Vulcanization-free hydrogenation catalyst as well as preparation method and application thereof

Abstract

The invention relates to the field of coal chemical industry, in particular to a vulcanization-free hydrogenation catalyst and a preparation method and application thereof. The invention discloses a vulcanization-free hydrogenation catalyst which comprises a carrier, sulfide of transition metal elements, oxide of rare earth elements and oxide of non-metal elements, the transition metal elements comprise Fe, Ni and Mo; the rare earth element comprises Ce; and the non-metallic element comprises P. According to the catalyst provided by the invention, sulfide of transition metal elements forms a Fe-Ni-Mo-S composite active component, the conversion rate of organic / inorganic sulfur can be effectively improved, the addition of the auxiliary agents P2O5 and CeO2 improves the dispersity of the active component, so that the active component can be fully utilized, trace O2 in the raw materials can be adsorbed, meanwhile, the electronic interference of heavy metals on active sites is relieved, and the catalytic activity of the catalyst is improved. The sintering of the active components in the reaction process can be effectively inhibited, and the stability of the catalyst is improved.

Description

Technical Field

[0001] This invention relates to the field of coal chemical technology, specifically to a sulfur-free hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] Organic sulfur compounds (such as thiols, thioethers, and thiophenes) are key harmful impurities in petroleum refining, natural gas purification, and coal chemical industries. They not only cause corrosion of downstream equipment and catalyst poisoning, but also generate SO2 during combustion, polluting the environment. Therefore, organic sulfur hydrogenation is one of the core processes for industrial gas / liquid purification. Currently, industrially used organic sulfur hydrogenation catalysts are mainly "sulfide-type metal catalysts" (such as Ni-Mo-S / Al2O3 and Co-Mo-S / Al2O3). These catalysts require "pre-sulfidation treatment" (usually using CS or H2S). Toxic sulfiding agents (such as H2S) can only have hydrogenation activity by converting the metal active components into sulfide active phases at 280-400℃. The following technical pain points cannot be ignored: (1) Safety and environmental risks: Presulfiding agents (such as H2S) are highly toxic and corrosive. During operation, leakage can easily cause personnel poisoning or equipment corrosion. In addition, the sulfidation tail gas needs to be treated separately (such as alkaline washing and adsorption), which increases environmental protection costs and process complexity; (2) Low process efficiency: The presulfidation process requires a separate reaction device (usually 24-48 hours), which prolongs the operation cycle of the device and has a significant impact on the production capacity of intermittent production scenarios; (3) Catalyst performance loss: If the temperature and sulfiding agent concentration are not properly controlled during the presulfidation process, it can easily lead to the agglomeration of active components or sintering of the carrier, which reduces the specific surface area and activity stability of the catalyst and shortens its service life; (4) Limited application scenarios: For low sulfur-containing raw materials (such as LNG and fine chemical tail gas), the "over-sulfidation" of traditional sulfidation catalysts may cause side reactions (such as hydrocarbon hydrocracking), which reduces the yield of the target product. Summary of the Invention

[0003] This invention provides a sulfur-free hydrogenation catalyst, its preparation method, and its application. Through innovative active component design and support modification, the catalyst can be directly added to the hydrogenation reaction without pre-sulfurization treatment after preparation. At the same time, it takes into account high hydrogenation activity, high selectivity, and long cycle stability, so as to solve the safety hazards, process pain points, and performance defects of traditional sulfurized catalysts, and meet the needs of petrochemical, natural gas purification and other fields for efficient, environmentally friendly and convenient hydrogenation processes.

[0004] In a first aspect, the present invention provides a sulfur-free hydrogenation catalyst, comprising a support, a sulfide of a transition metal element, an oxide of a rare earth element, and an oxide of a non-metal element; wherein the transition metal element comprises Fe, Ni, and Mo; the rare earth element comprises Ce; and the non-metal element comprises P.

[0005] In one optional embodiment, the mass ratio of the carrier, the sulfide of the transition metal element, the oxide of the rare earth element, and the oxide of the nonmetal element, by weight, is (75-85):(13-22):1:(1-2). In one optional embodiment, the molar ratio of Fe, Ni, and Mo in the sulfur-free hydrogenation catalyst is 1:(1-4):(1-4).

