A sulfur recovery tail gas hydrogenation catalyst and its preparation method

Abstract

This invention belongs to the field of catalyst technology and provides a sulfur recovery tail gas hydrogenation catalyst and its preparation method. The catalyst consists of a support and active components supported on the support. The active components are molybdenum sulfide, cobalt sulfide, and nickel sulfide. The support is prepared by mixing and molding an aluminum-titanium composite hydroxide with magnesium oxide, a pore-expanding agent, and a binder, followed by calcination. The aluminum-titanium composite hydroxide is prepared by a rapid co-precipitation-secondary crystallization method. By total weight of the catalyst, the content of molybdenum sulfide is 5-20 wt%, the content of cobalt sulfide is 1-5 wt%, the content of nickel sulfide is 0.5-5 wt%, the content of the aluminum-titanium composite metal oxide is 75-90 wt%, and the content of magnesium oxide is 1-10 wt%. The catalyst of this invention has the characteristics of high SO2 hydrogenation activity, strong organic sulfur hydrolysis ability, and good activity stability.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a sulfur recovery tail gas hydrogenation catalyst and a method for preparing the sulfur recovery tail gas hydrogenation catalyst. Background Technology

[0002] With increasingly stringent environmental regulations and heightened public awareness of environmental protection, the requirements for sulfur-containing compound emissions from petroleum processing and petrochemical plants are becoming increasingly stringent. To meet the requirements of the new environmental standards, most refineries and natural gas purification plants employ sulfur recovery processes for the treatment of sulfuric acid-containing gases, with a total sulfur recovery rate of over 99.80%. To meet this total sulfur recovery rate, most sulfur recovery units utilize reduction absorption processes.

[0003] In the Claus+SCOT sulfur recovery process, sulfuric acid-containing gases undergo a two-stage Claus conversion before entering a hydrogenation reactor. Under the action of a hydrogenation catalyst, elemental sulfur and sulfur-containing compounds in the tail gas are hydrogenated or hydrolyzed into hydrogen sulfide. Then, selective absorption with amine solution is used, and the purified tail gas is discharged into the atmosphere. In the above reduction absorption method, sulfur dioxide hydrogenation and organic sulfide hydrolysis are the key steps, involving the following main chemical reactions: SO₂ + 3H₂ = H₂S + 2H₂O, CO₂ + H₂O = CO₂ + H₂S, and CS₂ + 2H₂O = CO₂ + 2H₂S. Catalysts are required to accelerate the reaction rate during sulfur dioxide hydrogenation and organic sulfide hydrolysis.

[0004] Sulfur recovery tail gas hydrogenation catalysts generally consist of a support and active components. Existing catalysts primarily contain active components such as cobalt, molybdenum, nickel, and tungsten, while the supports mainly include alumina, silicon-modified alumina, and titanium dioxide. Catalysts using alumina as a support suffer from sulfation and lattice defects due to the presence of large amounts of SO2 and water vapor in the reaction medium. Patent documents CN1498674A and CN1621134A disclose sulfur tail gas hydrogenation catalysts using silicon-modified alumina as a support and cobalt and molybdenum as active centers; however, these catalysts require high hydrogenation temperatures and consume significant energy during application.

[0005] Currently, the sulfur dioxide hydrogenation activity, organic sulfide hydrolysis activity, and catalyst stability of sulfur recovery tail gas hydrogenation catalysts need to be improved. Summary of the Invention

[0006] In view of the above, the purpose of this invention is to provide a sulfur recovery tail gas hydrogenation catalyst and its preparation method. By adjusting the support structure and the dispersion of active components, the interaction between the active components and the support is controlled, so that the catalyst has high sulfur dioxide hydrogenation activity and organic sulfide hydrolysis activity under relatively mild conditions, and the catalyst has better stability.

[0007] The first aspect of the present invention provides a sulfur recovery tail gas hydrogenation catalyst, which comprises a support and an active component supported on the support; the active component is molybdenum sulfide, cobalt sulfide and nickel sulfide; the support is prepared by mixing aluminum-titanium composite hydroxide with magnesium oxide, pore expander and binder, molding and then calcining, and the aluminum-titanium composite hydroxide is prepared by a rapid co-precipitation-secondary crystallization method. Based on the total weight of the catalyst, the content of molybdenum sulfide is 5-20 wt%, the content of cobalt sulfide is 1-5 wt%, the content of nickel sulfide is 0.5-5 wt%, the content of aluminum-titanium composite metal oxide is 75-90 wt%, and the content of magnesium oxide is 1-10 wt%.

[0008] A second aspect of the present invention provides a method for preparing the above-mentioned sulfur recovery tail gas hydrogenation catalyst, the method comprising the following steps: 1) Titanium-aluminum composite hydroxide was prepared by a rapid co-precipitation-secondary crystallization method; 2) The titanium-aluminum composite hydroxide is mixed with magnesium oxide, a pore expander, and a binder, and then extruded and molded. The molded body is then calcined to obtain a carrier. 3) Prepare molybdenum-containing ionic liquids, cobalt-containing ionic liquids, and nickel-containing ionic liquids respectively; 4) Dissolve the ionic liquid obtained in step 3) in ethanol, then impregnate the support obtained in step 2), rotary evaporate, dry, and then calcine to obtain the catalyst precursor; 5) The catalyst precursor is sulfided to obtain the catalyst.

[0009] Compared with the prior art, the present invention has the following beneficial effects: The catalyst of the present invention is composed of metal sulfides, composite metal oxides, etc. The precursor of the metal sulfide is an ionic liquid, which is conducive to the uniform dispersion of the metal and promotes the sulfidation of the active metal. The precursor of the composite metal oxide is a titanium-aluminum composite hydroxide prepared by a rapid co-precipitation-secondary crystallization method. The titanium-aluminum composite hydroxide has a small and uniform particle size, which is conducive to increasing the specific surface area of ​​the support and improving the interaction with the active components. This makes the catalyst have the characteristics of high SO2 hydrogenation activity and strong organic sulfur hydrolysis ability. The SO2 hydrogenation and CS2 hydrolysis activities are maintained at 99.9% and 99.0%, respectively, and the catalytic performance is stable. It is particularly suitable as a catalyst for hydrogenation of sulfur recovery tail gas.

