 with a mesh size of 20-100.

[0081] (6) Use a low-speed tablet press to press the granulated material into a precursor E2 with an outer diameter of 20mm, 5 holes in the middle (hole diameter of 2mm), a column height of 12mm, and a total height of 20mm with arc surfaces at both ends.

[0082] (7) Precursor E2 was placed in air and naturally cured for 110 hours, and then calcined at 1300℃ for 6 hours in a calcining furnace to obtain calcined precursor F2. The water absorption rate of F2 was 32% and the bulk density was 0.88 kg / L.

[0083] (8) Weigh 404.16 g of nickel nitrate hexahydrate, 182.6 g of cobalt nitrate hexahydrate, 65.28 g of perrhenic acid dihydrate and 22.38 g of potassium nitrate soluble salt and dissolve them in 773.63 g of deionized water and stir well to obtain solution G2.

[0084] (9) Take 200 ml of calcined precursor F2 and place it in a high-pressure reaction vessel. Take 300 ml of G2 solution, add 3.6 g of ethylene glycol and stir until homogeneous. Add an appropriate amount of nitric acid to adjust the pH value to 3, then transfer it to a high-pressure reactor. Seal the reactor and pressurize it to 2 MPa. Heat it to 120 °C and impregnate it for 2 h. After impregnation, filter it and dry it at 130 °C for 5 h. Then calcine it at 450 °C for 5 h to obtain the first impregnation precursor H2.

[0085] (10) The precursor H2 obtained is impregnated and calcined twice in step (9) to obtain catalyst I2.

[0086] Example 3: A direct reduction iron process hydrocarbon reforming hydrogen production catalyst, comprising a support, an active component one, an active component two, an anti-coking agent, an electronic aid, and a structural aid; wherein... Carrier: Al2O3 60%, ZrO2 18%, totaling 78%; Active component 1: NiO 10%; Active component 2: 15% Co2O3; Structural aid: 3% calcium aluminate; Electronic additive: Cs2O 3%; Anti-carbon deposit additive: Nd2O3 1%, the total mass percentage is 100%.

[0087] The preparation method of the above catalyst includes the following steps: (1) Weigh 26.45 g of neodymium nitrate hexahydrate and dissolve it in 1200 g of deionized water and stir until homogeneous. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasound) to obtain mixed solution A3.

[0088] (2) Weigh 600 g of alumina that has passed through a 200-mesh sieve and 627.8 g of zirconium nitrate pentahydrate and add them to mixed solution A3. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, and add 1 mol / L potassium carbonate solution at a rate of 10 ml / min to adjust the pH value to 8.5. Then add 24 g of polyethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12 h, and the ultrasonic frequency to 40 kHz.

[0089] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 8 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B3.

[0090] (4) Weigh 60g of calcium aluminate, 16.2g of calcium stearate and 24.3g of guar gum powder and ball mill them with precursor B3 in a high-speed ball mill for 5h, and pass them through a 200-mesh sieve to obtain ball-milled material C3.

[0091] (5) Add 600g of desalinated water to C3 and mix evenly. Then dry at 120℃ until the moisture content is 10%. Then sieve through a dry granulator to obtain granulated material D3 with a mesh size of 20~100.

[0092] (6) Use a low-speed tablet press to press the granulated material into a precursor E3 with an outer diameter of 30mm, 7 holes in the middle (hole diameter of 2mm), a column height of 12mm, and a total height of 25mm with arc surfaces at both ends.

[0093] (7) Precursor E3 was placed in air and naturally cured for 30 hours, and then calcined at 1400℃ in a calcining furnace for 3 hours to obtain calcined precursor F3. The water absorption rate of calcined precursor F3 was 32% and the bulk density was 0.89 kg / L.

[0094] (8) Weigh 404.16 g of nickel nitrate hexahydrate, 182.6 g of cobalt nitrate hexahydrate and 43.2 g of cesium nitrate and dissolve them in 782 g of deionized water and stir until homogeneous to obtain solution G3.

[0095] (9) Take 200 ml of calcined precursor F3 and place it in a high-pressure reaction vessel. Take 300 ml of G2 solution, add 3.6 g of ethylene glycol and stir until homogeneous. Add an appropriate amount of nitric acid to adjust the pH value to 3, then transfer it to a high-pressure reactor. Seal the reactor and pressurize it to 2 MPa. Heat it to 120 °C and impregnate it for 4 h. After impregnation, filter the solution, then dry it at 130 °C for 5 h, and then calcine it at 450 °C for 5 h to obtain the first impregnation precursor H3.

[0096] (10) The precursor H3 obtained is subjected to the impregnation and calcination steps of step (9) twice to obtain catalyst I3.

[0097] Example 4: A direct reduction iron process hydrocarbon reforming hydrogen production catalyst, comprising a support, an active component one, an active component two, an anti-coking agent, an electronic aid, and a structural aid; wherein... Carrier: Al2O3 64%; Active component 1: NiO 15%; Active component 2: Co2O 38%; Structural aid: 8% calcium aluminate; Electronic additive: K2O 2%; Anti-carbon deposit additive: Pr2O3 3%, with a total mass percentage of 100%.

[0098] The preparation method of the above catalyst includes the following steps: (1) Weigh 79.1 g of praseodymium nitrate hexahydrate and dissolve it in 1500 g of deionized water. Stir until homogeneous, then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasonic equipment) to obtain mixed solution A4. 3.7 (2) Weigh 979 g of aluminum hydroxide that has passed through a 200-mesh sieve and add it to mixed solution A4. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, add 1 mol / L ammonia water at a rate of 10 ml / min to adjust the pH value to 9, and then add 12.4 g of polyethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12 h, and the ultrasonic frequency to 40 kHz.