[0006] In one optional embodiment, the specific surface area of ​​the sulfur-free hydrogenation catalyst is 200-280 m². 2 / g; In one optional embodiment, the average pore size of the sulfur-free hydrogenation catalyst is 3-20 nm; In one alternative embodiment, the support for the sulfur-free hydrogenation catalyst comprises molecular sieves and alumina.

[0007] Secondly, the present invention also provides a method for preparing a sulfur-free hydrogenation catalyst, comprising the following steps: S1, the carrier and binder are dispersed and mixed in water, dried and calcined to obtain an intermediate; S2, nickel source, molybdenum source, iron source, cerium source and phosphorus source are dissolved, then impregnated in equal amounts on intermediate, dried and calcined to obtain precursor; S3, add a first-stage sulfiding agent solution to the precursor for first-stage sulfidation, dry, then add a second-stage sulfiding agent solution for second-stage sulfidation to obtain the precursor sulfide. S4, after passivating the precursor sulfide with the addition of a passivating agent, a sulfide-free hydrogenation catalyst is obtained.

[0008] In an optional embodiment, in S1, the mass ratio of the molecular sieve, alumina, binder, and water is 1:(0.3-0.8):(0.1-0.4):(0.03-0.05):(1-2). It should be noted that the support of the sulfur-free hydrogenation catalyst also includes aluminum sol mixed and calcined. After calcination, the aluminum sol will also become alumina. The support has a high molecular sieve content, and the addition of aluminum sol can improve the strength. The mass ratio of aluminum sol to alumina is (0.1-0.4):(0.3-0.8).

[0009] In one optional embodiment, in S1, the drying temperature is 100-120°C and the time is 2-10 hours; In one optional embodiment, in S1, the calcination temperature is 400-600°C and the time is 8-12 hours.

[0010] In one optional embodiment, in step S2, the drying temperature is 100-120°C and the time is 2-10 hours; In one optional embodiment, in S2, the calcination temperature is 350-600°C and the time is 8-10 hours.

[0011] In one optional embodiment, in S3, the temperature of the first vulcanization stage is 80-100°C, and the time is 8-10 hours. In one optional embodiment, in step S3, the drying temperature is 100-120°C and the time is 8-10 hours. In one optional embodiment, in S3, the temperature of the second-stage vulcanization is 80-100°C and the time is 8-10 hours. In one optional embodiment, the mass ratio of the precursor sulfide, the first-stage sulfide solution, and the second-stage sulfide solution is 1:(1-3):(1-3).

[0012] In one optional implementation, in step S4, the passivation temperature is 90-150°C and the time is 2-4 hours. In one optional embodiment, in S4, the mass ratio of the passivating agent to the precursor sulfide is (1-4):1; In one optional embodiment, the passivating agent includes at least one of hydrogen peroxide solution and hydrotreated crude oil; Optionally, the mass concentration of hydrogen peroxide in the hydrogen peroxide solution is 1%-3%; Optionally, the mass concentration of ethanethiol in the hydrogenated crude oil is 1.5-2.5%; Optionally, the solvent in the hydrogen peroxide solution includes at least one of n-octane, cyclohexane, and n-heptane.

[0013] The molecular sieve includes a mesoporous molecular sieve with an average pore size of 2-50 nm; optionally, it is at least one of MCM-41, SBA-1, and MSU-1. In one optional embodiment, the specific surface area of ​​the alumina is ≥400 m². 2 / g; In one optional embodiment, the binder includes at least one of guar gum powder, methylcellulose, and citric acid; In one optional embodiment, the vulcanizing agent includes at least one of ammonium sulfide solution, dimethyl disulfide, and diethyl disulfide; Optionally, the mass concentration of the ammonium sulfide solution is 40%-44%; In one optional embodiment, the nickel source includes at least one of basic nickel carbonate, nickel nitrate, and nickel sulfate; In one optional embodiment, the molybdenum source includes at least one of ammonium tetramolybdate, ammonium heptamolybdate, and molybdenum trioxide; In one optional embodiment, the iron source includes at least one of ferrous sulfate, ferrous nitrate, and ferrous chloride; In one optional embodiment, the cerium source includes at least one of cerium sulfate, cerium nitrate, and cerium chloride; In one alternative embodiment, the phosphorus source comprises phosphoric acid.

[0014] Thirdly, the present invention also provides an application of a sulfur-free hydrogenation catalyst in the field of coal chemical industry.