[0010] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0011] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0012] According to a first aspect of the present invention, the present invention provides a sulfur recovery tail gas hydrogenation catalyst, the catalyst comprising a support and an active component supported on the support; the active component is molybdenum sulfide, cobalt sulfide and nickel sulfide; the support is prepared by mixing aluminum-titanium composite hydroxide with magnesium oxide, a pore-expanding agent and a binder, molding and then calcining, wherein the aluminum-titanium composite hydroxide is prepared by a rapid co-precipitation-secondary crystallization method. Based on the total weight of the catalyst, the content of molybdenum sulfide is 5-20 wt%, the content of cobalt sulfide is 1-5 wt%, the content of nickel sulfide is 0.5-5 wt%, the content of aluminum-titanium composite metal oxide is 75-90 wt%, and the content of magnesium oxide is 1-10 wt%.

[0013] In this invention, the primary particle size of the aluminum-titanium composite hydroxide is 550-600 nm, and the secondary particle size is 10-25 μm. The particle size during rapid co-precipitation is the primary particle size, and the particle size during secondary crystallization is the secondary particle size.

[0014] According to the present invention, the aluminum-titanium composite metal oxide contains 25-40 wt% titanium dioxide and 60-75 wt% aluminum oxide by weight.

[0015] In this invention, the specific surface area of ​​the carrier is 315-350 m². 2 / g.

[0016] Preferably, based on the total weight of the catalyst, the content of molybdenum sulfide is 8-15 wt%, the content of cobalt sulfide is 1-3 wt%, the content of nickel sulfide is 0.5-2 wt%, the content of aluminum-titanium composite metal oxide is 80-90 wt%, and the content of magnesium oxide is 3-8 wt%.

[0017] According to the present invention, the pore-expanding agent may be selected from at least one of polyethylene glycol, polyethylene oxide and guar gum powder, and its dosage may be conventionally selected according to the prior art. For example, the dosage of the pore-expanding agent may be 2-6 wt% based on the total weight of the carrier.

[0018] In this invention, the binder may be selected from at least one of nitric acid, acetic acid, oxalic acid and citric acid, and its dosage is the conventional dosage in the art, for example, the dosage of the binder is 2-10 wt% based on the total weight of the carrier.

[0019] According to a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned sulfur recovery tail gas hydrogenation catalyst, the method comprising the following steps: 1) Titanium-aluminum composite hydroxide was prepared by a rapid co-precipitation-secondary crystallization method; 2) The titanium-aluminum composite hydroxide is mixed with magnesium oxide, a pore expander, and a binder, and then extruded and molded. The molded body is then calcined to obtain a carrier. 3) Prepare molybdenum-containing ionic liquids, cobalt-containing ionic liquids, and nickel-containing ionic liquids respectively; 4) Dissolve the ionic liquid obtained in step 3) in ethanol, then impregnate the support obtained in step 2), rotary evaporate, dry, and then calcine to obtain the catalyst precursor; 5) The catalyst precursor is sulfided to obtain the catalyst.

[0020] In this invention, the preparation of titanium-aluminum composite hydroxide may include: (1) Dissolve Al(NO3)3·9H2O and Ti(SO4)2 to prepare a mixed salt solution, and dissolve NaOH and Na2CO3 to prepare an alkaline solution; (2) Add the mixed salt solution and the alkaline solution to the colloid mill at the same time and stir to obtain a titanium-aluminum composite hydroxide crystal nucleus suspension; (3) Add the crystal nucleus suspension to the reaction vessel for crystallization; (4) The product obtained in step (3) is filtered, washed, dried and crushed to obtain the titanium-aluminum composite hydroxide.

[0021] Specifically, in step (1), the molar ratio of Al(NO3)3·9H2O to Ti(SO4)2 is 2-5. 1. The molar concentration of the mixed salt solution is 0.5-1 mol / L; the molar ratio of NaOH to Na2CO3 is 1-3:1, and the molar concentration of the alkaline solution is 1.5-2 mol / L; In step (3), the crystallization conditions include: stirring and crystallizing at 70-130 °C for 10-15 h.

[0022] According to the present invention, in step 2), after extrusion, the material is dried at 130-160 °C for 2-6 h to obtain a molded body. The calcination temperature of the molded body is 500-600 °C and the calcination time is 3-8 h.

[0023] In step 3) of this invention, the preparation of the molybdenum-containing ionic liquid includes: dispersing tributylmethylammonium chloride in ethanol, slowly adding it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions, eluting with ethanol, collecting the eluent with pH > 8, and obtaining a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution; mixing the tributylmethylammonium hydroxide ethanol solution with H2MoO4, wherein the molar ratio of tributylmethylammonium hydroxide to H2MoO4 is 2:1, heating the mixed solution to 40-60 °C and stirring for 20-30 hours, then removing the solvent by rotary evaporation, and finally placing it in a vacuum oven at 60-100 °C for vacuum drying for 12-30 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is the molybdenum-containing ionic liquid.

[0024] The preparation of cobalt-containing ionic liquids includes: dissolving glycine in water, adding an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) to neutralize and generate quaternary ammonium glycine salt; and adding an equimolar amount of CoC to the above solution. ·6H2O, stir the reaction at 60-70 °C for 6-12 h; remove water and hydrolysis byproducts by rotary evaporation to obtain a viscous liquid or solid, and further wash and purify with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid.