[0099] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 6 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B4.

[0100] (4) Weigh 60g of calcium aluminate, 24.8g of graphite and 12.4g of guar gum powder and ball mill them with precursor B4 in a high-speed ball mill for 5h, and pass them through a 200-mesh sieve to obtain ball milled material C4.

[0101] (5) Add 600g of desalinated water to C4 and mix evenly. Then dry at 120℃ until the moisture content is 15%. Then sieve through a dry granulator to obtain granulated material D4 with a mesh size of 20~100.

[0102] (6) Use a low-speed tablet press to press the granulated material into a precursor E4 with an outer diameter of 20mm, 5 holes in the middle (hole diameter of 2mm), a column height of 12mm, and a total height of 20mm with arc surfaces at both ends.

[0103] (7) Precursor E4 was naturally cured in air for 30 hours, and then calcined at 1300℃ in a calcining furnace for 3 hours to obtain calcined precursor F4. The water absorption rate of calcined precursor F4 was 36% and 0.85 kg / L.

[0104] (8) Weigh 538.89 g of nickel nitrate hexahydrate, 259.7 g of cobalt nitrate hexahydrate and 39.79 g of potassium nitrate and dissolve them in 703.61 g of deionized water and stir until homogeneous to obtain solution G4.

[0105] (9) Measure 200 ml of carrier F4 and place it in a high-pressure reaction vessel. Measure 300 ml of G4 solution, add 5.1 g of ethylene glycol and stir until homogeneous. Add an appropriate amount of oxalic acid to adjust the pH to 3, then transfer to a high-pressure reactor. Seal the reactor and pressurize to 2 MPa. Heat the reactor to 120°C and impregnate for 4 h. After impregnation, filter the solution, then dry it at 130°C for 5 h, and then calcine it at 450°C for 5 h to obtain the first impregnation precursor H4.

[0106] (10) The precursor H4 obtained was impregnated and calcined twice in step (9) to obtain catalyst I4.

[0107] Example 5: A direct reduction iron process hydrocarbon reforming hydrogen production catalyst, comprising a support, an active component one, an active component two, an anti-coking agent, an electronic aid, and a structural aid; wherein... Carrier: Al2O3 51%, MgO 20%, totaling 71%; Active component 1: ReO2 12%; Active component 2: Co2O 36%; Structural aid: 6% calcium aluminate; Electronic additive: K2O 2%; Anti-carbon deposit additives: CeO2 2%, La2O3 1%, with a total mass percentage of 100%.

[0108] The preparation method of the above catalyst includes the following steps: (1) Weigh 50.49 g of cerium nitrate hexahydrate and 26.56 g of lanthanum nitrate hexahydrate, dissolve them in 1500 g of deionized water and stir until homogeneous. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasonic treatment) to obtain mixed solution A5. 3.7 (2) Weigh 510 g of alumina and 291.65 g of magnesium hydroxide that have passed through a 200-mesh sieve and add them to mixed solution A5. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, and add 1 mol / L potassium carbonate solution at a rate of 10 ml / min to adjust the pH value to 8.5. Then add 14 g of ethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12 h, and the ultrasonic frequency to 40 kHz.

[0109] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 6 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B5.

[0110] (4) Weigh 60g of calcium aluminate, 14.6g of graphite, 7.3g of calcium stearate and 14.6g of guar gum powder and ball mill them with precursor B5 in a high-speed ball mill for 5h, and pass them through a 200-mesh sieve to obtain ball-milled material C5.

[0111] (5) Add 500g of desalinated water to C5 and mix evenly. Then dry at 120℃ until the moisture content is 15%. Then sieve through a dry granulator to obtain granulated material D5 with a mesh size of 20~100.

[0112] (6) Use a low-speed tablet press to press the granulated material into a precursor E5 with an outer diameter of 25mm, 5 holes in the middle (hole diameter of 3mm), a column height of 12mm, and a total height of 25mm with arc surfaces at both ends.

[0113] (7) The precursor E5 was naturally cured in air for 72 hours, and then calcined at 1300℃ in a calcining furnace for 9 hours to obtain the modified carrier F5. The water absorption rate of the carrier F5 was 30%, and the bulk density was 0.91 kg / L.

[0114] (8) Weigh 175.47 g of perrhenic acid dihydrate, 245.42 g of cobalt nitrate hexahydrate and 50.14 g of potassium nitrate and dissolve them in 585.79 g of deionized water and stir until homogeneous to obtain solution G5.

[0115] (9) Measure 200 ml of carrier F5 and place it in a high-pressure reaction vessel. Measure 300 ml of G5 solution, add 1.82 g of citric acid and stir until homogeneous. Add an appropriate amount of oxalic acid to adjust the pH to 3, then transfer it to a high-pressure reactor. Seal the reactor and pressurize it to 2 MPa. Heat the reactor to 120 °C and impregnate for 4 h. After impregnation, filter the solution, then dry it at 130 °C for 5 h, and then calcine it at 450 °C for 5 h to obtain the first impregnation precursor H5.

[0116] (10) The precursor H5 obtained is impregnated and calcined once in step (9) to obtain catalyst I5.

[0117] Example 6: A direct reduction iron process hydrocarbon reforming hydrogen production catalyst, comprising a support, an active component one, an active component two, an anti-coking agent, an electronic aid, and a structural aid; wherein... Carrier: Al2O3 52%, MgO 20%, totaling 72%; Active component 1: NiO 12%; Active component 2: Co2O 36%; Structural aid: 6% calcium aluminate; Electronic additive: K2O 2%; Anti-carbon deposit additive: CeO22%, with a total mass percentage of 100%.