[0015] The technical solution of this invention has the following advantages: 1. The present invention provides a sulfur-free hydrogenation catalyst, comprising a support, sulfides of transition metal elements, oxides of rare earth elements, and oxides of non-metallic elements; wherein the transition metal elements include Fe, Ni, and Mo; the rare earth elements include Ce; and the non-metallic elements include those containing P.

[0016] The catalyst provided by this invention contains sulfides of transition metal elements, forming a Fe-Ni-Mo-S composite active component. This highly active crystalline structure exhibits excellent hydrogenation catalytic activity and can effectively improve the conversion rate of organic / inorganic sulfur. The addition of Fe reduces costs and improves the catalyst's resistance to poisoning. Furthermore, the weak interaction between FeS and the support through the "Fe-O-support" bond ensures the dispersibility of the active component while avoiding the formation of an "inert phase" caused by strong interactions, resulting in slow activity decay and extended service life after long-term use. The catalyst also incorporates oxides of rare earth elements and oxides of non-metallic elements as promoters, particularly the addition of P2O5 and CeO2. P2O5 promotes acid-catalyzed auxiliary reactions such as C / C bond breaking and isomerization in the hydrogenation reaction, enhancing the dispersibility of the active component and allowing for its full utilization. CeO2 possesses CeO2-like properties. 3+ / Ce 4+ The reversible valence state change can adsorb trace amounts of O2 in the raw materials (avoiding O2 oxidation of MoS2 to MoO3), while mitigating the electronic interference of heavy metals on the active sites. It can effectively inhibit the sintering of active components during the reaction process and improve the stability of the catalyst. The sulfur-free hydrogenation catalyst of the present invention does not require additional sulfurization treatment before use, avoiding the use of toxic and harmful sulfurizing agents, reducing safety and environmental risks, simplifying process steps, shortening start-up cycle, and reducing production energy consumption and costs.

[0017] 2. This invention provides a method for preparing a sulfur-free hydrogenation catalyst. The precursor is sulfurized using a sulfurizing agent, with two sulfurization processes ensuring complete sulfurization, which is safer than gas-phase sulfurization. In this catalyst preparation method, mesoporous molecular sieves and Al2O3 are used in combination as a support, which reduces the proportion of strongly acidic sites, decreases olefin polymerization, resists carbon deposition, increases specific surface area, improves the pore structure and surface acidity of the support, and enhances the dispersibility of the active components on the support surface, providing more active sites for the hydrogenation reaction. The passivation method used in this invention results in a mild reaction, and the oxidation rate is easily controlled by concentration and temperature, reducing the risk of overheating and catalyst burnout. In the liquid phase environment, the catalyst and passivator are in uniform contact, resulting in a more complete oxide film coverage. The catalyst preparation method of this invention is simple and convenient to operate, using conventional mixing, drying, and calcining equipment, requiring no special reaction devices (such as high-pressure reactors or inert gas circulation systems). The raw materials are all industrial-grade conventional chemicals, inexpensive and readily available, resulting in low cost and easy industrial production.

[0018] 3. The ammonium sulfide solution used in this invention is weakly alkaline, avoiding the problems caused by strongly alkaline sulfiding agents due to OH groups. - Excessive concentration leads to the formation of metal hydroxide impurities, which have weak reducing properties, avoid disordered metal ion valence states, and leave no harmful residual cations. Detailed Implementation

[0019] The following embodiments are provided to better understand the present invention, but the following embodiments do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the scope of protection of the present invention.

[0020] Unless otherwise defined, 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 belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having” and any variations thereof in the text of this application are intended to cover non-exclusive inclusion.

[0021] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments. The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers from a to b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed herein, and "0-5" is merely a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥ 2, it is equivalent to disclosing that the parameter can be, for example, integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0022] In the description of the embodiments of this application, the term "and / or" is merely a description of the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can represent three situations: A exists alone, A and B exist simultaneously, and B exists alone.

[0023] In the description of the embodiments of this application, the term "at least one" refers to one or more (including two).

[0024] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0025] Unless otherwise specified, all experimental steps or conditions in the examples were performed according to conventional experimental procedures and conditions in the art. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0026] Example 1 This embodiment provides a method for preparing a sulfur-free hydrogenation catalyst, and the specific steps and parameter settings are as follows: S1, 214.29g of molecular sieve (MCM-41) and 119.4g of (specific surface area = 400m²) 2Mix 50g of alumina powder and 50g of aluminum sol, add 8.5g of binder (guar gum powder) and 320ml of deionized water, grind thoroughly and evenly, extrude into strips with a diameter of 3mm, dry at 110℃ for 6h, then calcine at 500℃ for 10h, and cool to room temperature to obtain an intermediate.