[0025] The preparation of nickel-containing ionic liquids includes: dispersing tributylmethylammonium chloride in ethanol, slowly adding it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions, eluting with ethanol, collecting the eluent with pH > 10 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution; dissolving glycine in a small amount of water, adding an equal amount of NaOH solution while stirring to prepare a sodium glycine solution; and adding NiC... • 6H₂O dissolves in water to obtain a nickel salt solution; under vigorous stirring, a sodium glycine (Na[Gly]) solution is slowly added to the nickel salt solution, wherein glycine reacts with NiC The molar ratio of ·6H2O is 3:1; under stirring, the above solution is slowly added to the tributylmethylammonium hydroxide ethanol solution, and the reaction is continuously stirred at 50-70 °C for 4-6 hours; then the solvent is removed by rotary evaporation, and finally placed in a vacuum oven at 70-90 °C for vacuum drying for 20-30 hours to obtain tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]), which is a nickel-containing liquid.

[0026] According to the present invention, in step 4), the molybdenum-containing ionic liquid, the cobalt-containing ionic liquid, and the nickel-containing ionic liquid can be impregnated with the carrier in any order, either simultaneously, individually, or in a combination of two.

[0027] In step 4) of this invention, the mass ratio of molybdenum-containing ionic liquid to support is 1:1.5-3, the mass ratio of cobalt-containing ionic liquid to support is 1:10-60, and the mass ratio of nickel-containing ionic liquid to support is 1:50-150; stirring and impregnation are carried out for 20-30 h, vacuum drying is carried out at 60-100 ℃ for 12-30 h, calcination temperature is 350-550 ℃, and calcination time is 1-8 h.

[0028] In this invention, the sulfidation of the catalyst precursor can be carried out using conventional methods in the prior art. Preferably, the sulfidation conditions include: heating to 200 °C under nitrogen conditions at a heating rate of 1 °C / min, switching to hydrogen gas containing 2% hydrogen sulfide by volume, continuing to heat to 240 °C, holding at this temperature for 3 h, and ending the sulfidation process after the hydrogen sulfide at the reactor inlet and outlet has reached equilibrium.

[0029] The substances and parameters not limited in this invention can be selected according to existing technology, which is a conventional technical means in this field.

[0030] The present invention will be further described below with reference to embodiments. However, the invention is not limited to these embodiments.

[0031] The experimental methods and data for each embodiment and comparative example were obtained through the following methods: Particle size of titanium-aluminum composite hydroxide: determined by laser diffraction.

[0032] Specific surface area of ​​the carrier: determined by BET gas adsorption method.

[0033] Sulfidation of the catalyst precursor and evaluation of catalyst activity: The activity evaluation experiment was conducted on a 10 mL microreactor, which was made of stainless steel tubing with an inner diameter of 20 mm and placed in a constant temperature chamber. First, the catalyst precursor was sulfidated under the following conditions: heating to 200 °C under nitrogen atmosphere at a rate of 1 °C / min, switching to hydrogen gas containing 2% hydrogen sulfide by volume, continuing to heat to 240 °C, and holding at this temperature for 3 h. Sulfidation was then terminated after the hydrogen sulfide at the reactor inlet and outlet reached equilibrium. Next, a reaction gas was introduced for evaluation, containing hydrogen sulfide with a volume concentration of 1... 1.5%, sulfur dioxide volume concentration is 0.5%. 0.8%, hydrogen volume concentration of 3 4%, carbon disulfide volume concentration is 0.1%. 0.2%, water vapor volume concentration of 25 A mixture of 30% nitrogen and the remainder was used for catalytic reaction. The total gas flow rate was controlled at 1500 mL / min and 1750 mL / min (under standard conditions), and the reaction temperature was controlled at 220 ℃ and 240 ℃. The concentrations of hydrogen sulfide, sulfur dioxide, and carbon disulfide in the inlet and outlet gases of the apparatus were analyzed. Based on the analysis results, the hydrogenation conversion rate of sulfur dioxide and the hydrolysis rate of organic sulfur (carbon disulfide) of the catalyst were calculated. The catalyst activity evaluation device used can be a conventional Claus tail gas hydrogenation reactor. The contents of H2S, SO2, COS, and CS2 in the reactor inlet and outlet gases were analyzed online using a Shimadzu GC-2014 gas chromatograph, and sulfides were analyzed using a GDX-301 support.

[0034] Using the reaction SO2 + 3H2 → H2S + 2H2O as the index reaction, the tail gas hydrogenation activity of the catalyst is evaluated, and the Claus conversion rate of the catalyst is calculated according to the following formula:

[0035] Where M0 and M1 represent the volume concentrations of SO2 at the inlet and outlet, respectively. Samples are taken and analyzed every hour, and the results are averaged over 10 hours.

[0036] Using the reaction CS2 + 2H2O → 2H2S + CO2 as an indicator, the activity of the catalyst in the hydrolysis of organic sulfur was examined. The CS2 hydrolysis rate of the catalyst was calculated according to the following formula: .

[0037] Example 1

[0038] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 120 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize to 180 mesh to obtain titanium-aluminum composite hydroxide powder.

[0039] Step B: Preparation of the carrier: 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder and 8 g of nitric acid were mixed evenly, extruded into strips using a twin-screw extruder, dried at 150 ℃ for 4 hours, and then calcined at 550 ℃ for 5 hours to prepare the carrier.

[0040] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours. Then, remove the solvent by rotary evaporation and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal volume of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, wherein the molar ratio of glycine to NiCl2·6H2O was 3:1. 1. Under stirring, the above solution was slowly added to the [N4441]OH ethanol solution. The reaction was continuously stirred at 60 °C for 5 hours. Then, the solvent was removed by rotary evaporation. Finally, the solution was placed in a vacuum oven and dried under vacuum at 80 °C for 24 hours to obtain tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]), which is a nickel ion liquid.