[0118] The preparation method of the above catalyst includes the following steps: (1) Weigh 50.49 g of cerium nitrate hexahydrate and 26.56 g of lanthanum nitrate hexahydrate and dissolve them in 1500 g of deionized water and stir until homogeneous. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasound) to obtain mixed solution A6.

[0119] (2) Weigh 520 g of alumina and 200 g of magnesium oxide that have passed through a 200-mesh sieve and add them to mixed solution A6. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, and add 1 mol / L potassium carbonate solution at a rate of 10 ml / min to adjust the pH value to 8.5. Then add 14 g of ethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12 h, and the ultrasonic frequency to 40 kHz.

[0120] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 6 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B6.

[0121] (4) Weigh 60g of calcium aluminate, 14.6g of graphite, 7.3g of calcium stearate and 14.6g of guar gum powder and ball mill them with precursor B6 in a high-speed ball mill for 5h, and pass them through a 200-mesh sieve to obtain ball-milled material C6.

[0122] (5) Add 600g of desalinated water to C6 and mix evenly. Then dry at 120℃ until the moisture content is 15%. Then sieve through a dry granulator to obtain granulated material D6 with a mesh size of 20~100.

[0123] (6) Use a low-speed tablet press to compress the granulated material into a cylindrical shape with grooved sidewalls and a porous arc surface. The specific dimensions are as follows: outer diameter of the cylinder is 25mm, length of the cylinder itself is 12mm, total length of the two arc surfaces of the cylinder is 25mm, number of holes in the middle is 5 with a diameter of 3mm; number of grooves on the outer wall is 4 with a diameter of 4mm. The precursor E6 is obtained.

[0124] (7) Precursor E6 was naturally cured in air for 72 hours, and then calcined at 1300℃ for 6 hours in a calcining furnace to obtain calcined precursor F6. The water absorption rate of F6 was 32% and the bulk density was 0.88 kg / L.

[0125] (8) Weigh 485 g of nickel nitrate hexahydrate, 219 g of cobalt nitrate hexahydrate and 44.77 g of potassium nitrate and dissolve them in 738.72 g of deionized water and stir until homogeneous to obtain solution G6.

[0126] (9) Take 200 ml of calcined precursor F6 and place it in a high-pressure reaction vessel. Take 300 ml of G6 solution, add 5.28 g of citric acid and stir well. Add an appropriate amount of nitric acid to adjust the pH value to 4, then transfer it to a high-pressure reactor. Seal the reactor and pressurize it to 2 MPa. Heat it to 120 °C and impregnate it for 4 h. After impregnation, filter it and dry it at 130 °C for 5 h. Then calcine it at 450 °C for 5 h to obtain the first impregnation precursor H6.

[0127] (10) The precursor H6 obtained was impregnated and calcined twice in step (9) to obtain catalyst I6.

[0128] Example 7: A direct reduction iron process hydrocarbon reforming hydrogen production catalyst, comprising a support, an active component one, an active component two, an anti-coking agent, an electronic aid, and a structural aid; wherein... Carrier: Al2O3 50%, ZrO2 20%, totaling 70%; Active component 1: NiO 12%; Active component 2: Co2O 36%; Structural additives: 4% calcium aluminate, 4% magnesium aluminate; Electronic additive: K2O 2%; Anti-carbon deposit additives: CeO2 1%, La2O3 1%, with a total mass percentage of 100%.

[0129] The preparation method of the above catalyst includes the following steps: (1) Weigh 25.26 g of cerium nitrate hexahydrate and 26.56 g of lanthanum nitrate hexahydrate and dissolve them in 1500 g of deionized water and stir until homogeneous. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasound) to obtain mixed solution A7.

[0130] (2) Weigh 3678 g of aluminum nitrate nonahydrate and 697.56 g of zirconium nitrate pentahydrate through a 200-mesh sieve and add them to mixed solution A7. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, add 1 mol / L potassium carbonate solution at a rate of 10 ml / min to adjust the pH to 8.5, and then add 14 g of ethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12 h, and the ultrasonic frequency to 40 kHz.

[0131] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 6 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B7.

[0132] (4) Weigh 40g of calcium aluminate, 40g of magnesium aluminate, 32g of graphite, 14.6g of guar gum powder and the precursor B7 and ball mill them in a high-speed ball mill for 5h. Then pass them through a 200-mesh sieve to obtain the ball-milled material C7.

[0133] (5) Add 500g of desalinated water to C7 and mix evenly. Then dry at 120℃ until the moisture content is 15%. Then sieve through a dry granulator to obtain granulated material D6 with a mesh size of 20~100.

[0134] (6) Use a low-speed tablet press to press the granulated material into a precursor E7 with an outer diameter of 25mm, 5 holes in the middle (hole diameter of 3mm), a column height of 12mm, and a total height of 25mm with arc surfaces at both ends.

[0135] (7) Precursor E7 was naturally cured in air for 72 hours, and then calcined at 1100℃ in a calcining furnace for 6 hours to obtain calcined precursor F7. The water absorption rate of F7 was 35% and the bulk density was 0.86 kg / L.

[0136] (8) Weigh 443.42 g of nickel nitrate hexahydrate, 200.34 g of cobalt nitrate hexahydrate and 40.93 g of potassium nitrate and dissolve them in 761.07 g of deionized water and stir until homogeneous to obtain solution G7.