[0027] S2, 23.05g of molybdenum source (ammonium tetramolybdate), 19.85g of iron source (ferrous sulfate), 51.78g of nickel source (nickel nitrate), 2.44ml of phosphorus source (phosphoric acid), and 5.42g of cerium source (cerium chloride) were dissolved and then impregnated onto 200g of intermediate in equal amounts. The mixture was dried at 110℃ for 8 hours and then calcined at 500℃ for 9 hours to obtain the precursor.

[0028] S3. Add 100g of precursor to a double cone, vacuum and add 200ml of first-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 90℃ for 9h, then dry inside the double cone at 110℃ for 9h, then add 200ml of second-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 90℃ for 9h, and obtain precursor sulfide; S4, the precursor sulfide was passivated at 120°C for 3 hours using a 2% hydrogen peroxide solution (using n-octane as a solvent). After passivation, it was rinsed with n-octane and then purged with nitrogen and cooled to obtain a sulfide-free hydrogenation catalyst. The mass ratio of hydrogen peroxide solution to precursor sulfide was 3:1.

[0029] The mass ratio of the support, transition metal sulfides, rare earth oxides, and non-metal oxides in the obtained sulfur-free hydrogenation catalyst is 80:18:1:1.

[0030] Example 2 This embodiment provides a method for preparing a sulfur-free hydrogenation catalyst, and the specific steps and parameter settings are as follows: S1, 210.38g of molecular sieve (MCM-41) and 120.58g of (specific surface area = 400m²) 2 Mix 49g of alumina powder and 49g of aluminum sol, add 9g of binder (guar gum powder) and 320ml of deionized water, grind thoroughly and evenly, extrude into strips with a diameter of 3mm, dry at 110℃ for 6h, then calcine at 500℃ for 10h, and cool to room temperature to obtain an intermediate.

[0031] S2, 24.91g of molybdenum source (ammonium tetramolybdate), 23.66g of iron source (ferrous sulfate), 56.57g of nickel source (nickel nitrate), 5.05ml of phosphorus source (phosphoric acid), and 5.57g of cerium source (cerium chloride) were dissolved and then impregnated onto 200g of intermediate in equal amounts. The mixture was dried at 110℃ for 8 hours and then calcined at 500℃ for 9 hours to obtain the precursor.

[0032] S3. Add 100g of precursor to a double cone, vacuum and add 200ml of first-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 90℃ for 9h, then dry inside the double cone at 110℃ for 9h, then add 200ml of second-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 90℃ for 9h, and obtain precursor sulfide; S4, the precursor sulfide was passivated at 110°C for 3.5 h using a 2% hydrogen peroxide solution (using n-octane as a solvent). After passivation, it was rinsed with n-octane and then purged with nitrogen and cooled to obtain a sulfide-free hydrogenation catalyst. The mass ratio of hydrogen peroxide solution to precursor sulfide was 3:1.

[0033] The mass ratio of the support, transition metal sulfides, rare earth oxides, and non-metal oxides in the obtained sulfur-free hydrogenation catalyst is 78:19:1:2.

[0034] Example 3 This embodiment provides a method for preparing a sulfur-free hydrogenation catalyst, and the specific steps and parameter settings are as follows: S1, 220.41g of molecular sieve (MCM-41) and 89.55g of (specific surface area = 400m²) 2 Mix 80g of alumina powder and 80g of aluminum sol, add 7g of binder (guar gum powder) and 300ml of deionized water, grind thoroughly and evenly, extrude into strips with a diameter of 3mm, dry at 100℃ for 10h, then calcine at 400℃ for 12h, and cool to room temperature to obtain an intermediate.

[0035] S2, 12.34g of molybdenum source (ammonium tetramolybdate), 15.64g of iron source (ferrous sulfate), 28.13g of nickel source (nickel nitrate), 2.48ml of phosphorus source (phosphoric acid), and 5.26g of cerium source (cerium chloride) were dissolved and then impregnated onto 200g of intermediate in equal amounts. The mixture was dried at 100℃ for 10 hours and then calcined at 350℃ for 10 hours to obtain the precursor.

