Preparation method and application process of high-oxygen-resistant FeMo gas hydrogenation catalyst

Abstract

The invention discloses a preparation method and an application process of a high-oxygen-resistant FeMo gas hydrogenation catalyst. Preparing a hydrogenation waste agent doped with deoxidized and inactivated FeMo, wherein the eggshell-type loaded In accounts for 1.5-3.0% o to inhibit the de-sulfuration of the hydrogenation catalyst under the high-oxygen condition; the upper layer of the hydrogenation reactor is filled with a FeMo catalyst and ceramic balls which are uniformly mixed, the lower layer of the hydrogenation reactor is filled with the FeMo catalyst, gas enters from the lower part and exits from the upper part during vulcanization, and gas enters from the upper part and exits from the lower part during normal operation. According to the process, the FeMo hydrogenation catalyst inactivation waste agent is recycled, anti-sulfuration inactivation is avoided when the process is used in a coke oven gas environment with the oxygen content higher than 0.5%, and the process is green and economical.

Description

Technical Field

[0001] The invention relates to a preparation method of a high-oxygen resistant FeMo gas hydrogenation catalyst and an application process thereof, and belongs to the field of coal chemical industry. Background Art

[0002] my country is a major producer of coke, and a large amount of coke oven gas is produced as a byproduct. Coke oven gas has a good application prospect in the production of methanol / LNG. Methanol synthesis catalyst and methanation catalyst are used in the production of methanol and LNG. Their active components are Cu and Ni, respectively, which are very easy to react with sulfides and permanently deactivate. Therefore, it is of great significance to remove various sulfides in coke oven gas.

[0003] The sulfur content in coke oven gas is related to the total sulfur content of the coal charge. Generally, dry coal contains 0.5~1.2% (weight) total sulfur, of which 20~45% is transferred to coke oven gas, and hydrogen sulfide accounts for more than 95% of the total sulfur content. In addition to hydrogen sulfide, coke oven gas also contains carbonyl sulfide, carbon disulfide, thiophene, mercaptan, sulfide and other sulfides. The desulfurization process of coke oven gas is generally rough desulfurization first and then fine desulfurization. The so-called rough desulfurization is to remove hydrogen sulfide by wet method and activated carbon method. Fine desulfurization adopts the process of "pre-hydrogenation → primary hydrogenation → medium temperature desulfurization → secondary hydrogenation → zinc oxide desulfurization" to remove the total sulfur of the raw gas to 100ppb, meeting the requirements of subsequent processes. The active component of the hydrogenation catalyst is in the sulfide state, and the oxygen in the raw gas is toxic to it. At present, most pre-hydrogenation uses FeMo gas hydrogenation catalyst to remove oxygen from coke oven gas and protect the primary hydrogenation and secondary hydrogenation catalysts in the subsequent section.

[0004] In the FeMo hydrogenation reactor, the following chemical reactions related to the deoxygenation of coke oven gas occur: 2H2+O2=2H2O ΔH0=-197 KJ / mol (1) CO+3 H2=CH4+H2O ΔH0=-219 KJ / mol (2) CO2+4 H2=CH4+2H2O ΔH0=-165 KJ / mol (3) C2H4=CH4+C ΔH0=-22.7 KJ / mol (4) 2CO=CO2+C ΔH0=-172.3 KJ / mol (5) MoS2+ 2H2O ⇌MoO2+ 2H2S (6) From (1), it can be seen that deoxygenation is a highly exothermic reaction and a fast reaction. If the oxygen content of the coke oven gas is high, a large amount of heat will be generated quickly, causing local high temperature of the catalyst. Under high temperature conditions, methanation side reactions (2) and (3) will occur, generating more heat and causing the catalyst bed to overheat. Carbon deposition reactions (4) and (5) will also occur, blocking micropores and covering active sites, causing the hydrogenation catalyst to deactivate.