[0137] (9) Take 200 ml of calcined precursor F7 and place it in a high-pressure reaction vessel. Take 300 ml of G7 solution, add 5.28 g of citric acid and stir well. Add an appropriate amount of nitric acid to adjust the pH value to 3, then transfer it to a high-pressure reactor. Seal the reactor and pressurize it to 2 MPa. Heat it to 120 °C and impregnate it for 4 h. After impregnation, filter it and dry it at 130 °C for 5 h. Then calcine it at 450 °C for 5 h to obtain the first impregnation precursor H7.

[0138] (10) The precursor H7 obtained is repeated twice in step (9) to obtain catalyst I7.

[0139] Comparative Example 1: A catalyst for hydrogen production from hydrocarbon reforming using a direct reduction iron process, comprising the following feedstock by weight percentage: Carrier: Al2O3 60%, ZrO2 15%, totaling 75%; Active component 1: NiO 13%; Structural aid: 7% calcium aluminate; Electronic additive: K2O 2%; Anti-carbon deposit additives: CeO2 2% and La2O3 1%, with a total mass percentage of 100%.

[0140] The preparation method of the above catalyst includes the following steps: (1) Weigh 50.49 g of cerium nitrate hexahydrate and 25.46 g of lanthanum nitrate hexahydrate and dissolve them in 1000 g of deionized water and stir until homogeneous. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasound) to obtain mixed solution A8.

[0141] (2) Weigh 600 g of alumina that has passed through a 325-mesh sieve and 523.17 g of zirconium nitrate pentahydrate and add them to mixed solution A3. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, and add 1 mol / L potassium carbonate solution at a rate of 10 ml / min to adjust the pH value to 8.5. Then add 24 g of polyethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12 h, and the ultrasonic frequency to 40 kHz.

[0142] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 180°C for 8 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B8.

[0143] (4) Weigh 70g of calcium aluminate, 16.2g of calcium stearate and 24.3g of guar gum powder and ball mill them with precursor B8 in a high-speed ball mill for 5h, and pass them through a 200-mesh sieve to obtain ball-milled material C8.

[0144] (5) Add 500g of desalinated water to C8 and mix evenly. Then dry at 120℃ until the moisture content is 15%. Then sieve through a dry granulator to obtain granulated material D8 with a mesh size of 20~100.

[0145] (6) Use a low-speed tablet press to press the granulated material into a precursor E8 with an outer diameter of 25mm, 5 holes in the middle (hole diameter of 3mm), a column height of 12mm, and a total height of 25mm with arc surfaces at both ends.

[0146] (7) Precursor E8 was naturally cured in air for 72 hours, and then calcined at 1300℃ in a calcining furnace for 6 hours to obtain calcined precursor F8. The water absorption rate of F8 was 32% and the bulk density was 0.88 kg / L.

[0147] (8) Weigh 606.25 g of nickel nitrate hexahydrate and 44.76 g of potassium nitrate and dissolve them in 775 g of deionized water and stir until homogeneous to obtain solution G8.

[0148] (9) Take 200 ml of calcined precursor F8 and place it in a high-pressure reaction vessel. Take 300 ml of G8 solution, add 3.6 g of citric acid and stir well. Add an appropriate amount of nitric acid to adjust the pH value to 3, then transfer it to a high-pressure reactor. Then seal the reactor and pressurize it to 2 MPa. Heat it to 120 °C and impregnate it for 4 h. After impregnation, filter it, then dry it at 130 °C for 5 h, and then calcine it at 450 °C for 5 h to obtain the first impregnation precursor H8.

[0149] (10) The precursor H8 obtained is repeated twice in step (9) to obtain catalyst I8.

[0150] Comparative Example 2 A catalyst for hydrogen production from hydrocarbon reforming using a direct reduction iron process, comprising the following feedstock by weight percentage: Carrier: Al2O3 60%, ZrO2 15%, totaling 75%; Active component 1: NiO 12%; Active component 2: Co2O 38%; Electronic additive: K2O 2%; Anti-carbon deposit additives: CeO2 2% and La2O3 1%, with a total mass percentage of 100%.

[0151] The preparation method of the above catalyst includes the following steps: (1) Weigh 50.49 g of cerium nitrate hexahydrate and 26.56 g of lanthanum nitrate hexahydrate and dissolve them in 1500 g of deionized water and stir until homogeneous. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasound) to obtain mixed solution A9.

[0152] (2) Weigh 560 g of alumina and 523.17 g of zirconium nitrate hexahydrate through a 200-mesh sieve and add them to mixed solution A9. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, and add 1 mol / L potassium carbonate solution at a rate of 10 ml / min to adjust the pH to 8.5. Then add 14 g of ethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12 h, and the ultrasonic frequency to 40 kHz.

[0153] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 6 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B9.

[0154] (4) Weigh 60g of calcium aluminate, 14.6g of graphite, 7.3g of calcium stearate and precursor B5 and ball mill them in a high-speed ball mill for 5h. Then pass them through a 200-mesh sieve to obtain the ball-milled material C9.

[0155] (5) Add 600g of desalinated water to C9 and mix evenly. Then dry at 120℃ until the moisture content is 15%. Then sieve through a dry granulator to obtain granulated material D9 with a mesh size of 20~100.