[0041] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid, 2.6 g of cobalt-containing ionic liquid, and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support, and make the mass ratio of ionic liquid to support 0.5; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and calcine at 500 °C for 5 h to obtain the catalyst precursor.

[0042] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0043] Example 2

[0044] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0045] Step B: Preparation of the carrier: 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder and 8 g of nitric acid were mixed evenly, extruded into strips using a twin-screw extruder, dried at 150 ℃ for 4 hours, and then calcined at 550 ℃ for 5 hours to prepare the carrier.

[0046] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours. Then, remove the solvent by rotary evaporation and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, wherein the molar ratio of glycine to NiCl2·6H2O was 3:1. Under stirring, the above solution was slowly added to the [N4441]OH ethanol solution, and the reaction was continuously stirred at 60 °C for 5 hours. Then, the solvent was removed by rotary evaporation, and finally, the solution was placed in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]), which is a nickel ion liquid.

[0047] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid, 2.6 g of cobalt-containing ionic liquid, and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support, and make the mass ratio of ionic liquid to support 0.5; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and calcine at 500 °C for 5 h to obtain the catalyst precursor.

[0048] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0049] Example 3

[0050] Step A: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform suspension of titanium-aluminum composite hydroxide crystal nuclei. Transfer the crystal nuclei suspension to a reaction vessel and crystallize at 60 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after the reaction to obtain titanium-aluminum composite hydroxide powder.

[0051] Step B: Preparation of the carrier: 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder and 8 g of nitric acid were mixed evenly, extruded into strips using a twin-screw extruder, dried at 150 ℃ for 4 hours, and then calcined at 550 ℃ for 5 hours to prepare the carrier.

[0052] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours, then remove the solvent by rotary evaporation, and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, wherein the molar ratio of glycine to NiCl2·6H2O was 3:1. Under stirring, the above solution was slowly added to the [N4441]OH ethanol solution, and the reaction was continuously stirred at 60 °C for 5 hours. Then, the solvent was removed by rotary evaporation, and finally, the solution was placed in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]), which is a nickel ion liquid.

[0053] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid, 2.6 g of cobalt-containing ionic liquid, and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support, and make the mass ratio of ionic liquid to support 0.5; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and calcine at 500 °C for 5 h to obtain the catalyst precursor.

[0054] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0055] Example 4

[0056] Step A: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform suspension of titanium-aluminum composite hydroxide crystal nuclei. Transfer the crystal nuclei suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after the reaction to obtain titanium-aluminum composite hydroxide powder.

[0057] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 500 ℃ for 5 hours to prepare the carrier.

[0058] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours. Then, remove the solvent by rotary evaporation and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. The column was eluted with ethanol, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, wherein the molar ratio of glycine to NiCl2·6H2O was 3:1. The above solution was slowly added to [N4441]OH ethanol solution under stirring, and the reaction was carried out under stirring at 60 °C for 5 hours. Then the solvent was removed by rotary evaporation, and finally the solution was placed in a vacuum oven and dried under vacuum at 80 °C for 24 hours to obtain tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]), which is a nickel ion liquid.

[0059] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid, 2.6 g of cobalt-containing ionic liquid, and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support to make the mass ratio of ionic liquid to support 0.5; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; vacuum dry the product at 80 °C for 24 h, and then heat it at 500 °C. The catalyst precursor was obtained by calcination at ℃ for 5 h.

[0060] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0061] Example 5

[0062] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0063] Step B: Preparation of the carrier: 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder and 8 g of nitric acid were mixed evenly, extruded into strips using a twin-screw extruder, dried at 150 ℃ for 4 hours, and then calcined at 600 ℃ for 5 hours to prepare the carrier.

[0064] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours. Then, remove the solvent by rotary evaporation and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong-base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal volume of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, with a molar ratio of glycine to NiCl2·6H2O of 3:1. The above solution was then slowly added to the [N4441]OH ethanol solution under stirring, and the reaction was continued at 60 °C for 5 hours. The solvent was then removed by rotary evaporation, and finally the product was placed in a vacuum oven and dried at 80 °C for 24 hours to obtain tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]), which is a nickel-containing liquid.

[0065] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid, 2.6 g of cobalt-containing ionic liquid, and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support to make the mass ratio of ionic liquid to support 0.5; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; vacuum dry the product at 80 °C for 24 h, and then heat it at 500 °C. The catalyst precursor was obtained by calcination at ℃ for 5 h.

[0066] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0067] Example 6

[0068] Step A: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform suspension of titanium-aluminum composite hydroxide crystal nuclei. Transfer the crystal nuclei suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after the reaction to obtain titanium-aluminum composite hydroxide powder.

[0069] Step B: Preparation of the carrier: 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder and 8 g of nitric acid were mixed evenly, extruded into strips using a twin-screw extruder, dried at 150 ℃ for 4 hours, and then calcined at 450 ℃ for 5 hours to prepare the carrier.

[0070] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours, then remove the solvent by rotary evaporation, and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, wherein the molar ratio of glycine to NiCl2·6H2O was 3:1. The above solution was then slowly added to the [N4441]OH ethanol solution under stirring, and the reaction was carried out at 60 °C for 5 hours with continuous stirring. The solvent was then removed by rotary evaporation, and finally the product was placed in a vacuum oven and dried at 80 °C for 24 hours to obtain tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]), which is a nickel-containing liquid.

[0071] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid, 2.6 g of cobalt-containing ionic liquid, and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support to make the mass ratio of ionic liquid to support 0.5; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; vacuum dry the product at 80 °C for 24 h, and then heat it at 500 °C. The catalyst precursor was obtained by calcination at ℃ for 5 h.

[0072] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0073] Example 7

[0074] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0075] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 550 ℃ for 5 hours to form a carrier.

