A downhole in-situ oil shale exploitation synchronous hydrogen production catalyst and a preparation method thereof

Abstract

This application relates to the field of catalysts for in-situ oil shale extraction, and particularly to a catalyst for simultaneous hydrogen production during in-situ oil shale extraction and its preparation method. The preparation method includes the following steps: S1, preparation of a pretreated support: S101, preparation of an intercalated support; S102, oleophilic modification; S2, metal loading: S201, immersing the pretreated support obtained in S1 into a metal impregnation solution, stirring, and then concentrating under reduced pressure to obtain a metal-loaded support; S202, adding molybdenum disulfide and nickel phosphide to the metal-loaded support, adding a dispersant, and stirring to obtain a doped support; S203, aging the doped support in a sealed environment to obtain an aged support; S3, catalyst molding. This application provides a catalyst for simultaneous hydrogen production during in-situ oil shale extraction and its preparation method to solve the problems of low energy utilization efficiency and the inability to simultaneously achieve shale oil extraction and hydrogen production in related technologies.

Description

Technical Field

[0001] This application relates to the field of catalyst technology for in-situ oil shale mining, and in particular to a catalyst for simultaneous hydrogen production in in-situ oil shale mining and its preparation method. Background Technology

[0002] Oil shale is a high-ash sedimentary rock containing combustible organic matter. It is an unconventional oil and gas resource, and due to its abundant resources and feasibility of development, it is considered a crucial alternative energy source for the 21st century. Traditional oil shale extraction primarily utilizes surface retorting technology, but this method suffers from problems such as large land occupation, severe environmental pollution, and low resource utilization. Currently, in-situ underground extraction has become the mainstream development direction for the efficient utilization of oil shale resources due to its advantages of not requiring open-pit mining, minimal disturbance, and low cost.

[0003] As a clean and efficient secondary energy source, hydrogen energy is experiencing a continuous increase in market demand. During the in-situ mining of oil shale, the hydrocarbons (such as long-chain alkanes and aromatics) produced by kerogen pyrolysis and the water vapor naturally present in the reservoir provide abundant substrates for in-situ hydrogen production. Achieving synergistic production of oil and hydrogen has become a key direction for enhancing the added value of oil shale development.

[0004] Existing technologies often use transition metal salts, liquid acids, or conventional inorganic solid acids as pyrolysis catalysts. Although these can reduce the pyrolysis temperature to some extent, they still have many inherent drawbacks: liquid acids and soluble transition metal salts have high fluidity and are easily infiltrated into the micropores and fractures of oil shale with formation fluids, causing permeability pollution and permanent pore blockage. At the same time, existing in-situ catalytic technologies for oil shale mostly focus on the single objective of oil production, making it difficult to achieve simultaneous extraction and hydrogen production. Summary of the Invention

[0005] This application provides a catalyst for simultaneous hydrogen production during in-situ extraction of downhole oil shale and its preparation method, in order to solve the problems of low energy utilization efficiency and inability to achieve simultaneous extraction and hydrogen production in in-situ extraction technologies in related technologies.

[0006] In a first aspect, a method for preparing a catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale is provided, comprising the following steps: S1. Preparation of pretreated carrier: S101, Preparation of intercalation carrier: After grinding the composite carrier into powder, add it to the hydrotalcite suspension and stir at 55~60℃ for 1~2h to obtain the intercalation carrier. The composite carrier includes zeolite, sepiolite and biochar in a mass ratio of 6:(2~3):1. S102, lipophilic modification: The intercalated carrier is immersed in a lipophilic modifier and refluxed at 75~80℃ for 2~3h. After filtration and washing, the lipophilic modification is completed. The lipophilic modifier includes decanoic acid and 2-furan methylamine in a mass-volume ratio of 3:(1.5~2). S2, Metal Load: S201. The pretreated carrier prepared in S1 is immersed in a metal impregnation solution, stirred at 30~32℃, and then concentrated under reduced pressure at 40~45℃ to obtain a metal-supported carrier. The metal impregnation solution is prepared by adding sodium molybdate, indium trichloride tetrahydrate, and zinc ferrite to deionized water at a molar ratio of 2:(0.8~1.2):1, followed by adding sodium hexametaphosphate to obtain the metal impregnation solution. The concentration of zinc ferrite is 0.1 mol / L. S202. Molybdenum disulfide and nickel phosphide are added to the metal support carrier, and after adding a dispersant, the mixture is stirred to obtain a doped carrier; the amount of molybdenum disulfide added is 4-5% of the mass of the metal support carrier, and the amount of nickel phosphide added is 2-3% of the mass of the metal support carrier; S203. The doped support is aged in a sealed environment to obtain an aged support; S3, Catalyst Forming: The aging carrier is mixed with deionized water and stirred, and then granulated into granular preforms with a particle size of 2-5 mm by a granulation mechanism. After drying the raw material, a catalyst for simultaneous hydrogen production from in-situ mining of downhole oil shale is obtained.

