Efficient sulfur recovery organic sulfur hydrolysis catalyst, preparation method and organic sulfur recovery process

Abstract

The invention provides an efficient sulfur recovery organic sulfur hydrolysis catalyst, a preparation method and an organic sulfur recovery process. The preparation method comprises the following steps: mixing metatitanic acid with a high-temperature-resistant raw material and an extrusion aid, adding a modifier, a dispersant and active metal salt, and kneading to obtain a semi-finished product; and mixing the semi-finished product with an aluminum-containing compound, kneading, forming, drying and roasting to obtain the catalyst, wherein the modifier is one or a combination of more than two of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid. The invention also provides the catalyst prepared by the method and an organic sulfur recovery process. The catalyst provided by the invention has the characteristics of high titanium content, relatively high strength, large specific surface area, stable organic sulfur hydrolysis rate higher than 95%, and long service life.

Description

Technical Field

[0001] The invention relates to an efficient sulfur recovery organic sulfur hydrolysis catalyst, a preparation method and an organic sulfur recovery process, and belongs to the technical field of sulfur recovery. Background Art

[0002] USP 4,388,288 directly uses powdered TiO2, water and molding additives to mix and mold. The technical solution of this patent does not use sol. There are two examples that use tableting. The added reagents are carbon black and polyethylene glycol. The calcination temperatures are 600℃ and 350℃ respectively. The specific surface area of ​​the former is less than 60m 2 / g, the decomposition temperature of the latter cannot reach the temperature at which metatitanic acid decomposes into titanium oxide, and cannot be used as a sulfur recovery catalyst. The implementation example of the patent is to add only cellulose, which may reduce the amount of water added, but increase the wear of the machine.

[0003] USP 4,113,660 mainly uses the sol method in the preparation process. The sol is prepared from hydrochloric acid and metatitanic acid in advance and diluted in the subsequent preparation process. Although the catalyst prepared by this method has high strength, its specific surface area is relatively small. In the examples of the patent, only two examples of the catalyst prepared have a specific surface area of ​​more than 100m 2 / g, aluminum hydroxide is added in the preparation process, the content is high, and the ratio with metatitanic acid exceeds 1:1, or silica sol and clay are added, and the ratio with metatitanic acid is about 0.7:1. This agent is mainly used as a nitric oxide conversion catalyst with a specific surface area of ​​less than 115m 2 / g.

[0004] CN101069582A discloses a Claus sulfur recovery catalyst and its preparation method. The method mainly adds aluminosilicate and ammonium sulfate. The catalyst produced by this method has a low titanium oxide content of 65%-85%, and only the COS conversion rate is high under certain conditions.

[0005] CN1126595A discloses a TiO2-based bifunctional sulfur recovery catalyst and its preparation method. The catalyst is prepared by mixing metatitanic acid, aluminum oxide or aluminum hydroxide and a prepared alkaline earth metal oxide precursor solution, extruding through an extruder, and drying and roasting to obtain a finished catalyst. The titanium oxide content is 10-90%, the activated aluminum oxide is 9.5-89.5%, and the alkaline earth metal oxide content is 0.5-10%. Compared with traditional aluminum oxide catalysts, it has the advantages of large specific surface area and high strength, but the CS2 hydrolysis activity is low under high space velocity. The direct oxidation performance of hydrogen sulfide is also low.

[0006] CN1029594A discloses a room temperature organic sulfur hydrolysis catalyst and its preparation method. The catalyst is composed of 2%-25% of the carrier weight of potassium carbonate and a spherical alumina carrier, wherein the content of potassium carbonate is preferably 4%-16%. The preparation method of the catalyst is to impregnate the γ-Al2O3 carrier with a potassium carbonate aqueous solution, and after the potassium carbonate content reaches the required level, dry it at room temperature to 120°C. The catalyst has a good hydrolysis effect on COS, CS2, etc., and also has a good absorption effect on hydrogen sulfide. Under the conditions of room temperature -50°C, COS content 1-5 mg / m, and air velocity 2000, the hydrolysis conversion rate is greater than 95%, and it can be widely used as a hydrolysis catalyst in the petrochemical industry.