[0036] S3. Add 100g of precursor to a double cone, vacuum and add 150ml of first-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 100℃ for 8h, dry inside the double cone at 100℃ for 10h, then add 150ml of second-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 80℃ for 10h, and obtain precursor sulfide. S4, the precursor sulfide was passivated at 150°C for 2 hours using a 2% hydrogen peroxide solution (using n-octane as a solvent). After passivation, it was rinsed with n-octane and then purged with nitrogen and cooled to obtain a sulfide-free hydrogenation catalyst. The mass ratio of hydrogen peroxide solution to precursor sulfide was 4:1.

[0037] The mass ratio of the support, transition metal sulfides, rare earth oxides, and non-metal oxides in the obtained sulfur-free hydrogenation catalyst is 85:13:1:1.

[0038] Example 4 This embodiment provides a method for preparing a sulfur-free hydrogenation catalyst, and the specific steps and parameter settings are as follows: S1, 190.82g of molecular sieve (MCM-41) and 156.72g of (specific surface area = 400m²) 2 Mix 30g of alumina powder and 30g of aluminum sol, add 9g of binder (guar gum powder) and 350ml of deionized water, grind thoroughly and evenly, extrude into strips with a diameter of 3mm, dry at 120℃ for 2h, then calcine at 600℃ for 8h, and cool to room temperature to obtain an intermediate.

[0039] S2, 29.99g of molybdenum source (ammonium tetramolybdate), 26.59g of iron source (ferrous sulfate), 73.43g of nickel source (nickel nitrate), 5.32ml of phosphorus source (phosphoric acid), and 5.77g of cerium source (cerium chloride) were dissolved and then impregnated onto 200g of intermediate in equal amounts. The mixture was dried at 120℃ for 2 hours and then calcined at 600℃ for 8 hours to obtain the precursor.

[0040] S3. Add 100g of precursor to a double cone, vacuum and add 250ml of first-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 80℃ for 10h, dry inside the double cone at 120℃ for 8h, then add 250ml of second-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 100℃ for 8h, and obtain precursor sulfide. S4, the precursor sulfide was passivated at 90°C for 4 hours using a 1% hydrogen peroxide solution (using n-octane as a solvent). After passivation, it was rinsed with n-octane and then purged with nitrogen and cooled to obtain a sulfide-free hydrogenation catalyst. The mass ratio of hydrogen peroxide solution to precursor sulfide was 1:1.

[0041] The mass ratio of the support, transition metal sulfides, rare earth oxides, and non-metal oxides in the obtained sulfur-free hydrogenation catalyst is 75:22:1:2.

[0042] Example 5 This embodiment provides a method for preparing a sulfur-free hydrogenation catalyst, and the specific steps and parameter settings are as follows: S1, 214.29g of molecular sieve (MCM-41) and 134.33g of (specific surface area = 400m²) 2 Mix alumina powder (g), add 9g binder (guar gum powder) and 380ml deionized water, grind thoroughly and evenly, extrude into strips with a diameter of 3mm, dry at 110℃ for 6h, then calcine at 500℃ for 10h, and cool to room temperature to obtain an intermediate.

[0043] S2, 23.05g of molybdenum source (ammonium tetramolybdate), 19.85g of iron source (ferrous sulfate), 51.78g of nickel source (nickel nitrate), 2.44ml of phosphorus source (phosphoric acid), and 5.42g of cerium source (cerium chloride) were dissolved and then impregnated onto 200g of intermediate in equal amounts. The mixture was dried at 110℃ for 8 hours and then calcined at 500℃ for 9 hours to obtain the precursor.

[0044] S3. Add 100g of precursor to a double cone, vacuum and add 200ml of first-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 90℃ for 9h, then dry inside the double cone at 110℃ for 9h, then add 200ml of second-stage vulcanizing agent solution (42% ammonium sulfide solution), vulcanize at 90℃ for 9h, and obtain precursor sulfide; S4, the precursor sulfide was passivated at 120°C for 3 hours using a 2% hydrogen peroxide solution (using n-octane as a solvent). After passivation, it was rinsed with n-octane and then purged with nitrogen and cooled to obtain a sulfide-free hydrogenation catalyst. The mass ratio of hydrogen peroxide solution to precursor sulfide was 3:1.

[0045] The mass ratio of the support, transition metal sulfides, rare earth oxides, and non-metal oxides in the obtained sulfur-free hydrogenation catalyst is 80:18:1:1.