[0007] Preferably, in step S101, the mass concentration of the hydrotalcite suspension is 10 wt%, and the mass ratio of the hydrotalcite to the composite carrier is 1:(4~5).

[0008] Preferably, step S1 further includes step S103, which includes: S103. The lipophilic modified carrier is immersed in an 8wt% polyferric silicate solution, ammonium sulfate is added, and the mixture is ultrasonically dispersed at 45~50℃ for 0.5~1h, then allowed to stand and filtered. The amount of ammonium sulfate added is 3% of the mass of the lipophilic modified carrier.

[0009] Preferably, in S201, the amount of sodium hexametaphosphate added is 1.5 to 2% of the sum of the masses of sodium molybdate, indium trichloride tetrahydrate, and zinc ferrite.

[0010] Preferably, in step S201, the solid-liquid ratio of the pretreated carrier prepared in step S1 to the metal impregnation solution is 1:1. The vacuum concentration conditions are: vacuum degree -0.08MPa.

[0011] Preferably, in step S202, the amount of dispersant added is 1% of the mass of the metal support carrier; The dispersant is selected from guar gum.

[0012] Preferably, in S203, the aging conditions are: temperature 28~30℃, relative humidity 50~60%, and time 10~12h.

[0013] Preferably, in step S3, the drying conditions include: drying at 50-60°C with forced air for 3-4 hours, followed by vacuum drying at 110-120°C for 5-6 hours.

[0014] Secondly, a catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale is provided, which is prepared by any one of the preparation methods for the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale as described in any of the above 8.

[0015] The beneficial effects of the technical solution provided in this application include: This application provides a catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale and its preparation method. Multiple materials are used as a composite support, giving it a high specific surface area and a hierarchical porous structure. Simultaneously, the layered structure of hydrotalcite is inserted into the support pores to enhance the catalyst's mechanical stability and provide sites for subsequent surface modification and metal loading. During oleophilic modification, esterification and amide bonding form a hydrophobic-oleophilic interface, ensuring contact between the catalyst and the kerogen of the oil shale, and reducing the in-situ pyrolysis initiation temperature and To of the oil shale. 50 The pyrolysis characteristic temperature; this application achieves metal loading through impregnation, in which molybdenum species form active sites on the catalyst surface, promoting the cracking of oil shale kerogen by reducing reaction activation, indium ions can optimize the electronic structure of the catalyst surface and enhance hydrogen production activity, zinc ferrite inhibits the agglomeration and sintering of active components under high temperature reaction conditions, and the addition of molybdenum disulfide and metal phosphides in the subsequent S202 step provides sulfide active sites, accelerating the formation and recombination of hydrogen free radicals, and finally the catalyst is obtained after aging and granulation, solving the problems in related technologies. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0017] Figure 1 A flowchart illustrating the preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale provided in this application; Figure 2 A flowchart for step S2, the preparation of the pretreatment vector, is provided in this application; Figure 3 A flowchart for step S3, metal load, provided in this application. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0019] See Figures 1-3 As shown, this application provides a catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale and its preparation method.

[0020] The zeolite used in the following examples and comparative examples is industrial-grade nano-sized ZSM-5 zeolite molecular sieve with a modulus of 25 and a particle size of 200~400nm; the sepiolite is fibrous with a length of 5~15μm and a specific surface area ≥250m². 2 / g; the hydrotalcite is magnesium aluminum hydrotalcite; the zinc ferrite particle size is ≤0.15mm; decanoic acid, 2-furanylamine, ammonium sulfate (aluminum ammonium sulfate), sodium molybdate, indium trichloride tetrahydrate, and sodium hexametaphosphate are all analytical grade; polyferric silicate is industrial grade, degree of polymerization 20, iron content ≥11%; guar gum is food grade; molybdenum disulfide is layered hexagonal crystal system, particle size ≤5μm; The biochar preparation method used in the following examples and comparative examples is as follows: Corn stalks are washed with water, dried at 60°C to constant weight, crushed to a particle size of 1-2 mm, placed in a tube furnace filled with nitrogen, heated to 550°C at a heating rate of 5°C / min, and carbonized at a constant temperature for 2 hours; after cooling to room temperature, the carbonized product is mixed with KOH at a mass ratio of 1:2, and twice the amount of deionized water is added to prepare a slurry, which is then placed in a muffle furnace and activated at 700°C for 1 hour. After cooling, biochar is obtained.