[0156] (6) Use a low-speed tablet press to compress the granulated material into a cylindrical shape with grooved sidewalls and a porous arc surface. The specific dimensions are as follows: outer diameter of the cylinder 25mm, cylinder length 12mm, total length of the two arc surfaces of the cylinder 25mm, number of central holes 5, diameter 3mm; number of outer wall grooves 4, diameter 4mm. This yields the precursor E9. (7) Precursor E9 was naturally cured in air for 72 hours, and then calcined at 1300℃ for 6 hours in a calcining furnace to obtain calcined precursor F9. The water absorption rate of F9 was 25% and the bulk density was 0.94 kg / L.

[0157] (8) Weigh 620.8 g of nickel nitrate hexahydrate, 186.99 g of nickel nitrate hexahydrate and 44.76 g of potassium nitrate and dissolve them in 700 g of deionized water and stir until homogeneous to obtain solution G9.

[0158] (9) Take 200 ml of calcined precursor F9 and place it in a high-pressure reaction vessel. Take 300 ml of G9 solution, add 3.6 g of citric acid and stir well. Add an appropriate amount of nitric acid to adjust the pH value to 5, then transfer it to a high-pressure reactor. Then seal the reactor and pressurize it to 2 MPa. Heat it to 120 °C and impregnate it for 4 h. After impregnation, filter it, then dry it at 130 °C for 5 h, and then calcine it at 450 °C for 5 h to obtain the first impregnation precursor H9.

[0159] (10) The precursor H9 obtained is repeated twice in step (9) to obtain catalyst I9.

[0160] Comparative Example 3: A catalyst for hydrogen production from hydrocarbon reforming using a direct reduction iron process, comprising the following feedstock by weight percentage: Carrier: Al2O3 50%, MgO 20%, totaling 72%; Active component 1: NiO 10%; Active component 2: Co2O 39%; Structural aid: 6% calcium aluminate; Anti-carbon deposit additives: CeO2 2% and La2O3 1%, with a total mass percentage of 100%.

[0161] The preparation method of the above catalyst includes the following steps: (1) Weigh 50.49 g of cerium nitrate hexahydrate and 26.56 g of lanthanum nitrate hexahydrate and dissolve them in 1500 g of deionized water and stir until homogeneous. Then transfer the mixed solution to a high-pressure hydrothermal reactor (with ultrasound) to obtain mixed solution A10.

[0162] (2) Weigh 500 g of alumina and 220 g of magnesium oxide that have passed through a 200-mesh sieve and add them to the mixed solution A10. Set the stirring speed to 1000 r / min, raise the temperature to 75℃, and add 1 mol / L potassium carbonate solution at a rate of 10 ml / min to adjust the pH value to 8.5. Then add 14 g of ethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2 MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12 h, and the ultrasonic frequency to 40 kHz.

[0163] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 6 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor B10.

[0164] (4) Weigh 60g of calcium aluminate, 14.6g of graphite, 7.3g of calcium stearate and 14.6g of guar gum powder and ball mill them with precursor B10 in a high-speed ball mill for 5h, and pass them through a 200-mesh sieve to obtain ball milled material C10.

[0165] (5) Add 600g of desalinated water to C10 and mix evenly. Then dry at 120℃ until the moisture content is 15%. Then sieve through a dry granulator to obtain granulated material D10 with a mesh size of 20~100.

[0166] (6) Use a low-speed tablet press to compress the granulated material into a cylindrical shape with grooved sidewalls and a porous arc surface. The specific dimensions are: outer diameter of the cylinder 25mm, total length of the cylinder 25mm, no hole in the middle, resulting in precursor E10.

[0167] (7) The precursor E10 was naturally cured in air for 125 hours, and then calcined at 1300℃ in a calcining furnace for 6 hours to obtain the modified carrier F10. The water absorption rate of the calcined precursor F10 was tested to be 25%. The bulk density is 0.94 kg / L.

[0168] (8) Weigh 517.33 g of nickel nitrate hexahydrate and 210.36 g of nickel nitrate hexahydrate and dissolve them in 775 g of deionized water and stir until homogeneous to obtain solution G10.

[0169] (9) Take 200 ml of calcined precursor F10 and place it in a high-pressure reaction vessel. Take 300 ml of G10 solution, add 3.6 g of citric acid and stir well. Add an appropriate amount of nitric acid to adjust the pH value to 3, then transfer it to a high-pressure reactor. Then seal the reactor and pressurize it to 2 MPa. Heat it to 120°C and impregnate it for 4 h. After impregnation, filter it, then dry it at 130°C for 5 h, and then calcine it at 450°C for 5 h to obtain the first impregnation precursor H10.

[0170] (10) The precursor H10 obtained is repeated twice in step (9) to obtain catalyst I10.

[0171] Comparative Example 4: A catalyst for hydrogen production from hydrocarbon reforming using a direct reduction iron process, comprising the following feedstock by weight percentage: Carrier: Al2O3 50%, ZrO2 23%, totaling 73%; Active component 1: NiO 10%; Active component 2: Co2O 39%; Structural aid: 6% pure calcium aluminate; Electronic additives: K2O 2%; the total mass percentage is 100%. The preparation method of the above catalyst includes the following steps: (1) Weigh 500g of alumina and 802.2g of zirconium nitrate pentahydrate through a 200-mesh sieve and add them to a high-pressure hydrothermal reactor (with ultrasound). Then add 1500g of deionized water, set the stirring speed to 1000r / min, raise the temperature to 75℃, add 1mol / L potassium carbonate solution at a rate of 10ml / min to adjust the pH to 8.5, and then add 14g of ethylene glycol. Slowly start the high-pressure hydrothermal reactor, keep the stirring speed constant, set the pressure of the hydrothermal reactor to 2MPa, the hydrothermal reaction temperature to 140℃, the reaction time to 12h, and the ultrasonic frequency to 40KHz.