[0046] Comparative Example 1 This comparative example provides a method for preparing a sulfur-free hydrogenation catalyst. The only difference from Example 1 is that cerium chloride of equal mass is used to replace nickel nitrate, ammonium tetramolybdate, and ferrous sulfate.

[0047] Comparative Example 2 This comparative example provides a method for preparing a sulfur-free hydrogenation catalyst, which differs from Example 1 only in that an equal mass of nickel nitrate is used to replace cerium chloride and phosphoric acid.

[0048] Comparative Example 3 This comparative example provides a method for preparing a sulfur-free hydrogenation catalyst. The only difference from Example 1 is that ferrous sulfate is replaced with an equal mass of nickel nitrate and ammonium tetramolybdate (mass ratio 1:1).

[0049] Comparative Example 4 This comparative example provides a method for preparing a sulfur-free hydrogenation catalyst. The only difference from Example 1 is that nickel nitrate is replaced with an equal mass of ferrous sulfate and ammonium tetramolybdate (mass ratio 1:1).

[0050] Comparative Example 5 This comparative example provides a method for preparing a sulfur-free hydrogenation catalyst. The only difference from Example 1 is that ammonium tetramolybdate is replaced with an equal mass of nickel nitrate and ferrous sulfate (mass ratio 1:1).

[0051] Comparative Example 6 This comparative example provides a method for preparing a sulfur-free hydrogenation catalyst, which differs from Example 1 only in that an equal mass of lanthanum chloride is used to replace cerium chloride.

[0052] Comparative Example 7 This comparative example provides a method for preparing a sulfur-free hydrogenation catalyst, which differs from Example 1 only in that an equal mass of boric acid is used to replace phosphoric acid.

[0053] Experimental Example 1 The sulfur-free hydrogenation catalysts obtained in each embodiment and comparative example were characterized by performance testing. The specific testing methods are as follows: Specific surface area and pore size were tested using an ASAP2460 fully automated specific surface area and pore size analyzer manufactured by Micro Instruments, Inc., USA. Table 1 Characterization performance data

[0054] Experiment Example 2 The sulfur-free hydrogenation catalysts obtained in each embodiment and comparative example were subjected to operating condition simulation to test their organic sulfur / inorganic sulfur conversion rate and service life. The specific test methods are as follows: The specific process is as follows: First, the catalyst was loaded into the reactor, and the temperature and pressure were adjusted to the required conditions. After purging with nitrogen, the raw material gas was introduced to start the experiment. The initial reaction activity was measured after 10 hours of reaction and the conversion rate was tested after 400 hours of reaction.

[0055] The conversion rate is calculated as follows: Conversion rate = (Outlet impurity concentration / Inlet impurity concentration) × 100% The impurity concentration was detected using a gas chromatograph A60 from Changzhou Pannuo Instrument Co., Ltd.

[0056] Table 2 Reactor reaction conditions

[0057] Table 3. Components of Raw Gas

[0058] The specific test results are shown in the table below: Table 4 Catalyst Performance Test

[0059] Table 5. Catalyst stability test after 400 hours

[0060] The data above demonstrates that this invention, by constructing a complete system with nickel, molybdenum, and iron as core active components and cerium and phosphorus as specific promoters, and combining this with an optimized two-step sulfidation and passivation process, successfully prepared a sulfidation-free hydrogenation catalyst with high initial activity and excellent stability. Its performance advantages are highly dependent on this complete and optimized formulation system. The absence of any key active component (especially the synergistic system composed of Ni, Mo, and Fe) or the replacement of any key promoter (the combination of Ce and P) will lead to a significant decrease in the catalyst's initial activity and long-term stability. Therefore, compared with existing technologies, this invention has significant advantages in terms of service life, conversion efficiency, stability, and broad applicability.

[0061] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A sulfur-free hydrogenation catalyst, characterized by, The carrier, sulfides of transition metal elements, oxides of rare earth elements and oxides of non-metal elements; The transition metal elements include Fe, Ni and Mo; The rare earth elements include Ce; The non-metal elements include P.

2. The sulfur-free hydrogenation catalyst according to claim 1, characterized in that, The mass ratio of the carrier, sulfides of transition metal elements, oxides of rare earth elements and oxides of non-metal elements is (75-85):(13-22):1:(1-2) by weight; And / or, the molar ratio of Fe, Ni and Mo in the sulfur-free hydrogenation catalyst is 1:(1-4):(1-4).