[0021] Example 1 The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale provided in this embodiment includes the following steps: S1. Preparation of pretreated carrier: S101, Preparation of intercalation carrier: 100g of composite carrier is put into a ball mill, 5g of deionized water is added, and the mixture is ground to a particle size of 50~100μm. The mixed powder is added to 200g of hydrotalcite suspension with a concentration of 10wt%, and stirred at 55℃ for 2h to obtain intercalation carrier. S102, lipophilic modification: The prepared intercalation carrier is mixed with the lipophilic modifier at a mass ratio of 10:1, and refluxed at 80°C for 2 hours. After filtration and washing, the lipophilic modification is completed. S103. Immerse 90g of the oleophilic modified carrier into an 8wt% polyferric silicate solution at a mass ratio of 1:10, add 2.7g of ammonium alum, ultrasonically disperse at 50℃ for 1h, let stand and filter to complete the preparation of the pretreated carrier.

[0022] The composite carrier is a mixture of 60g zeolite, 30g sepiolite and 10g biochar, and the lipophilic modifier is a mixture of 6g decanoic acid and 4mL 2-furanylamine.

[0023] S2, Metal Load: S201. Immerse 90g of the pretreated carrier prepared in S1 into the metal impregnation solution at a solid-liquid ratio of 1:1. Stir at 30°C and then concentrate under reduced pressure at 40°C until there is no free liquid (-0.08MPa) to obtain the metal-supported carrier. The method for preparing the metal impregnation solution is as follows: 4.12g of sodium molybdate, 2.93g of indium trichloride tetrahydrate, and 2.41g of zinc ferrite are added to 100g of deionized water, and then 0.19g of sodium hexametaphosphate is added to obtain the metal impregnation solution. S202. Add 4g of molybdenum disulfide and 2g of nickel phosphide to 90g of metal support, then add 0.9g of guar gum, and stir in a high-speed mixer at 1500r / min for 20min to obtain the doped support. S203. Place the doped support in a sealed container and age it for 12 hours at 30°C and 60% relative humidity to obtain the aged support. S3, Catalyst Forming: 90g of aging carrier was mixed with 7.2g of deionized water and stirred, and then granulated into granular preforms with a particle size of 2-5mm by a granulation mechanism. The green body was dried: first, it was dried at 60℃ for 4 hours (air blowing rate 5L / min) to remove surface free water, and then dried at 120℃ and -0.08MPa under vacuum for 6 hours to remove internal bound water, thus obtaining the catalyst.

[0024] Example 2 The difference from Example 1 is that step S103 is not performed in this example.

[0025] Example 3 The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale provided in this embodiment includes the following steps: S1. Preparation of pretreated carrier: S101, Preparation of intercalation carrier: 100g of composite carrier is put into a ball mill, 5g of deionized water is added, and the mixture is ground to a particle size of 50~100μm. The mixed powder is added to 250g of hydrotalcite suspension with a concentration of 10wt%, and stirred at 60℃ for 1h to obtain intercalation carrier. S102, lipophilic modification: The prepared intercalation carrier is mixed with the lipophilic modifier at a mass ratio of 10:1, and refluxed at 75°C for 3 hours. After filtration and washing, the lipophilic modification is completed. S103. Immerse 90g of the oleophilic modified carrier into an 8wt% polyferric silicate solution at a mass ratio of 1:10, add 2.7g of ammonium alum, ultrasonically disperse at 45℃ for 1h, let stand and filter to complete the preparation of the pretreated carrier.

[0026] The composite carrier is a mixture of 60g zeolite, 30g sepiolite and 10g biochar, and the lipophilic modifier is a mixture of 8g decanoic acid and 4mL 2-furanylamine.