[0076] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours, then remove the solvent by rotary evaporation, and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, with a molar ratio of glycine to NiCl2·6H2O of 3:1. This solution was then slowly added to the [N4441]OH ethanol solution under stirring. The reaction was carried out at 60 °C with continuous stirring for 5 hours. The solvent was then removed by rotary evaporation, and finally the solution was placed in a vacuum oven at 80 °C. Tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]) was prepared by vacuum drying at ℃ for 24 hours, thus obtaining a nickel-containing liquid.

[0077] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid in 100 mL of ethanol, add the support to make the mass ratio of ionic liquid to support 0.07; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then at 400 °C... Calcination at ℃ for 2 hours.

[0078] Step E: Dissolve 2.6 g of cobalt-containing ionic liquid in 100 mL of ethanol, add the supported product obtained in step D, stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then heat at 400 °C. Calcination at ℃ for 2 hours.

[0079] Step F: Dissolve 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the supported product obtained in step E, stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then heat at 500 °C. The catalyst precursor was obtained by calcination at ℃ for 5 h.

[0080] Step G: The catalyst precursor is sulfided to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0081] Example 8

[0082] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0083] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 550 ℃ for 5 hours to form a carrier.

[0084] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours. Then, remove the solvent by rotary evaporation and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, with a molar ratio of glycine to NiCl2·6H2O of 3:1. This solution was then slowly added to the [N4441]OH ethanol solution under stirring. The reaction was carried out at 60 °C with continuous stirring for 5 hours. The solvent was then removed by rotary evaporation, and finally the solution was placed in a vacuum oven at 80 °C. Tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]) was prepared by vacuum drying at ℃ for 24 hours, thus obtaining a nickel-containing liquid.

[0085] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid and 2.6 g of cobalt-containing ionic liquid in 100 mL of ethanol, add the support to make the mass ratio of ionic liquid to support 0.09; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then at 400 °C... Calcination at ℃ for 2 hours.

[0086] Step E: Dissolve 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the supported product obtained in step D, stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then heat at 500 °C. The catalyst precursor was obtained by calcination at ℃ for 5 h.

[0087] Step F: The catalyst precursor is sulfided to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0088] Example 9

[0089] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0090] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 550 ℃ for 5 hours to form a carrier.

[0091] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours. Then, remove the solvent by rotary evaporation and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, with a molar ratio of glycine to NiCl2·6H2O of 3:1. This solution was then slowly added to the [N4441]OH ethanol solution under stirring. The reaction was carried out at 60 °C with continuous stirring for 5 hours. The solvent was then removed by rotary evaporation, and finally the solution was placed in a vacuum oven at 80 °C. Tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]) was prepared by vacuum drying at ℃ for 24 hours, thus obtaining a nickel-containing liquid.

[0092] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support to make the mass ratio of ionic liquid to support 0.08; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then at 400 °C... Calcination at ℃ for 2 hours.

[0093] Step E: Dissolve 2.6 g of cobalt-containing ionic liquid in 100 mL of ethanol, add the loaded product obtained in step D, stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then heat it at 500 °C. The catalyst precursor was obtained by calcination at ℃ for 5 h.

[0094] Step F: The catalyst precursor is sulfided to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0095] Example 10

[0096] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0097] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 550 ℃ for 5 hours to form a carrier.

[0098] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours, then remove the solvent by rotary evaporation, and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, with a molar ratio of glycine to NiCl2·6H2O of 3:1. This solution was then slowly added to the [N4441]OH ethanol solution under stirring. The reaction was carried out at 60 °C with continuous stirring for 5 hours. The solvent was then removed by rotary evaporation, and finally the solution was placed in a vacuum oven at 80 °C. Tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]) was prepared by vacuum drying at ℃ for 24 hours, thus obtaining a nickel-containing liquid.

[0099] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid in 100 mL of ethanol, add the support to make the mass ratio of ionic liquid to support 0.07; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then at 400 °C... Calcination at ℃ for 2 hours.

[0100] Step E: Dissolve 2.6 g of cobalt-containing ionic liquid and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the loaded product obtained in step D, stir at room temperature for 24 h, and remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then heat it at 500 °C. The catalyst precursor was obtained by calcination at ℃ for 5 h.

[0101] Step F: The catalyst precursor is sulfided to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0102] Example 11

[0103] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0104] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 550 ℃ for 5 hours to form a carrier.

[0105] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours, then remove the solvent by rotary evaporation, and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, with a molar ratio of glycine to NiCl2·6H2O of 3:1. This solution was then slowly added to the [N4441]OH ethanol solution under stirring. The reaction was carried out at 60 °C with continuous stirring for 5 hours. The solvent was then removed by rotary evaporation, and finally the solution was placed in a vacuum oven at 80 °C. Tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]) was prepared by vacuum drying at ℃ for 24 hours, thus obtaining a nickel-containing liquid.

[0106] Step D: Dissolve 26.4 g of molybdenum-containing ionic liquid, 4.3 g of cobalt-containing ionic liquid, and 2.68 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support to make the mass ratio of ionic liquid to support 0.4; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and then heat it at 500 °C. The catalyst precursor was obtained by calcination at ℃ for 5 h.

[0107] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 8 wt% molybdenum sulfide, 2.6 wt% cobalt sulfide, 2 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0108] Example 12

[0109] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0110] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 550 ℃ for 5 hours to form a carrier.

[0111] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours, then remove the solvent by rotary evaporation, and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, with a molar ratio of glycine to NiCl2·6H2O of 3:1. This solution was then slowly added to the [N4441]OH ethanol solution under stirring. The reaction was carried out at 60 °C with continuous stirring for 5 hours. The solvent was then removed by rotary evaporation, and finally the solution was placed in a vacuum oven at 80 °C. Tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]) was prepared by vacuum drying at ℃ for 24 hours, thus obtaining a nickel-containing liquid.