[0007] CN1134312A discloses an organic sulfur hydrolysis catalyst and its preparation method. The catalyst is composed of 4-20% (by weight) titanium dioxide and γ-alumina. The preparation method is to mix the refined aluminum hydroxide and titanium hydroxide in proportion and then roll them into balls, treat the semi-finished balls with a special washing liquid, and then activate and calcine them. The catalyst has a good hydrolysis effect on carbonyl sulfide, carbon disulfide, mercaptan, thioether, etc. At the same time, it can further convert the hydrogen sulfide produced by hydrolysis into elemental sulfur for recycling. At an air velocity of 1800h -1 , COS content up to 5000 mg / m 3 Under the following conditions, the hydrolysis conversion rate is ≥90%, and it can be widely used in desulfurization devices in various industries to hydrolyze organic sulfur.

[0008] CN1189394A discloses a low-temperature organic sulfur hydrolysis catalyst and its preparation, belonging to the field of catalyst preparation. The catalyst is composed of (NH4)6Mo7O containing 0.5-8% of the carrier weight. 24 ·4H2O and 3-10% of the carrier weight of K2CO3 and a low-density spherical γ-Al2O3 carrier. The preparation method is to (NH4)6Mo7O 24 ·4H2O aqueous solution is impregnated into spherical γ-Al2O3 by equal volume impregnation method, and then impregnated with K2CO3 aqueous solution after drying and calcination for activation. The catalyst has a good hydrolysis catalytic effect on organic sulfur such as COS and CS2, has a long service life and a certain anti-oxidation poisoning ability. At room temperature to 100℃, COS content 1-10mgS / m 3 and airspeed 2000h -1 Under the following conditions, the hydrolysis conversion rate is greater than 98, and it can be used for the hydrolysis and removal of organic sulfur in synthetic ammonia, C1 chemistry, petroleum and natural gas chemical raw materials.

[0009] CN1593751A discloses a rare earth hydroxide catalyst for low-medium and low-temperature carbonyl sulfide hydrolysis and a preparation method thereof. The catalyst is a rare earth hydroxide, and its chemical molecular formula is: Re(OH)3, wherein Re represents La, Pr, Nd, Sm, Eu, Gd. Compared with the existing COS hydrolysis catalyst, the catalyst has the advantages of high low-medium and low-temperature activity, large operating flexibility, good oxidation resistance and sulfur resistance, and simple preparation method. However, the catalyst itself has unsatisfactory sulfur dioxide resistance and poor sulfate resistance, and no reports on Claus conversion rate have been found.

[0010] CN103894175B discloses a medium-low temperature sulfur recovery organic sulfur hydrolysis catalyst and its preparation and application. Based on 100% by weight of the catalyst, the catalyst components are: 50-75% titanium oxide, 20-50% activated aluminum oxide, 0.5-10% soluble titanium sulfate salt, 0.5-10% sulfuric acid, 1-10% zirconium oxide, 2-10% cerium nitrate, and 2-10% zirconium nitrate; the strength is 60-150 N / cm; the specific surface area is 150-300 m 2 / g; bulk density is 0.6-0.8g / ml; 20ml of catalyst is loaded into the reactor, the reaction temperature is 170-270℃, the inlet gas composition is H2S 6.0%, SO23.0%, H2O 30%, COS 0.5%, and the rest is N2, and the gas volume space velocity is 500-2000h -1 The catalyst organic sulfur hydrolysis rate is greater than 85%. The invention mainly relies on the action of medium-content titanium oxide and other metals and compounds to improve the organic sulfur hydrolysis effect under low temperature conditions.