[0027] S2, Metal Load: S201. Immerse 90g of the pretreated carrier prepared in S1 into the metal impregnation solution at a solid-liquid ratio of 1:1. Stir at 32°C and concentrate under reduced pressure at 45°C until no free liquid remains (-0.08MPa) to obtain the metal-supported carrier. The method for preparing the metal impregnation solution is as follows: 4.12g of sodium molybdate, 2.35g of indium trichloride tetrahydrate, and 2.41g of zinc ferrite are added to 100g of deionized water, and then 0.178g of sodium hexametaphosphate is added to obtain the metal impregnation solution. S202. Add 3.6g of molybdenum disulfide and 2.7g of nickel phosphide to 90g of metal support, then add 0.9g of guar gum, and stir in a high-speed mixer at 1500r / min for 20min to obtain the doped support. S203. Place the doped support in a sealed container and age it for 10 hours at 28°C and 50% relative humidity to obtain the aged support. S3, Catalyst Forming: 90g of aging carrier was mixed with 7.2g of deionized water and stirred, and then granulated into granular preforms with a particle size of 2-5mm by a granulation mechanism. The green body was dried: first, it was dried at 50℃ for 4 hours (air blowing rate 5L / min) to remove surface free water, and then dried at 110℃ and -0.08MPa under vacuum for 6 hours to remove internal bound water, thus obtaining the catalyst.

[0028] Example 4 The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale provided in this embodiment includes the following steps: S1. Preparation of pretreated carrier: S101, Preparation of intercalation carrier: 108g of composite carrier was put into a ball mill, 5g of deionized water was added, and the mixture was ground to a particle size of 50~100μm. The mixed powder was added to 200g of hydrotalcite suspension with a concentration of 10wt%, and stirred at 55℃ for 2h to obtain intercalation carrier. S102, lipophilic modification: The prepared intercalation carrier is mixed with the lipophilic modifier at a mass ratio of 10:1, and refluxed at 80°C for 2 hours. After filtration and washing, the lipophilic modification is completed. S103. Immerse 100g of the oleophilic modified carrier into an 8wt% polyferric silicate solution at a mass ratio of 1:10, add 3g of ammonium alum, ultrasonically disperse at 50℃ for 1h, let stand and filter to complete the preparation of the pretreated carrier.

[0029] The composite carrier is a mixture of 72g zeolite, 24g sepiolite and 12g biochar, and the lipophilic modifier is a mixture of 6g decanoic acid and 4mL 2-furanylamine.

[0030] S2, Metal Load: S201. Immerse 90g of the pretreated carrier prepared in S1 into the metal impregnation solution at a solid-liquid ratio of 1:1. Stir at 30°C and then concentrate under reduced pressure at 40°C until there is no free liquid (-0.08MPa) to obtain the metal-supported carrier. The method for preparing the metal impregnation solution is as follows: 4.12g of sodium molybdate, 3.52g of indium trichloride tetrahydrate, and 2.41g of zinc ferrite are added to 100g of deionized water, and then 0.15g of sodium hexametaphosphate is added to obtain the metal impregnation solution. S202. Add 5g of molybdenum disulfide and 2g of nickel phosphide to 100g of metal support, then add 1g of guar gum, and stir in a high-speed mixer at 1500r / min for 20min to obtain the doped support. S203. Place the doped support in a sealed container and age it for 12 hours at 30°C and 60% relative humidity to obtain the aged support. S3, Catalyst Forming: 90g of aging carrier was mixed with 7.2g of deionized water and stirred, and then granulated into granular preforms with a particle size of 2-5mm by a granulation mechanism. The green body was dried: first, it was dried at 60℃ for 3 hours (air blowing rate 5L / min) to remove surface free water, and then dried at 120℃ and -0.08MPa under vacuum for 5 hours to remove internal bound water, thus obtaining the catalyst.

[0031] Comparative Example 1 The difference between this comparative example and Example 1 is that hydrotalcite is not added in step S101, and the hydrotalcite suspension is replaced with an equal amount of deionized water; and step S102 is not performed.

[0032] Comparative Example 2 The difference between this comparative example and Example 1 is that step S202 is not performed.

[0033] Comparative Example 3 The difference between this comparative example and Example 1 is that step S103 and step S202 are not performed.

[0034] The effectiveness of the in-situ hydrogen production catalyst (hereinafter referred to as "catalyst") prepared by the above-described embodiments and comparative examples was verified.

[0035] Shale oil yield and hydrogen production testing: Determination of kerogen content in oil shale (using chloroform extraction method); Oil shale was crushed to a particle size of 2-5 mm, and 50 g was weighed for later use. 50 g of oil shale was mixed with 5 g of catalyst and placed in a reactor. Nitrogen gas (5 MPa pressure) was introduced, and the temperature was increased to 450 °C at a rate of 5 °C / min. The reactor was held at 450 °C for 4 hours, during which time the shale oil was collected using a condenser, and the hydrogen production was detected by gas chromatography. After the holding period, the reactor was cooled to room temperature, and the shale oil in the condenser was removed. The condenser was rinsed three times with anhydrous ethanol, and the washings were combined and weighed.