[0005] In addition, the equilibrium constant of reaction (6): Kp=P 2 H2O / P 2 H2S (7) According to the Gibbs-Helmholtz equation and the data provided by the literature, the equilibrium constant equation for the reaction is: Kp=exp(-4△G / RT) (8) Where △G = -1.92T ln(T) + 2.465×10 -3 T 2 +8.75×10 4 / T + 7.4046T +20099.49 At the plant's hydrogenation operating temperature, the equilibrium constant Kp of the desulfurization reaction of molybdenum sulfide increases sharply with increasing temperature.

[0006] According to (7) and (8), the water generated by the rapid deoxygenation reaction will rapidly increase the local water vapor concentration of the catalyst, and the resulting temperature rise will rapidly increase the equilibrium constant Kp of the molybdenum sulfide desulfurization reaction, causing reaction (6) to proceed quickly to the right, and MoS2 will be converted into MoO2, which manifests as the deactivation of the catalyst.

[0007] Industrial applications show that the oxygen content of coke oven gas is generally below 0.3%, and the service life of ordinary FeMo pre-hydrogenation is half a year. Generally, two towers are set up, one in operation and one in reserve, to match the one-year replacement cycle of primary hydrogenation. At present, the raw material coke oven gas oxygen content of the coke oven gas of the coke oven gas production methanol / LNG enterprises is high, and the maximum content is often greater than 0.5% (the general hydrogenation catalyst requires the oxygen content to be less than 0.5%), and the oxygen content of 1.25% in extreme conditions is usually 0.6~0.8%. Ordinary FeMo pre-hydrogenation will be deactivated within less than a week of operation, and frequent replacement will affect production and bring economic losses. Therefore, it is very meaningful to develop high-oxygen resistant FeMo hydrogenation.

[0008] The presulfurized hydrogenation catalysts disclosed in patents such as CN 112439421 A and CN 101797508 A all modify the carrier and use a dispersant to evenly disperse the active components and improve the hydrogenation activity. Many FeMo gas hydrogenation patents do not solve the problem of high oxygen resistance, nor do they recycle FeMo hydrogenation waste agents. Summary of the invention

[0009] In view of the shortcomings of the prior art, the present invention provides a method for preparing a high-oxygen resistant FeMo gas hydrogenation catalyst and its application process. The FeMo catalyst uses small-pore pseudo-boehmite and large-pore pseudo-boehmite as supports, respectively, and the catalyst precursors Ⅰ and Ⅱ are prepared by co-precipitation. Ⅰ and Ⅱ are mixed with crushed FeMo hydrogenation waste agent, extruded, dried, and roasted to obtain an eggshell-shaped loading of 1.5-3.0‰ In; the upper layer of the hydrogenation reactor is filled with FeMo catalyst and porcelain balls evenly mixed, and the lower layer is filled with FeMo catalyst. During sulfurization, the gas enters from the bottom and exits from the top, and during normal operation, the gas enters from the top and exits from the bottom; the process recycles the deactivated FeMo hydrogenation catalyst waste agent, and it will not be deactivated by reverse sulfurization when used in a coke oven gas environment with an oxygen content higher than 0.5%, which is green and economical.

[0010] The present invention is achieved through the following technical solutions: (i) When preparing the FeMo hydrogenation catalyst, deoxidized and inactivated FeMo hydrogenation waste is added to form an inactive "oxygen leakage" site in the structure, thereby reducing the deoxidation load and effectively transferring heat and dispersing the water vapor content inside the catalyst.