[0011] CN102335617B discloses a method for sulfur recovery and organic sulfur hydrolysis. The method comprises the following steps: loading 20 ml of catalyst into a reactor, the reaction temperature being 190-360°C, the inlet gas composition being H2S2%, O2 1%, H2O 3%, and the remainder being N2, and the gas volume space velocity being 500-6000 h -1 The catalyst is composed of titanium oxide, activated alumina and additives. Based on the weight of the catalyst, the content of titanium oxide is 80-95%, the content of activated alumina is 4-15%, the content of soluble titanium sulfate salt is 0.5-10%, and the content of sulfuric acid is 0.5-10%; the strength is 250-400N / cm; the specific surface area is 150-300m 2 / g; the bulk density is 0.6-0.8g / ml. This method can repeat the patent data below 90% titanium oxide content. If the titanium oxide content is above 90%, especially above 95%, the physical and chemical properties of the catalyst are poor, especially the strength, which is mostly below 100N / cm, which is not conducive to industrial application.

[0012] At present, sulfur recovery and recovery equipment is usually designed with a two-stage Claus reactor, loaded with catalysts, and converting hydrogen sulfide, sulfur dioxide, and organic sulfur. The sulfur recovery organic sulfur hydrolysis catalyst is mainly a high-temperature (above 300°C) catalyst, which is usually loaded in the lower part of the first-stage reactor. Generally, titanium oxide carriers are used, or modified with other active metals, but titanium oxide catalysts with higher contents are mostly used. Therefore, the preparation of high-content titanium oxide catalysts can improve the catalyst efficiency. Compared with the original catalyst, the organic sulfur hydrolysis efficiency can be increased by 5-15%. The titanium oxide content of existing titanium-based catalysts is generally low, below 85%, but titanium-based catalysts with high titanium oxide content (≥85%) generally have poor strength, below 100N / cm, and are not suitable for industrial applications. Summary of the invention

[0013] To solve the above technical problems, the object of the present invention is to provide a highly efficient sulfur recovery organic sulfur hydrolysis catalyst and a preparation method thereof, wherein the catalyst has high strength, specific surface area, COS hydrolysis rate and Claus activity.

[0014] To achieve the above object, the present invention provides a method for preparing an efficient sulfur recovery organic sulfur hydrolysis catalyst, which comprises the following steps:

[0015] Mixing metatitanic acid with a high temperature resistant raw material and an extrusion aid, and then adding a modifier, a dispersant, and an active metal salt to knead to obtain a semi-finished product, wherein the mass ratio of the metatitanic acid, the high temperature resistant raw material, the modifier, the dispersant, and the active metal salt is 10-15:0.5-1:1-2:0.5-15:0.5-2;

[0016] The semi-finished product is mixed with an aluminum-containing compound in a mass ratio of 4-8:1-2, and then kneaded, molded, dried, and calcined to obtain the catalyst;

[0017] Wherein, the modifier is one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid.

[0018] In the above preparation method, preferably, the mass ratio of titanic acid, high temperature resistant raw material, modifier, dispersant and active metal salt is 10:0.5:1:0.5:2.

[0019] In the above preparation method, preferably, the particle size of the metatitanic acid is 200-300 meshes. The catalyst strength can be increased by crushing the metatitanic acid to increase the fineness, adding a modifier, a dispersant, and an active metal salt to modify the metatitanic acid, adding an aluminum compound, kneading, and molding.

[0020] In the above preparation method, the titanic acid modification mainly uses acid modification to peptize part of the titanic acid. Preferably, the modifier is nitric acid with a concentration of 2%-15%.

[0021] In the above preparation method, preferably, the high temperature resistant raw material includes one or a combination of two or more of cement, polyurethane, methyl methacrylate resin, and polypropylene, and more preferably cement.

[0022] In the above preparation method, preferably, the dispersant includes one or a combination of two or more of ethanol, ethylenediamine, citric acid, polyethylene glycol, and polypropylene glycol, more preferably ethanol.

[0023] In the above preparation method, because the catalyst precursor is calcined at 500-600°C to form a catalyst, preferably, the active metal salt is a metal salt that does not decompose and can melt under 500-600°C conditions, and more preferably is one or a combination of two or more of TiOSO4, Ti(SO4)2, VOSO4.