[0036] The yield Y is calculated based on the kerogen content and shale oil quality.

[0037] In the formula, Y represents the shale oil yield (%). m1 represents the mass (g) of shale oil collected in the experiment. m2 is the mass (g) of kerogen contained in 50g of oil shale.

[0038] Pyrolysis temperature test: Oil shale was crushed to a particle size ≤0.15mm, and free oil was removed by Soxhlet extraction to obtain kerogen. Catalyst and kerogen were weighed at a mass ratio of 1:10, ground in an agate mortar for 10 minutes, and 10mg was placed in an alumina crucible. The mixture was heated under a nitrogen atmosphere (gas flow rate 50mL / min, heating rate 10℃ / min, temperature range 30~800℃). The temperature corresponding to a 50% weight loss was determined from the temperature-weight loss curve (T0). 50 ).

[0039] Temperature resistance test: Place the catalyst into a tableting tool, apply a pressure of 10 MPa and hold for 5 minutes to form a sample tablet with a diameter of 10 mm and a thickness of 2 mm, and weigh the initial mass m0.

[0040] Place the sample piece on the sample stage, set the air atmosphere and heating program (5℃ / min to 800℃), and keep it at 800℃ for 1 hour. After naturally cooling to room temperature, take out the sample, weigh the mass (m1) after pyrolysis, determine the diameter (d1) and thickness (h1) after pyrolysis, and calculate the volume after pyrolysis.

[0041] Calculate the mass retention rate and volume expansion rate separately.

[0042] In the formula, m0 is the initial mass (g) of the sample piece. m1 is the mass (g) of the sample piece after pyrolysis.

[0043] In the formula, V0 is the initial volume of the sample piece (mm). 2 ); V1 is the volume of the sample after pyrolysis (mm). 2 ); The formula for calculating the volume is: Salt and alkali resistance (pH range) test: The catalyst was pulverized to a particle size ≤0.15mm, dried to constant weight, and 0.5g was accurately weighed and placed in a 50mL centrifuge tube. 50mL of buffer solution corresponding to the pH was added (pH=3, 5, 7, 9, 11, adjusted with 0.1mol / L HCl and 0.1mol / L NaOH). The tube was then sealed and placed in a constant temperature water bath shaker.

[0044] The shaking conditions were: temperature 30℃, rotation speed 150 r / min, shaking for 24 h. After shaking, the solution was allowed to stand for 30 min, filtered through a 0.22 μm filter membrane, and the filtrate was collected. The pH value of the filtrate was measured using a pH meter, and the pH change was calculated (ΔpH = |filtrate pH - initial pH|). The concentrations of Mo, In, and Bi ions in the filtrate were determined using ICP-MS, and the metal dissolution rate was calculated. The criteria for determining the catalyst's acid and alkali resistance pH range are: metal leaching rate <5% and ΔpH change <0.5.

[0045] The performance parameters are shown in Table 1.

[0046] Table 1 Compared to Example 1, Example 2 did not perform step S103, resulting in a lower yield. In Example 1, after step S104, the Al produced after the decomposition of ammonium sulfate was reduced. 3+The formation of Lewis acid sites with the support enhances the catalytic cracking ability; Comparative Example 1, without the addition of hydrotalcite and without lipophilic modification, has poor lipophilicity, insufficient contact between the catalyst and kerogen, and the catalyst is prone to agglomeration in the oil phase reaction system, resulting in a decrease in yield; In Example 1, the multi-metal oxides formed by metal support synergistically with the acidic sites provided by polyferric silicate and ammonium sulfate in step S103 reduce the activation energy of kerogen fracture, compared with the comparative example T 50 Significantly reduced, T 50 The lower the value, the more significant the effect of the catalyst in reducing the activation energy of kerogen pyrolysis.

[0047] Regarding mass retention and volume expansion rate, the examples were generally higher than the comparative examples. In Example 1, the layered structure of the hydrotalcite was stably bonded to the carrier, and sodium hexametaphosphate inhibited the aggregation of metal components. Example 2 lacked the crosslinking of polyferric silicate, resulting in a slight decrease in structural stability, but it was still higher than the comparative examples. Comparative Example 1 lacked hydrotalcite, and the carrier had no layered support structure, leading to an increased volume expansion rate. Comparative Examples 2 and 3 showed increased volume expansion rates and decreased mass retention rates.