[0011] The FeMo catalyst preparation method comprises the following steps: (1) First add a certain amount of water, heat to 55-65°C, add a calculated amount of small-pore pseudo-boehmite, stir to form a slurry, add a calculated amount of ferric nitrate and stir for 10-30 minutes, then add a calculated amount of ammonium molybdate, maintain the temperature at 60°C, adjust the pH value to 5.8-7.0 with ammonia water, stir for 40-55 minutes, wait until the slurry turns yellow, filter press to form a cake, dry at 100-120°C, and crush to obtain a catalyst precursor I, in which the content of each component by weight is: Fe2O3 is 2.8%-4.2%, MoO3 is 7.3%-10.5%, and Al2O3 is 85.3%-89.9%. ; (2) replacing the small-pore pseudo-boehmite in step (1) with large-pore pseudo-boehmite to obtain a catalyst precursor II, wherein the contents of each component by weight are: 2.8% to 4.2% for Fe2O3, 7.3% to 10.5% for MoO3, and 85.3% to 89.9% for Al2O3; (3) The deactivated FeMo hydrogenation waste agent is crushed, and the precursor I, precursor II, and FeMo hydrogenation waste agent are mixed in a mass ratio of (2.5-4.0):(1.5-2.8):(2.3-3.5), and after grinding evenly, an appropriate amount of deionized water is added, and after stirring and rolling evenly, the mixture is extruded and formed. After standing for 3.5 hours, the mixture is dried at 110-130°C for 2.0-4.0 hours, and then calcined at 420-650°C for 3-5 hours to obtain the catalyst precursor III; (ii) Eggshell-type loading of In on FeMo catalyst inhibits desulfurization of hydrogenation catalyst under high oxygen conditions. Studies have found that adding In to hydrogenation catalysts can inhibit desulfurization under high oxygen conditions. The reason may be that In can prevent the formation and desorption of H2S, making it difficult for the equilibrium of reaction (6) mentioned above to move to the right. The loading method is: Prepare a 1% In(NO3)3 solution, take the calculated amount of dilution, and over-impregnate the above-mentioned precursor III of the catalyst for 20 to 26 hours, then dry at 115 to 140°C for 2.5 to 3.5 hours, and then calcine at 400 to 600°C for 5 to 7 hours to obtain the catalyst; (III) Setting an "oxygen leakage" position for catalyst loading. The upper layer of the hydrogenation reactor is filled with FeMo catalyst and porcelain balls in an evenly mixed volume, and the lower layer is filled with FeMo catalyst. The porcelain balls have no deoxygenation activity and can reduce the total amount of heat released by deoxygenation in the upper layer of the reactor. At the same time, the porcelain balls are also heat-receiving bodies, which can disperse the heat generated by deoxygenation in the upper layer and prevent exothermic side reactions such as methanation and carbon deposition caused by temperature rise. The volume ratio of the upper and lower layers of the hydrogenation reactor is 1:3~1:1.

[0012] (IV) During sulfidation, the gas enters from the bottom and exits from the top, and during normal operation, the gas enters from the top and exits from the bottom. The applicant found during the experiment that when the oxygen-containing coke oven gas enters from the top and exits from the bottom, the top of the hydrogenation catalyst bed will be reversed and the color will become lighter. The gas enters from the bottom and exits from the top during sulfidation, and the heat of sulfidation is transferred to the upper part, so that the upper catalyst is strengthened under high temperature conditions, making the generated MoS2 more stable, and enhancing the anti-high oxygen reverse sulfidation performance of the hydrogenation catalyst at the top of the bed.