[0112] Step D: Dissolve 49.5 g of molybdenum-containing ionic liquid, 1.63 g of cobalt-containing ionic liquid, and 2.68 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support to make the mass ratio of ionic liquid to support 0.7; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; vacuum dry the product at 80 °C for 24 h, and then heat it at 500 °C. The catalyst precursor was obtained by calcination at ℃ for 5 h.

[0113] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 15 wt% molybdenum sulfide, 1 wt% cobalt sulfide, 2 wt% nickel sulfide, 5 wt% magnesium oxide, and 77 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0114] Example 13

[0115] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 525 g of Al(NO3)3·9H2O and 86.4 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0116] Step B: Preparation of the carrier: 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 5 g of guar gum powder and 8 g of nitric acid were mixed evenly, extruded into strips using a twin-screw extruder, dried at 150 ℃ for 4 hours, and then calcined at 550 ℃ for 5 hours to prepare the carrier.

[0117] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours. Then, remove the solvent by rotary evaporation and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, wherein the molar ratio of glycine to NiCl2·6H2O was 3:1. Under stirring, the above solution was slowly added to the [N4441]OH ethanol solution, and the reaction was continuously stirred at 60 °C for 5 hours. Then, the solvent was removed by rotary evaporation, and finally, the solution was placed in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]), which is a nickel ion liquid.

[0118] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid, 2.6 g of cobalt-containing ionic liquid, and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support, and make the mass ratio of ionic liquid to support 0.5; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and calcine at 500 °C for 5 h to obtain the catalyst precursor.

[0119] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 30 wt% and aluminum oxide is 70 wt%).

[0120] Comparative Example 1

[0121] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Add the mixed salt solution and alkaline solution dropwise to the reaction vessel at a constant pH of 9, and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize to 180 mesh to obtain titanium-aluminum composite hydroxide powder.

[0122] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 550 ℃ for 5 hours to form a carrier.

[0123] Step C: Add 7 mL of citric acid to 100 mL of deionized water, heat to above 70 °C, and while stirring continuously, add 5.2 g CoCl2·6H2O, 12.3 g H2MoO4, and 3.3 g NiC. •6H2O is added to form a stable solution, thus obtaining the co-impregnation solution of the active component. 100 g of the support is impregnated with the above co-impregnation solution for 1 hour, dried at 130 °C for 4 hours, and calcined at 500 °C for 5 hours to obtain the catalyst precursor.

[0124] Step D: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0125] Comparative Example 2

[0126] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Simultaneously and rapidly pour the mixed salt solution and alkali solution into a colloid mill and continue stirring for 3 minutes to form a uniform titanium-aluminum composite hydroxide crystal nucleus suspension. Transfer the crystal nucleus suspension to a reaction vessel and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize the solid product after reaction to obtain titanium-aluminum composite hydroxide powder.

[0127] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 550 ℃ for 5 hours to form a carrier.

[0128] Step C: Add 7 mL of citric acid to 100 mL of deionized water, heat to above 70 °C, and while stirring continuously, add 5.2 g CoCl2·6H2O, 12.3 g H2MoO4, and 3.3 g NiC. •6H2O is added to form a stable solution, thus obtaining the co-impregnation solution of the active component. 100 g of the support is impregnated with the above co-impregnation solution for 1 hour, dried at 130 °C for 4 hours, and calcined at 500 °C for 5 hours to obtain the catalyst precursor.

[0129] Step D: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0130] Comparative Example 3

[0131] Step A: Preparation of titanium-aluminum composite hydroxide: Dissolve 450 g of Al(NO3)3·9H2O and 115.2 g of Ti(SO4)2 in 2000 mL of deionized water and stir until completely dissolved. Dissolve 96.0 g of NaOH and 122.4 g of Na2CO3 in 2000 mL of deionized water. Add the mixed salt solution and alkali solution dropwise to the reaction vessel at a constant pH of 9, and crystallize at 90 °C with stirring for 12 hours. After crystallization, allow to cool naturally to room temperature. Filter, wash, dry, and pulverize to 180 mesh to obtain the titanium-aluminum composite hydroxide.

[0132] Step B: Mix 200 g of titanium-aluminum composite hydroxide, 6 g of magnesium oxide, 10 g of guar gum powder, and 8 g of nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder, dry it at 150 ℃ for 4 hours, and then calcine it at 550 ℃ for 5 hours to form a carrier.

[0133] Step C: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours. Then, remove the solvent by rotary evaporation and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, wherein the molar ratio of glycine to NiCl2·6H2O was 3:1. The above solution was then slowly added to the [N4441]OH ethanol solution under stirring, and the reaction was carried out at 60 °C for 5 hours with continuous stirring. The solvent was then removed by rotary evaporation, and finally the product was placed in a vacuum oven and dried at 80 °C for 24 hours to obtain tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]), which is a nickel-containing liquid.

[0134] Step D: Dissolve 33.0 g of molybdenum-containing ionic liquid, 2.6 g of cobalt-containing ionic liquid, and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support, and make the mass ratio of ionic liquid to support 0.5; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and calcine at 500 °C for 5 h to obtain the catalyst precursor.

[0135] Step E: Sulfide the catalyst precursor to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: 10 wt% molybdenum sulfide, 1.6 wt% cobalt sulfide, 1 wt% nickel sulfide, 5 wt% magnesium oxide, and 82.4 wt% aluminum-titanium composite metal oxide (of which, titanium dioxide is 40 wt% and aluminum oxide is 60 wt%).

[0136] Comparative Example 4

[0137] Step A: Mix 91.76g aluminum hydroxide, 58g titanium hydroxide, 6g magnesium oxide, 10g guar gum powder, and 8g nitric acid evenly, then extrude the mixture into strips using a twin-screw extruder. Dry the strips at 150°C for 4 hours, and then calcine them at 550°C for 5 hours to form a carrier.