[0048] Examples 1-4 all maintained a pH range of 4-10 for acid and alkali resistance. This is because the hydrophobic layer formed by the lipophilic modification blocked the corrosion of the carrier by the acid and alkali solutions. Comparative Example 1 did not undergo lipophilic modification, and its acid and alkali resistance range narrowed to 5-9. Comparative Example 3, due to the lack of treatment in steps S103 and S202, had a weaker bonding force between the metal and the carrier, and its acid and alkali resistance range was only 5-7.

[0049] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A method for preparing a catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale, characterized in that, It includes the following steps: S1. Preparation of pretreated carrier: S101, Preparation of intercalation carrier: After grinding the composite carrier into powder, add it to the hydrotalcite suspension and stir at 55~60℃ for 1~2h to obtain the intercalation carrier. The composite carrier includes zeolite, sepiolite and biochar in a mass ratio of 6:(2~3):

1. S102, lipophilic modification: The intercalated carrier is immersed in a lipophilic modifier and refluxed at 75~80℃ for 2~3h. After filtration and washing, the lipophilic modification is completed. The lipophilic modifier includes decanoic acid and 2-furan methylamine in a mass-volume ratio of 3:(1.5~2). S2, Metal Load: S201. The pretreated carrier prepared in S1 is immersed in a metal impregnation solution, stirred at 30~32℃, and then concentrated under reduced pressure at 40~45℃ to obtain a metal-supported carrier. The metal impregnation solution is prepared by adding sodium molybdate, indium trichloride tetrahydrate, and zinc ferrite to deionized water at a molar ratio of 2:(0.8~1.2):1, followed by adding sodium hexametaphosphate to obtain the metal impregnation solution. The concentration of zinc ferrite is 0.1 mol / L. S202. Molybdenum disulfide and nickel phosphide are added to the metal support carrier, and after adding a dispersant, the mixture is stirred to obtain a doped carrier; the amount of molybdenum disulfide added is 4-5% of the mass of the metal support carrier, and the amount of nickel phosphide added is 2-3% of the mass of the metal support carrier; S203. The doped support is aged in a sealed environment to obtain an aged support; S3, Catalyst Forming: The aging carrier is mixed with deionized water and stirred, and then granulated into granular preforms with a particle size of 2-5 mm by a granulation mechanism. After drying the raw material, a catalyst for simultaneous hydrogen production from in-situ mining of downhole oil shale is obtained.

2. The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale as described in claim 1, characterized in that: In step S101, the mass concentration of the hydrotalcite suspension is 10 wt%, and the mass ratio of hydrotalcite to the composite carrier is 1:(4~5).

3. The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale as described in claim 1, characterized in that: The S1 further includes step S103, which includes: S103. The lipophilic modified carrier is immersed in an 8wt% polyferric silicate solution, ammonium sulfate is added, and the mixture is ultrasonically dispersed at 45~50℃ for 0.5~1h, then allowed to stand and filtered. The amount of ammonium sulfate added is 3% of the mass of the lipophilic modified carrier.

4. The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale as described in claim 1, characterized in that: In S201, the amount of sodium hexametaphosphate added is 1.5 to 2% of the sum of the masses of sodium molybdate, indium trichloride tetrahydrate, and zinc ferrite.

5. The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale as described in claim 1, characterized in that: In S201, the solid-liquid ratio of the pretreated carrier prepared in S1 to the metal impregnation solution is 1:

1. The vacuum concentration conditions are: vacuum degree -0.08MPa.

6. The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale as described in claim 1, characterized in that: In step S202, the amount of dispersant added is 1% of the mass of the metal support carrier; The dispersant is selected from guar gum.

7. The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale as described in claim 1, characterized in that: In the S203, the aging conditions are: temperature 28~30℃, relative humidity 50~60%, and time 10~12h.

8. The preparation method of the catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale as described in claim 1, characterized in that: In S3, the drying conditions include: drying at 50~60℃ with forced air for 3~4 hours, followed by vacuum drying at 110~120℃ for 5~6 hours.

9. A catalyst for simultaneous hydrogen production in in-situ mining of downhole oil shale, characterized in that, It is prepared by the preparation method of the synchronous hydrogen production catalyst for in-situ mining of downhole oil shale as described in any one of claims 1 to 8.

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