[0024] In the above preparation method, preferably, the aluminum-containing compound comprises aluminum xerogel, calcium oxide, and silicon dioxide;

[0025] Wherein, based on the total weight of the aluminum-containing compound as 100%, the contents of the aluminum xerogel, calcium oxide and silicon dioxide are 98%-99%, 0.5%-1% and 0.5%-1% respectively.

[0026] In the above preparation method, the aluminum-containing compound may also contain a trace amount of sodium oxide. Preferably, the sodium content of the aluminum-containing compound is less than 300 ppm. By controlling the sodium content to be less than 300 ppm, the stability of the Claus conversion rate of the catalyst will not be affected. By washing, centrifuging, filtering and separating the aluminum-containing compound multiple times to dissolve the alkali metal sodium therein, the sodium content of the aluminum-containing compound can be reduced from 1% to 300 ppm.

[0027] In the above preparation method, preferably, the particle size of the aluminum-containing compound is 200-300 mesh.

[0028] In the above preparation method, preferably, an extrusion aid is added during the preparation of the semi-finished product, and the amount of the extrusion aid is 5-10% of the total weight of the material. The extrusion aid includes one or a combination of two or more of sesbania powder, hydroxymethyl cellulose, hydroxyethyl cellulose, polyethylene oxide, and polyethylamide.

[0029] In the above preparation method, preferably, the drying includes shade drying and oven drying processes, the shade drying time is 1-2 days, the oven drying temperature is 100-160° C., and the oven drying time is 5-10 hours.

[0030] In the above preparation method, preferably, the calcination temperature is 500-600° C. and the calcination time is 3-5 hours.

[0031] The modification and molding process of the catalyst of the present invention can be carried out by a screw extrusion process, that is, an acid solution as a modifier is added to metatitanic acid, mixed evenly, and kneaded once, and an extrusion aid is added while mixing, so that the extrusion process can be smooth and the surface of the extruded catalyst strip can be guaranteed to be smooth. After kneading, an aluminum-containing compound is added, kneaded, molded, and then dried in the shade for 1-2 days, dried at a temperature of 100-160° C. for 5-10 hours, and roasted at a roasting temperature of 500-600° C. for 3-5 hours to obtain a catalyst.

[0032] The present invention also provides a high-efficiency sulfur recovery organic sulfur hydrolysis catalyst, which is prepared by the above preparation method.

[0033] According to a specific embodiment of the present invention, preferably, the specific surface area of ​​the catalyst is 100-200m 2 / g, the average crushing strength is 150-230N / cm, the bulk density is 0.6-0.8g / ml, and the absolute content of titanium oxide in the catalyst body is 90-97%.

[0034] According to a specific embodiment of the present invention, preferably, based on the total mass of the catalyst, the titanium content of the catalyst is 95-97%.

[0035] According to a specific embodiment of the present invention, the catalyst provided by the present invention can be made into any suitable shape, such as a clover shape.

[0036] The present invention also provides an organic sulfur recovery process, which is carried out by using the above-mentioned high-efficiency sulfur recovery organic sulfur hydrolysis catalyst.

[0037] In the above organic sulfur recovery process, preferably, during the recovery process, the volume space velocity of the organic sulfur-containing gas is 10000h -1 .

[0038] The present invention improves the dispersibility of titanium oxide by adding a certain ratio of organic matter, which helps to increase the solubility of active metals, thereby ultimately increasing the titanium oxide content; at the same time, a certain ratio of acid modifier and high-temperature resistant raw materials are added to modify metatitanic acid, so that the catalyst strength is greatly improved under the condition of high titanium oxide content (≥85%); at the same time, by controlling the sodium content, the acceleration of the sulfation rate caused by alkaline metals such as sodium oxide can be avoided, and the influence of too high or too low sodium content on the Claus conversion rate can be avoided.