[0013] Beneficial effects of the present invention: ⑴ Fundamentally solve the problem of deactivation of FeMo gas hydrogenation catalyst under high oxygen conditions. First, in the preparation of FeMo hydrogenation catalyst, not only small-pore pseudo-boehmite and large-pore pseudo-boehmite are used as carriers for co-precipitation to obtain a variety of active sites for hydrodesulfurization, deoxygenation, and deolefination, but also deoxygenation-inactivated FeMo hydrogenation waste agent is added to form a structural "oxygen leakage" inactive site, which reduces the deoxygenation load and can effectively transfer heat and disperse water vapor content inside the catalyst. Secondly, the catalyst is loaded with an "oxygen leakage" position. The upper layer of the hydrogenation reactor is filled with FeMo catalyst and porcelain balls of equal volume and mixed uniformly, and the lower layer is filled with FeMo catalyst. The porcelain balls have no deoxygenation activity and can reduce the total amount of heat released by deoxygenation in the upper layer of the reactor. At the same time, the porcelain balls are also heat-receiving bodies, which can disperse the heat generated by deoxygenation in the upper layer to prevent side reactions such as methanation and carbon deposition caused by temperature rise. As mentioned above, the deoxygenation reaction is exothermic, and the heat is not dissipated in time, resulting in local high temperature of the catalyst. The high temperature condition will cause the methanogenic side reaction, generate more heat, and make the catalyst bed temperature soar. On the one hand, the carbon deposition reaction occurs, blocking the micropores and covering the active sites, so that the hydrogenation catalyst is deactivated. On the other hand, the water generated by the rapid deoxygenation reaction will rapidly increase the local water vapor concentration of the catalyst, and the resulting temperature rise will rapidly increase the equilibrium constant Kp of the desulfurization reaction of molybdenum sulfide, resulting in the conversion of MoS2 to MoO2, which manifests as the deactivation of the catalyst. The present invention sets an "oxygen leakage" position in the preparation and filling of the hydrogenation catalyst, reduces the deoxygenation load both microscopically and macroscopically, controls the heat release and the total amount of generated water, and at the same time, the inactive sites of the FeMo hydrogenation waste agent inside the catalyst and the uniformly mixed porcelain balls outside can well disperse the heat and water vapor content, thereby effectively inhibiting carbon deposition and desulfurization reactions, and fundamentally solving the problem of deactivation of the FeMo gas hydrogenation catalyst under high oxygen conditions.

[0014] ⑵The problem of desulfurization is solved well. The present invention solves the problem of inhibiting the desulfurization of hydrogenation catalysts under high oxygen conditions from the aspects of the preparation and application process of hydrogenation catalysts. First, a FeMo hydrogenation catalyst is prepared, and an eggshell-type In is loaded. As mentioned above, the applicant has found that the addition of In to the hydrogenation catalyst can inhibit desulfurization under high oxygen conditions. The reason may be that In can prevent the formation and desorption of H2S, making it difficult for the MoS2+ 2H2O⇌MoO2+ 2H2S equilibrium to move to the right. Secondly, in terms of the application process of the hydrogenation catalyst, the gas is in and out from the bottom during sulfurization, and the gas is in and out from the top during normal operation. When doing experiments, the applicant found that the oxygen-containing coke oven gas is in and out from the top, and the top of the hydrogenation catalyst bed will be desulfurized and the color will become lighter. The gas is in and out from the bottom during sulfurization, and the heat of sulfurization is transferred to the upper part, so that the upper catalyst is strengthened under high temperature conditions, so that the generated MoS2 is more stable, and the anti-high oxygen desulfurization performance of the hydrogenation catalyst at the top of the bed is enhanced.

[0015] ⑶ Recycling of deactivated FeMo hydrogenation waste agent. When preparing FeMo hydrogenation catalyst, the present invention incorporates deoxidized deactivated FeMo hydrogenation waste agent to form an "oxygen leakage" inactive site in the structure, which changes the idea of ​​waste agent utilization. FeMo hydrogenation waste agent has good structural compatibility with the new agent and has good thermal stability. On the one hand, it reduces the deoxidation load, and on the other hand, it can effectively transfer heat and disperse water vapor content inside the catalyst. By recycling the deactivated FeMo hydrogenation catalyst waste agent, the utilization problem of FeMo hydrogenation waste agent is solved, which is green and economical. DETAILED DESCRIPTION

[0016] The present invention will be further described in detail below in conjunction with specific embodiments, but the embodiments provided are only examples and should not be construed as limiting the scope of the present invention. Example 1