[0172] (3) The slurry obtained in (2) is filtered and washed three times, then dried at 150°C for 6 hours, and then calcined at 500°C for 4 hours to obtain the modified carrier precursor A11.

[0173] (4) Weigh 60g of calcium aluminate, 14.6g of graphite, 7.3g of calcium stearate and 14.6g of guar gum powder and ball mill them with precursor A11 in a high-speed ball mill for 5h, and pass them through a 200-mesh sieve to obtain ball milled material B11.

[0174] (5) Add 600g of desalinated water to B11 and mix evenly. Then dry at 120℃ until the moisture content is 15%. Then sieve through a dry granulator to obtain granulated material C11 with a mesh size of 20~100.

[0175] (6) Use a low-speed tablet press to press the granulated material into a precursor D11 with an outer diameter of 25mm, 5 holes in the middle (hole diameter of 3mm), a column height of 12mm, and a total height of 25mm with arc surfaces at both ends.

[0176] (7) The precursor D11 was naturally cured in air for 72 hours, and then calcined at 1300℃ in a calcining furnace for 6 hours to obtain the modified carrier E11. The water absorption rate of the carrier E11 was 32% and the bulk density was 0.88 kg / L.

[0177] (8) Weigh 404.16 g of nickel nitrate hexahydrate, 164.34 g of cobalt nitrate hexahydrate and 44.77 g of potassium nitrate and dissolve them in 758 g of deionized water and stir until homogeneous to obtain solution F11.

[0178] (9) Take 200 ml of calcined precursor E11 and place it in a high-pressure reaction vessel. Take 300 ml of F11 solution, add 5.28 g of citric acid and stir well. Add an appropriate amount of nitric acid to adjust the pH value to 3, then transfer it to a high-pressure reactor. Seal the reactor and pressurize it to 2 MPa. Heat it to 120 °C and impregnate it for 4 h. After impregnation, filter it and dry it at 130 °C for 5 h. Then calcine it at 450 °C for 5 h to obtain the first impregnation precursor G11.

[0179] (10) The precursor G11 obtained was impregnated and calcined twice in step (9) to obtain catalyst H11.

[0180] The operation steps of the evaluation device are as follows: according to Figure 1 A schematic diagram of the structure of an evaluation device for a dechlorinating agent used for deep removal of organochlorine from raw gas at room temperature is shown. Connect the various components and then operate according to the following steps: 1. Catalyst loading: Crush the formed catalyst into particles of 1.5-2mm size, and weigh 6ml of the catalyst, taking a mass of m. 0，It is loaded into a straight-through (fixed bed) reactor 21 with an inner diameter of 20 mm.

[0181] 2. Air tightness test: After installing reactor 21, close ball valves 7, 10, 15, 16, 26, 29, and 30. Switch the three-way ball valve to the main reaction pipeline. Close needle valve 32, open ball valve 4, open the nitrogen cylinder valve, and slowly open the nitrogen pressure reducing valve 5. Set the nitrogen flow meter to 500 ml / min. When pressure gauge 24 displays a pressure reading of 2 MPa, close the nitrogen cylinder valve and ball valve 4. Perform an air tightness test using soap bubbles. After confirming no leaks, open back pressure valve 28, ball valve 29, and needle valve 31 to purge the nitrogen.

[0182] 3. Raw material gas concentration test: After the airtightness test, close ball valve 29, open ball valve 30, and switch the three-way ball valve to the feed gas analysis line. Turn on the gas chromatograph and select the current analytical method. After the chromatograph baseline stabilizes, open the gas cylinder valve of feed gas cylinder 3, open ball valve 10, slowly open feed gas pressure reducing valve 11, and turn on feed gas mass flow meter 12, setting the flow rate to 500 ml / min. Slowly open needle valve 33 and observe whether the bubbles in the absorption bottle at the chromatograph exhaust port are continuous and uniform. After the bubbles in the absorption bottle at the chromatograph exhaust port stabilize, sample and analyze. Calculate the corresponding sample analysis based on the chromatographic integral area multiple times and take the average inlet concentration CH4-C. 01 CO2-C 02 H2-C 03 CO-C 04 N2-C 05 .

[0183] 4. Reduction Operation: After step 3 is completed, close ball valve 10, open ball valves 4, 7, 29, and 30, switch the three-way ball valve back to the main reaction line, open the nitrogen cylinder valve, slowly open the nitrogen pressure reducing valve to adjust the nitrogen flow rate to 900 ml / L, and then adjust the system pressure to 0.5 MPa through pressure reducing valve 28. After stabilization, open the 10% vol hydrogen and nitrogen cylinder valves and cylinder pressure reducing valve 8, adjust the flow meter 9 to a flow rate of 100 ml / min, and after the gas flow stabilizes, adjust needle valves 29 and 32 until a continuous and uniform gas is discharged from the gas chromatograph exhaust port. Then sample and analyze the nitrogen content in the gas. After completion, turn on the tube furnace power supply. The preheating section heats up to 350℃ at a rate of 10℃ / min, and the heating section heats up to 500℃ at a rate of 5℃ / min, then start timing. The operation record is as follows (reduction space velocity 1000 h⁻¹, reduction temperature 500℃, reduction pressure 0.5 MPa): Table 1-1 Restore Operation