[0138] Step B: Disperse tributylmethylammonium chloride in ethanol and slowly add it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Elute with ethanol and collect the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Mix the tributylmethylammonium hydroxide ([N4441]OH) ethanol solution with molybdic acid, wherein the molar ratio of [N4441]OH to H2MoO4 is 2:1. Heat the mixed solution to 50 °C and stir for 24 hours, then remove the solvent by rotary evaporation, and finally place it in a vacuum oven at 80 °C for vacuum drying for 24 hours to obtain tributylmethylammonium molybdate ([N4441]2MoO4), which is a molybdenum ion-containing liquid. Glycine was dissolved in water, and an equimolar amount of tributylmethylammonium hydroxide ([N4441]OH) was added to neutralize it and generate quaternary ammonium glycinate. An equimolar amount of CoCl2·6H2O was added to the above solution, and the mixture was stirred at 65 °C for 10 h. Water and hydrolysis byproducts were removed by rotary evaporation to obtain a viscous liquid or solid. The solid was further purified by washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate ([N4441][Co(Gly)3]), which is a cobalt ion-containing liquid. Tributylmethylammonium chloride was dispersed in ethanol and slowly added to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions. Eluent was used for elution, and the eluent with pH > 10 was collected to obtain a tributylmethylammonium hydroxide ([N4441]OH) ethanol solution. Glycine was dissolved in a small amount of water, and an equal amount of NaOH solution was added under stirring to prepare a sodium glycinate (Na[Gly]) solution. NiCl2·6H2O was dissolved in water to prepare a nickel salt solution. The sodium glycinate solution was slowly added to the nickel salt solution under vigorous stirring, with a molar ratio of glycine to NiCl2·6H2O of 3:1. This solution was then slowly added to the [N4441]OH ethanol solution under stirring. The reaction was carried out at 60 °C with continuous stirring for 5 hours. The solvent was then removed by rotary evaporation, and finally the solution was placed in a vacuum oven at 80 °C. Tributylmethylammonium-tris(glycine)nickelate ([N4441][Ni(Gly)3]) was prepared by vacuum drying at ℃ for 24 hours, thus obtaining a nickel-containing liquid.

[0139] Step C: Dissolve 33.0 g of molybdenum-containing ionic liquid, 2.6 g of cobalt-containing ionic liquid, and 1.64 g of nickel-containing ionic liquid in 100 mL of ethanol, add the support, and make the mass ratio of ionic liquid to support 0.5; stir at room temperature for 24 h, remove most of the ethanol by rotary evaporation; dry the product under vacuum at 80 °C for 24 h, and calcine at 500 °C for 5 h to obtain the catalyst precursor.

[0140] Step D: The catalyst precursor is sulfided to obtain a sulfur recovery tail gas hydrogenation catalyst. Catalyst composition: molybdenum sulfide 10 wt%, cobalt sulfide 1.6 wt%, nickel sulfide 1 wt%, magnesium oxide 5 wt%, titanium dioxide 33 wt%, and aluminum oxide 49.4 wt%.

[0141] The parameters of the titanium-aluminum composite hydroxides and supports prepared in each embodiment and comparative example are shown in Table 1.

[0142] Table 1

[0143] The catalytic performance of the catalysts in each embodiment and comparative example under the conditions of reaction temperature of 220℃ and total gas flow rate of 1500 mL / min is shown in Table 2.

[0144] Table 2

[0145] The catalytic performance of catalysts in some examples and comparative examples at different reaction temperatures (220℃, 240℃) and a total gas flow rate of 1500 mL / min is shown in Table 3.

[0146] Table 3

[0147] The catalytic performance of catalysts in some examples and comparative examples at a reaction temperature of 220°C and different space velocities (1500 mL / min and 1750 mL / min) is shown in Table 4.

[0148] Table 4

[0149] As shown in Tables 1-4, the titanium-aluminum composite hydroxide prepared by this invention has a small and uniform particle size, a large specific surface area, and high reaction activity. The activity of SO2 hydrogenation reaches 99.9%, and the activity of CS2 hydrolysis reaches 99.0%. Moreover, the activity stability is good under different reaction temperatures and space velocities.

[0150] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A catalyst for hydrogenation of sulfur recovery tail gas, characterized in that, The catalyst consists of a support and active components loaded on the support; the active components are molybdenum sulfide, cobalt sulfide and nickel sulfide; the support is prepared by mixing and molding titanium-aluminum composite hydroxide with magnesium oxide, pore expander and binder, and then calcining it, and the titanium-aluminum composite hydroxide is calcined to form titanium-aluminum composite metal oxide. Based on the total weight of the catalyst, the content of molybdenum sulfide is 5-20 wt%, the content of cobalt sulfide is 1-5 wt%, the content of nickel sulfide is 0.5-5 wt%, the content of titanium-aluminum composite metal oxide is 75-90 wt%, and the content of magnesium oxide is 1-10 wt%. The preparation of the titanium-aluminum composite hydroxide includes the following steps: (1) Dissolve Al(NO3)3·9H2O and Ti(SO4)2 to prepare a mixed salt solution, and dissolve NaOH and Na2CO3 to prepare an alkaline solution; (2) Add the mixed salt solution and the alkaline solution to the colloid mill at the same time and stir to obtain a titanium-aluminum composite hydroxide crystal nucleus suspension; (3) Add the crystal nucleus suspension to the reaction vessel for crystallization; (4) The product obtained in step (3) is filtered, washed, dried and crushed to obtain the titanium-aluminum composite hydroxide.