[0017] The hydrogenation reactor is filled with 30 m 3 The upper layer is filled with FeMo catalyst and porcelain balls evenly mixed, and the lower layer is filled with FeMo catalyst. The volume ratio of the upper and lower layers is 1:3. Among them, the porcelain balls are 3.75 m 3 , FeMo hydrogenation catalyst 26.25m 3 , about 17.06 tons, the preparation process is as follows: (1) First add 27.72m 3 water, heated to 55°C, added 17 tons of small-pore pseudo-boehmite containing 30% Al2O3, stirred into a slurry, added 0.404 tons of Fe(NO3)3·9H2O and stirred for 10 minutes, and then added the calculated amount of 0.404 tons of (NH4)6Mo7O 24 ·4H2O, maintain the temperature at 60℃, adjust the pH value to 5.8 with ammonia water, stir for 40 minutes, wait for the slurry to turn yellow, filter press into cake, dry at 100℃, and crush to obtain 5.68 tons of catalyst precursor I; (2) Add 16.68m 3 Heat water to 55°C, add 4.38 tons of macroporous pseudo-boehmite containing 70% Al2O3, stir into slurry, add 0.239 tons of Fe(NO3)3·9H2O and stir for 10 minutes, then add 0.313 tons of (NH4)6Mo7O 24 ·4H2O, maintain the temperature at 60℃, adjust the pH value to 5.8 with ammonia water, stir for 40 minutes, wait for the slurry to turn yellow, filter press into cake, dry at 100℃, and crush to obtain 3.42 tons of catalyst precursor II; (3) The deactivated FeMo hydrogenation waste agent was crushed, and 5.68 tons of catalyst precursor I, 3.42 tons of catalyst precursor II, and 7.96 tons of FeMo hydrogenation waste agent were mixed (mass ratio of 2.5:1.5:3.5), ground evenly, added with an appropriate amount of deionized water, stirred and rolled evenly, and then extruded into a mold. After standing for 3.5 hours, it was dried at 110°C for 4.0 hours, and then calcined at 420°C for 5 hours to obtain the catalyst precursor III; (4) Prepare 1% In(NO3)3 solution. Take 2.55 ml of 1% In(NO3)3 solution. 3 + Water 31.45m 3 34m 3 solution, add 17 tons of precursor III, soak until the solution is colorless, the immersion time is 20 hours, then dry at 115°C for 3.5 hours, and then calcine at 400°C for 7 hours to obtain about 17.06 tons of catalyst; the prepared FeMo hydrogenation catalyst has a mass ratio of: Fe2O3 is 2.8%, MoO3 is 7.3%, Al2O3 is 89.9%, and In is 1.5‰.

[0018] During the sulfidation of FeMo hydrogenation catalyst, the gas enters from the bottom and exits from the top, while during normal operation, the gas enters from the top and exits from the bottom.

[0019] Coke oven gas volume 50000m 3 / h, the oxygen content is 0.55%, and after seven months of operation, the temperature rise is 70~85℃, and the hydrogenation catalytic activity is good. Example 2

[0020] The hydrogenation reactor is filled with 50 m 3 The upper layer is filled with FeMo catalyst and porcelain balls evenly mixed, and the lower layer is filled with FeMo catalyst. The volume ratio of the upper and lower layers is 1:2. Among them, the porcelain balls are 8.33 m 3 , FeMo hydrogenation catalyst 41.67m 3 , about 25 tons, the preparation process is as follows: (1) First add 53.58m 3 Heat water to 60°C, add 15.6 tons of small-pore pseudo-boehmite containing 60% Al2O3, stir into slurry, add 1.161 tons of Fe(NO3)3·9H2O and stir for 20 minutes, then add 1.42 tons of (NH4)6Mo7O 24 ·4H2O, maintain the temperature at 60℃, adjust the pH value to 6.4 with ammonia water, stir for 47 minutes, wait for the slurry to turn yellow, filter press into cake, dry at 110℃, and crush to obtain 10.98 tons of catalyst precursor I; (2) Add 37.62m 3water, heated to 60°C, added 9.38 tons of macroporous pseudo-boehmite containing 70% Al2O3, stirred into a slurry, added 0.808 tons of Fe(NO3)3·9H2O and stirred for 20 minutes, and then added 1.006 tons of (NH4)6Mo7O 24 ·4H2O, maintain the temperature at 60℃, adjust the pH value to 6.4 with ammonia water, stir for 47 minutes, wait for the slurry to turn yellow, filter press into cake, dry at 110℃, and crush to obtain 7.71 tons of catalyst precursor II; (3) The deactivated FeMo hydrogenation waste agent was crushed, and 10.98 tons of catalyst precursor I, 7.71 tons of catalyst precursor II, and 6.31 tons of FeMo hydrogenation waste agent were mixed (mass ratio of 4.0:2.8:2.3), ground evenly, added with an appropriate amount of deionized water, stirred and rolled evenly, and then extruded into a mold. After standing for 3.5 hours, it was dried at 120°C for 3.0 hours, and then calcined at 550°C for 4 hours to obtain the catalyst precursor III; (4) Prepare 1% In(NO3)3 solution. Take 7.5 ml of 1% In(NO3)3 solution. 3 + Water 42.5m 3 Matched to 50m 3 solution, add 25 tons of precursor III, soak until the solution is colorless, the immersion time is 23 hours, then dry at 135°C for 3.0 hours, and then calcine at 500°C for 6 hours to obtain about 25 tons of catalyst; the prepared FeMo hydrogenation catalyst has a mass ratio of: Fe2O3 is 4.2%, MoO3 is 10.5%, Al2O3 is 85.3%, and In is 3.0‰.