[0184] 5. Activity Test: After step 4 is completed, maintain the system temperature and pressure constant. First, close the 10% vol hydrogen and nitrogen cylinder valves, pressure reducing valve, and ball valve 7. Simultaneously, adjust the nitrogen flow rate to 500 min / L. Turn on the horizontal flow pump and balance, setting the flow rate to 1.6 ml / min, and calibrate whether the flow rate matches the mass displayed on the balance. After completion, raise the temperature to 550℃, then open the feed gas cylinder valve, pressure reducing valve 11, and ball valve 10. Adjust the flow rate to 1000 ml / min using a mass flow meter. Then, close the nitrogen cylinder valve and pressure reducing valve, and simultaneously adjust the feed gas flow rate to 2000 ml / min. Determine the hot spot thermometer position of the bed using the central temperature measuring conduit. Once the bed hot spot temperature no longer changes, perform gas chromatography-mass spectrometry (GC-MS) sampling and analysis. The sampling and analysis interval is 1 hour, and the stability evaluation time is 20 hours. (Nitrogen is used as an internal standard.) 6. Shutdown: After step 5 is completed, maintain the system temperature and pressure unchanged. First, open the nitrogen cylinder valve and adjust the flow rate to 500 ml / min. Then, close the raw material gas cylinder, pressure reducing valve, and ball valve 10. Turn off the preheating and heating sections of the heating furnace. When the furnace temperature drops to 30°C, turn off the horizontal flow pump. Then, disassemble reactor 21, remove the catalyst, and send it for carbon content analysis.

[0185] 7. Composition of raw gas: CH4 25% vol, CO2 20% vol, H2 35% vol, CO 19% vol, N 21% vol.

[0186] 8. Test conditions: reaction temperature 550℃, test space velocity 2000h. -1 The test pressure was 0.5 MPa and the water-to-air ratio was 0.5.

[0187] Table 1 Catalyst performance test results

[0188] The embodiments described above merely illustrate specific implementation methods of this application, and while the descriptions are detailed and specific, they should not be construed as limiting the scope of protection of this application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the technical solution of this application, and these modifications and improvements all fall within the scope of protection of this application.

[0189] This background section is provided to generally present the context of the invention. The work of the currently named inventors, the work to the extent described in this background section, and aspects of this section that did not constitute prior art at the time of application are neither expressly nor impliedly acknowledged as prior art to the invention.

Claims

1. A catalyst for hydrogen production from hydrocarbon reforming using the direct reduction iron process, characterized in that, The catalyst comprises a support, an active component one, an active component two, an anti-coking agent, an electronic aid, and a structural aid; wherein the support is an aluminum-containing material with a highly stable structure, accounting for 60-80% of the catalyst by weight; the active component one, in its oxidation state, accounts for 10-15% of the catalyst by weight; the active component two accounts for 5-10% of the catalyst by weight; the anti-coking agent is a metal oxide with oxygen storage function, accounting for 1-3% of the catalyst by weight; the electronic aid accounts for 1-3% of the catalyst by weight; the structural aid accounts for 3-8% of the catalyst by weight; and the total weight percentage of the catalyst is 100%.

2. The hydrocarbon reforming hydrogen production catalyst for direct reduction iron process as described in claim 1, characterized in that: The carrier is a combination of one or more of Al2O3, MgO, CaO, ZrO2, and TiO2; the first active component is a combination of any one or two of Ni and Re metal oxides; the second active component is a combination of any one or two of Co and Fe metal oxides; the anti-carbon deposition agent is a combination of any one or more of CeO2, La2O3, Sm2O3, Pr2O3, Nd2O3, Cr2O3, and SnO2; the electronic additive is a combination of any one or more of Na, K, Rb, and Cs; and the structural additive is a combination of any one or more of calcium aluminate, magnesium aluminate, potassium aluminate, and sodium aluminate.

3. The method for preparing a hydrocarbon reforming hydrogen production catalyst for direct reduction iron process as described in claim 1 or 2, characterized in that... Includes the following steps: (1) Dissolve the soluble salt of the anti-carbon deposition additive in deionized water and stir until homogeneous to obtain mixed solution A. Then transfer mixed solution A to a high-pressure hydrothermal reactor. The mass salt concentration of solution A is 1-5%. (2) Add the raw materials of the carrier to the high-pressure hydrothermal reactor, set the rotation speed and temperature, add an appropriate amount of alkali to adjust the pH value, and then add the modified synthetic dispersant; slowly start the high-pressure hydrothermal reactor, keep the rotation speed constant, set the pressure of the hydrothermal reactor, and carry out the hydrothermal reaction at a certain hydrothermal reaction temperature to obtain the slurry; (3) The slurry obtained in (2) is filtered and washed, dried and then calcined to obtain modified carrier precursor B; (4) Add the structural aid, release agent and pore-forming agent to the precursor B and ball mill them in a high-speed ball mill, then sieve them to obtain the ball-milled material C; (5) Add demineralized water to the ball-milled material C and mix and stir evenly, then prepare granulated material D by dry granulation machine; (6) Use a rotary tablet press to press the granulated material D to obtain a cylindrical arc-shaped porous or cylindrical sidewall grooved arc-shaped porous precursor E; (7) Precursor E was placed in air for natural curing, and then calcined in a calcining furnace at high temperature to obtain calcined precursor F. The water absorption rate and bulk density of calcined precursor F were measured. (8) Dissolve the salt of active component one, the salt of active component two and the salt of electronic additive in deionized water, stir evenly to obtain precursor solution G, the total salt mass concentration of solution G is 29-35%; (9) Place the calcined precursor F in a high-pressure reactor, then measure the precursor solution G, add a dispersant to the precursor solution G and stir evenly, add pH adjustment solution to adjust the pH value to between 2 and 4 and then transfer it to the high-pressure reactor. Under closed conditions, heat up, pressurize and impregnate. After impregnation, filter, then dry and calcine to obtain the precursor H. (10) Repeat the impregnation and calcination steps in (9) with the obtained precursor H to obtain catalyst I, which is the hydrocarbon reforming hydrogen production catalyst of the direct reduction iron process.