3. The sulphur-free hydrogenation catalyst according to claim 1 or 2, characterised in that The non-sulfided hydrogenation catalyst has a specific surface area of 200-280 m 2 / g; And / or, the average pore size of the sulfur-free hydrogenation catalyst is 3-20 nm; And / or, the carrier of the sulfur-free hydrogenation catalyst includes molecular sieve and alumina.

4. A process for the preparation of the sulphur-free hydrogenation catalyst according to any one of claims 1 to 3, characterised in that The method comprises the following steps: S1, the carrier, binder is dispersed in water, mixed, dried and calcined to obtain an intermediate; S2, the nickel source, molybdenum source, iron source, cerium source and phosphorus source are dissolved, and the intermediate is impregnated with an equal amount, dried and calcined to obtain a precursor; S3, a first sulfuration agent solution is added to the precursor for first sulfuration, dried, and a second sulfuration agent solution is added for second sulfuration to obtain a precursor sulfide; S4, a passivation agent is added to the precursor sulfide for passivation to obtain a sulfur-free hydrogenation catalyst.

5. The process for preparing a sulfur-free hydrogenation catalyst according to claim 4, characterized by, In S1, the carrier includes molecular sieve and alumina; Optionally, the mass ratio of the molecular sieve, alumina, binder, water is 1:(0.3-0.8):(0.1-0.4):(0.03-0.05):(1-2); And / or, in S1, the preparation process of the intermediate further includes adding an aluminum sol; Optionally, the mass ratio of the aluminum sol to alumina is (0.1-0.4):(0.3-0.8); And / or, the drying temperature is 100-120℃, and the time is 2-10h; And / or, the calcination temperature is 400-600℃, and the time is 8-12h.

6. The process for the preparation of a non-sulfided hydrogenation catalyst according to claim 4 or 5, characterized in that, In S2, the drying temperature is 100-120℃, and the time is 2-10h; And / or, the calcination temperature is 350-600℃, and the time is 8-10h.

7. Process for the preparation of a sulphur-free hydrogenation catalyst according to any one of claims 4 to 6, characterised in that In S3, the first sulfuration temperature is 80-100℃, and the time is 8-10h; And / or, the drying temperature is 100-120℃, and the time is 8-10h; And / or, the second sulfuration temperature is 80-100℃, and the time is 8-10h; And / or, the mass ratio of the precursor sulfide, the first sulfuration agent solution and the second sulfuration agent solution is 1:(1-3):(1-3).

8. Process for the preparation of a sulphur-free hydrogenation catalyst according to any one of claims 4 to 7, characterised in that, In S4, the passivation temperature is 90-150℃, and the time is 2-4h; And / or, the mass ratio of the passivation agent to the precursor sulfide is (1-4):1; And / or, the passivation agent includes at least one of hydrogen peroxide solution and hydrocracking crude oil; Optionally, the mass concentration of hydrogen peroxide in the hydrogen peroxide solution is 1%-3%; Optionally, the hydrocracking crude oil includes ethanethiol, and the mass concentration of ethanethiol is 1.5-2.5%; Optionally, the solvent in the hydrogen peroxide solution includes at least one of n-octane, cyclohexane and n-heptane.

9. Process for the preparation of a sulphur-free hydrogenation catalyst according to any one of claims 4 to 8, characterised in that The molecular sieve comprises a mesoporous molecular sieve with an average pore size of 2-50 nm; and optionally at least one of MCM-41, SBA-1, MSU-1; and / or the specific surface area of the aluminium oxide is > 400 m 2 / g; And / or, the binder comprises at least one of sesbania powder, methyl cellulose, citric acid; And / or, the vulcanizing agent comprises at least one of ammonium sulfide solution, dimethyl disulfide, diethyl disulfide; Optionally, the mass concentration of the ammonium sulfide solution is 40%-44%; And / or, the nickel source comprises at least one of basic nickel carbonate, nickel nitrate, nickel sulfate; And / or, the molybdenum source comprises at least one of ammonium tetramolybdate, ammonium heptamolybdate, molybdenum trioxide; And / or, the iron source comprises at least one of ferrous sulfate, ferrous nitrate, ferrous chloride; And / or, the cerium source comprises at least one of cerous sulfate, cerous nitrate, cerous chloride; And / or, the phosphorus source comprises phosphoric acid.

10. Application of the sulfur-free hydrogenation catalyst of any one of claims 1-3 or prepared by the preparation method of any one of claims 4-9 in the field of coal chemical industry.

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