[0021] During the sulfidation of FeMo hydrogenation catalyst, the gas enters from the bottom and exits from the top, while during normal operation, the gas enters from the top and exits from the bottom.

[0022] Coke oven gas volume 80000m 3 / h, oxygen content is 0.65%, after half a year of operation, the temperature rises to 85~90℃, and the hydrogenation catalytic activity is good. Example 3

[0023] The hydrogenation reactor is filled with 80 m 3 The upper layer is filled with FeMo catalyst and porcelain balls evenly mixed, and the lower layer is filled with FeMo catalyst. The volume ratio of the upper and lower layers is 1:1. Among them, the porcelain balls are 20 m 3 , FeMo hydrogenation catalyst 60m 3 , about 34.8 tons, the preparation process is as follows: (1) First add 67.05m 3Heat water to 65°C, add 40.33 tons of small-pore pseudo-boehmite containing 30% Al2O3, stir into slurry, add 1.035 tons of Fe(NO3)3·9H2O and stir for 30 minutes, then add 1.509 tons of (NH4)6Mo7O 24 ·4H2O, maintain the temperature at 60℃, adjust the pH value to 7.0 with ammonia water, stir for 55 minutes, wait for the slurry to turn yellow, filter press into cake, dry at 120℃, and crush to obtain 13.74 tons of catalyst precursor I; (2) plus 44.11m 3 Heat water to 65°C, add 12.91 tons of macroporous pseudo-boehmite containing 70% Al2O3, stir into slurry, add 0.681 tons of Fe(NO3)3·9H2O and stir for 30 minutes, then add 0.993 tons of (NH4)6Mo7O 24 ·4H2O, maintain the temperature at 60℃, adjust the pH value to 7.0 with ammonia water, stir for 55 minutes, wait for the slurry to turn yellow, filter press into cake, dry at 120℃, and crush to obtain 9.04 tons of catalyst precursor II; (3) The deactivated FeMo hydrogenation waste agent was crushed, and 13.74 tons of catalyst precursor I, 9.04 tons of catalyst precursor II, and 12.02 tons of FeMo hydrogenation waste agent were mixed (mass ratio of 3.2:2.1:2.8), ground evenly, added with an appropriate amount of deionized water, stirred and rolled evenly, and then extruded into a mold. After standing for 3.5 hours, it was dried at 130°C for 2.0 hours, and then calcined at 650°C for 3 hours to obtain the catalyst precursor III; (4) Prepare 1% In(NO3)3 solution. Take 8.0 ml of 1% In(NO3)3 solution. 3 + Water 61.6m 3 39.6m 3 solution, add 34.8 tons of precursor III, soak until the solution is colorless, the immersion time is 26 hours, then dry at 140°C for 2.5 hours, and then calcine at 600°C for 5 hours to obtain 34.8 tons of catalyst; the prepared FeMo hydrogenation catalyst has a mass ratio of: Fe2O3 is 3.0%, MoO3 is 8.9%, Al2O3 is 88.1%, and In is 2.3‰.