4. The method for preparing a hydrocarbon reforming hydrogen production catalyst using a direct reduction iron process as described in claim 3, characterized in that: The soluble salt of the anti-carbon deposit additive mentioned in step (1) is one or a combination of several of cerium nitrate, lanthanum nitrate, samarium nitrate, praseodymium nitrate, cerium oxalate, and lanthanum oxalate; The carrier raw material mentioned in step (2) is one or a combination of several of the following: alumina, aluminum nitrate, aluminum hydroxide, calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium nitrate, zirconium nitrate, zirconium oxalate, and titanium dioxide; the stirring speed when the carrier raw material is added to the mixed solution A is 600~1500 r / min, and the temperature is 70~80℃; the alkali is one or a combination of several of the following: potassium carbonate, ammonia, ethylenediamine, triethylamine, and aniline, and the pH value is adjusted to 7-10 by adding the alkali; the modified synthetic dispersant is any one or a combination of several of the following: ethylene glycol, 1,2-propanediol, glycerol, and polyethylene glycol; the amount of modified synthetic dispersant added is 3~8% of the weight of the carrier; the pressure of the hydrothermal reactor is 0.5~3 MPa, the hydrothermal reaction temperature is 120~180℃, the reaction time is 4~24 h, and the ultrasonic frequency is 10KHz~50KHz.

5. The method for preparing a hydrocarbon reforming hydrogen production catalyst using a direct reduction iron process as described in claim 3, characterized in that: The slurry in step (3) is filtered and washed 3 times; the drying conditions are 120~200℃ for 2~10h, and the calcination conditions are 500℃ for 3~8h. The release agent mentioned in step (4) is one or more of graphite, calcium stearate, magnesium stearate and sodium stearate, and the amount added is 1-3% of the weight of precursor B; the pore-forming agent is one or more of guar gum powder, starch, polyethyl cellulose, polyvinyl alcohol and polycaprolactone, and the amount added is 1-3% of the weight of precursor B; the ball milling time in the high-speed ball mill is 2-10 hours, and the ball milled product is passed through a 200-mesh sieve.

6. The method for preparing a hydrocarbon reforming hydrogen production catalyst for direct reduction iron process as described in claim 3, characterized in that: In step (5), the amount of demineralized water added is 10-20% of the weight of the ball milled material C; the particle size of the granulated material D is sieve that passes through 20-100 mesh. The specific dimensions of the cylindrical arc-shaped porous shape in step (6) are as follows: outer diameter of cylinder 10~40mm, length of cylinder 10~15mm, total length of the two arc surfaces of cylinder 10~30mm, number of intermediate holes 3~10, diameter of holes 1~5mm; the specific dimensions of the cylindrical sidewall grooved arc-shaped porous shape are as follows: outer diameter of cylinder 10~40mm, length of cylinder 10~15mm, total length of the two arc surfaces of cylinder 10~30mm, number of intermediate holes 3~10, diameter of holes 1~5mm; number of outer wall grooves 2~8, diameter of grooves 3~8mm.

7. The method for preparing a hydrocarbon reforming hydrogen production catalyst using a direct reduction iron process as described in claim 3, characterized in that: In step (7), the natural curing time is 24~120h; the high-temperature calcination temperature in the calcining furnace is 1000~1500℃, and the time is 3~10h; The salt of active component one mentioned in step (8) is one or more of nickel nitrate, nickel oxalate, ferric nitrate, and ferric oxalate; the salt of active component two is one or more of cobalt nitrate, perrhenic acid, and cobalt oxalate; and the salt of electronic additive is one or more of sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, and potassium oxalate.

8. The method for preparing a hydrocarbon reforming hydrogen production catalyst for direct reduction iron process as described in claim 3, characterized in that: In step (9), the volume ratio of calcined precursor F to precursor solution G is 1-2; the pH adjustment solution is an acid or a base, wherein the acid is one or a combination of nitric acid, formic acid, acetic acid, oxalic acid, hydrochloric acid, and phosphoric acid; the base is one or a combination of ammonia, ethylenediamine, and phenylethylamine; the dispersant is one or a combination of citric acid, tartaric acid, polyethylene glycol, ethylene glycol, and polypyrrolidone; the amount of dispersant used is 1-3% of the weight of the carrier; the high-pressure autoclave is sealed and heated to 100-150℃ and pressurized to 1-3MPa for 1-5 hours, filtered after immersion, dried at 100-200℃ for 2-8 hours, and then calcined at 400-600℃ for 3-10 hours; in step (10), the immersion and calcination steps in step (9) are repeated 1-3 times with the obtained precursor H.

9. The application of a hydrocarbon reforming hydrogen production catalyst prepared by any of the methods described in claims 3-8 in the hydrocarbon reforming hydrogen production process using the direct reduction iron process.

10. The application as described in claim 9, characterized in that, The catalyst operating conditions are: reactant inlet temperature of 500~800℃ and reaction volume hourly space velocity of 1000~3000 h⁻¹. -1 The reaction pressure is 0.1~0.8MPa, the water-to-carbon ratio is 0.2~0.8, the inlet methane volume concentration is ≤30%, and the inlet carbon dioxide volume concentration is ≤20%.

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