2. The sulfur recovery tail gas hydrogenation catalyst according to claim 1, wherein, The primary particle size of the titanium-aluminum composite hydroxide is 550-600 nm, and the secondary particle size is 10-25 μm. Based on the weight of the titanium-aluminum composite metal oxide, the titanium dioxide content in the titanium-aluminum composite metal oxide is 25-40 wt%, and the aluminum content is 60-75 wt%. The specific surface area of ​​the carrier is 315-350 m². 2 / g.

3. The sulfur recovery tail gas hydrogenation catalyst according to claim 1, wherein, Based on the total weight of the catalyst, the content of molybdenum sulfide is 8-15 wt%, the content of cobalt sulfide is 1-3 wt%, the content of nickel sulfide is 0.5-2 wt%, the content of titanium-aluminum composite metal oxide is 80-90 wt%, and the content of magnesium oxide is 3-8 wt%.

4. The sulfur recovery tail gas hydrogenation catalyst according to claim 1, wherein, The pore-expanding agent is selected from at least one of polyethylene glycol, polyethylene oxide, and guar gum powder, and the amount of the pore-expanding agent is 2-6 wt% based on the total weight of the carrier. The binder is selected from at least one of nitric acid, acetic acid, oxalic acid and citric acid, and the amount of the binder is 2-10 wt% based on the total weight of the carrier.

5. The method for preparing the sulfur recovery tail gas hydrogenation catalyst according to any one of claims 1-4, characterized in that, The preparation method includes the following steps: 1) Titanium-aluminum composite hydroxide was prepared by a rapid co-precipitation-secondary crystallization method; 2) The titanium-aluminum composite hydroxide is mixed with magnesium oxide, a pore expander, and a binder, and then extruded and molded. The molded body is then calcined to obtain a carrier. 3) Prepare molybdenum-containing ionic liquids, cobalt-containing ionic liquids, and nickel-containing ionic liquids respectively; 4) Dissolve the ionic liquid obtained in step 3) in ethanol, then impregnate the support obtained in step 2), rotary evaporate, dry, and then calcine to obtain the catalyst precursor; 5) The catalyst precursor is sulfided to obtain the catalyst.

6. The method for preparing the sulfur recovery tail gas hydrogenation catalyst according to claim 5, wherein, In step (1), the molar ratio of Al(NO3)3·9H2O and Ti(SO4)2 is 2-5:1, and the molar concentration of the mixed salt solution is 0.5-1 mol / L; the molar ratio of NaOH and Na2CO3 is 1-3:1, and the molar concentration of the alkaline solution is 1.5-2 mol / L. In step (3), the crystallization conditions include: stirring and crystallizing at 70-130 °C for 10-15 h.

7. The method for preparing the sulfur recovery tail gas hydrogenation catalyst according to claim 5, wherein, In step 2), after extrusion, the material is dried at 130-160 ℃ for 2-6 h to obtain a molded body. The calcination temperature of the molded body is 500-600 ℃ and the calcination time is 3-8 h.

8. The method for preparing the sulfur recovery tail gas hydrogenation catalyst according to claim 5, wherein, In step 3), the preparation of the molybdenum-containing ionic liquid includes: dispersing tributylmethylammonium chloride in ethanol, slowly adding it to an exchange column packed with a strong base anion exchange resin activated by hydroxide ions, eluting with ethanol, collecting the eluent with pH > 8 to obtain a tributylmethylammonium hydroxide ethanol solution; mixing the tributylmethylammonium hydroxide ethanol solution with H2MoO4, wherein the molar ratio of tributylmethylammonium hydroxide to H2MoO4 is 2:1, heating the mixed solution to 40-60 ℃ and stirring for 20-30 hours, then removing the solvent by rotary evaporation, and finally placing it in a vacuum oven at 60-100 ℃ for vacuum drying for 12-30 hours to obtain tributylmethylammonium molybdate, which is the molybdenum-containing ionic liquid; The preparation of cobalt-containing ionic liquids includes: dissolving glycine in water, adding an equimolar amount of tributylmethylammonium hydroxide, neutralizing to form a quaternary ammonium glycine salt solution; adding an equimolar amount of CoCl2·6H2O to the above solution, stirring the reaction at 60-70 °C for 6-12 h; purifying by rotary evaporation and washing with ethanol to obtain tributylmethylammonium-tris(glycine)cobaltate, thus obtaining the cobalt-containing ionic liquid; The preparation of nickel-containing ionic liquids includes: dispersing tributylmethylammonium chloride in ethanol, slowly adding it to an exchange column packed with a strong-base anion exchange resin activated by hydroxide ions, eluting with ethanol, collecting the eluent with pH > 10 to obtain a tributylmethylammonium hydroxide ethanol solution; dissolving glycine in a small amount of water, adding an equal amount of NaOH solution under stirring to prepare a sodium glycinate solution; dissolving NiCl2·6H2O in water to obtain a nickel salt solution; slowly adding the sodium glycinate solution to the nickel salt solution under vigorous stirring to form a mixed solution, wherein the molar ratio of glycine to NiCl2·6H2O is 3:1; slowly adding the above mixed solution to the tributylmethylammonium hydroxide ethanol solution under stirring, and continuously stirring the reaction at 50-70 °C for 4-6 hours; then removing the solvent by rotary evaporation, and finally placing it in a vacuum oven at 70-90 °C. The nickel-containing liquid was obtained by vacuum drying at ℃ for 20-30 hours.

9. The method for preparing the sulfur recovery tail gas hydrogenation catalyst according to claim 8, wherein, In step 4), the mass ratio of molybdenum-containing ionic liquid to support is 1:1.5-3, the mass ratio of cobalt-containing ionic liquid to support is 1:10-60, and the mass ratio of nickel-containing ionic liquid to support is 1:50-150; the mixture is stirred and impregnated for 20-30 h, vacuum dried at 60-100 ℃ for 12-30 h, and calcined at 350-550 ℃ for 1-8 h.

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