[0024] During the sulfidation of FeMo hydrogenation catalyst, the gas enters from the bottom and exits from the top, while during normal operation, the gas enters from the top and exits from the bottom.

[0025] Coke oven gas volume 100000m 3 / h, the oxygen content is 0.68%, and after running for half a year, the temperature rises by 75~95℃, and the hydrogenation catalytic activity is good.

Claims

1. A preparation method of a high oxygen resistant FeMo gas hydrogenation catalyst and its application process, characterized in that: FeMo catalysts are respectively supported by small-pore pseudo-boehmite and large-pore pseudo-boehmite, and catalyst precursors Ⅰ and Ⅱ are prepared by co-precipitation. Ⅰ and Ⅱ are mixed with crushed FeMo hydrogenation waste agent to extrude strips, dry, and roast, and then loaded with 1.5-3.0‰ In in eggshell shape; the upper layer of the hydrogenation reactor is filled with FeMo catalyst and porcelain balls evenly mixed, and the lower layer is filled with FeMo catalyst. During sulfidation, gas enters from the bottom and exits from the top, and during normal operation, gas enters from the top and exits from the bottom; the FeMo catalyst preparation method comprises the following steps: (1) First add a certain amount of water, heat to 55-65°C, add a calculated amount of small-pore pseudo-boehmite, stir to form a slurry, add a calculated amount of ferric nitrate and stir for 10-30 minutes, then add a calculated amount of ammonium molybdate, maintain the temperature at 60°C, adjust the pH value to 5.8-7.0 with ammonia water, stir for 40-55 minutes, wait until the slurry turns yellow, filter press to form a cake, dry at 100-120°C, and crush to obtain the catalyst precursor I; (2) replacing the small-pore pseudo-boehmite in step (1) with large-pore pseudo-boehmite to obtain catalyst precursor II; (3) The deactivated FeMo hydrogenation waste agent is crushed, and the precursor I, precursor II, and FeMo hydrogenation waste agent are mixed in a mass ratio of (2.5-4.0):(1.5-2.8):(2.3-3.5), and after grinding evenly, an appropriate amount of deionized water is added, and after stirring and rolling evenly, the mixture is extruded and formed. After standing for 3.5 hours, the mixture is dried at 110-130°C for 2.0-4.0 hours, and then calcined at 420-650°C for 3-5 hours to obtain the catalyst precursor III; (4) Prepare a 1% In(NO3)3 solution, dilute it with the calculated amount, and use it to impregnate the catalyst precursor III in excess for 20 to 26 hours. Then dry it at 115 to 140°C for 2.5 to 3.5 hours, and then calcine it at 400 to 600°C for 5 to 7 hours to obtain the catalyst.

2. The method for preparing a high oxygen resistant FeMo gas hydrogenation catalyst and its application process according to claim 1, characterized in that: The volume ratio of the upper and lower layers is 1:3~1:1, wherein the upper layer is filled with FeMo catalyst and porcelain balls in an evenly mixed manner of equal volumes.

3. The preparation method of a high oxygen resistant FeMo gas hydrogenation catalyst and its application process according to claim 1, characterized in that: In step (2), the content of each component in the catalyst precursor I obtained by weight percentage is as follows: Fe2O3 is 2.8% to 4.2%, MoO3 is 7.3% to 10.5%, and Al2O3 is 85.3% to 89.9%.

4. The method for preparing a high oxygen resistant FeMo gas hydrogenation catalyst and its application process according to claim 1, characterized in that: Step (3) The content of each component in the catalyst precursor II is as follows: Fe2O3 is 2.8% to 4.2%, MoO3 is 7.3% to 10.5%, and Al2O3 is 85.3% to 89.9% by weight. 。