[0039] The catalyst provided by the present invention has the characteristics of high titanium content, high strength, large specific surface area, stable organic sulfur hydrolysis rate higher than 95%, and long service life. DETAILED DESCRIPTION

[0040] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0041] Raw materials preparation:

[0042] Currently, the commercially available titanic acid (numbered as titanic acid A) and aluminum-containing compounds (numbered as aluminum-containing compounds A) are relatively coarse, usually around 100 meshes, which is not conducive to catalyst molding and has an impact on the catalyst strength, abrasion and appearance.

[0043] The present invention adopts air crushing and grinding to grind, and a grinding aid is added during the grinding process, preferably an alkyd resin is used. After treatment, the obtained titanic acid and aluminum-containing compound are numbered as titanic acid B and aluminum-containing compound B (respectively B1: sodium content of about 5000ppm, B2: sodium content of about 3000ppm, B3: sodium content of about 300ppm; the sodium content of the aluminum-containing compound is determined by an analytical instrument XPS), and are set aside. The fineness after crushing is 200-300 meshes.

[0044] Comparative Example 1

[0045] This comparative example provides a method for preparing an efficient sulfur recovery organic sulfur hydrolysis catalyst, which comprises the following steps:

[0046] Weigh 100 g of dry powder of titanic acid A and titanic acid B, 5 g of cement and 4 g of sesbania dry powder respectively and mix them evenly. Add 35 g of 11% nitric acid, wherein 4 g of VOSO4 and 4 g of ethanol are added to the nitric acid solution. Knead twice and set aside. Label them as semi-finished products A and semi-finished products B.

[0047] Weigh 13 g of dry powder of aluminum-containing compound B1 and knead it twice with 100 g of semi-finished product A and semi-finished product B, respectively. The content of alkali metal impurity sodium in the aluminum-containing compound B1 is about 5000 ppm. Use a ф4 mm perforated plate to extrude strips, dry in the shade (air purging) for 10 hours and 96 hours respectively, then dry at 130°C for 10 hours, and calcine at 520°C for 3 hours to obtain catalysts A and B.

[0048] The specific surface area of ​​catalyst A sample is 150m 2 / g, bulk density is 0.78g / ml, average crushing strength is 152N / cm, and the appearance is rough.

[0049] The specific surface area of ​​catalyst B sample is 160m 2 / g, bulk density is 0.78g / ml, average crushing strength is 176N / cm, and the appearance is smooth.

[0050] Comparative Example 2

[0051] This comparative example provides a method for preparing an efficient sulfur recovery organic sulfur hydrolysis catalyst, which comprises the following steps:

[0052] Weigh 13 g of dry powder of aluminum-containing compound B2, mix it with 100 g of semi-finished product B for 30 minutes, and knead it twice. The content of alkali metal impurity sodium in the aluminum-containing compound B2 is about 3000 ppm. Use a ф4 mm perforated plate to extrude it into strips, dry it in the shade (air purging) for 96 hours, then dry it at 130°C for 10 hours, and calcine it at 520°C for 3 hours to obtain catalyst C.

[0053] The specific surface area of ​​the catalyst C sample is 155 m 2 / g, bulk density is 0.75g / ml, and average crushing strength is 170N / cm.

[0054] Example 1

[0055] This embodiment provides a method for preparing an efficient sulfur recovery organic sulfur hydrolysis catalyst, which comprises the following steps:

[0056] Weigh 13 g of dry powder of aluminum-containing compound B3, mix it with 100 g of semi-finished product B and 4 g of sesbania dry powder for 30 minutes, and knead it twice. The content of alkali metal impurity sodium in the aluminum-containing compound B3 is about 300 ppm. Use a ф4 mm perforated plate to extrude it into strips, dry it in the shade (air purge) for 96 hours, then dry it at 130°C for 10 hours, and calcine it at 520°C for 3 hours to obtain catalyst D.

[0057] The specific surface area of ​​the catalyst D sample is 151 m 2 / g, bulk density is 0.75g / ml, and average crushing strength is 172N / cm.

[0058] According to the experimental results of Examples 2 and 3, the strength test results of the catalyst samples prepared from aluminum-containing compound B2 (alkaline metal sodium content of about 3000 ppm) and aluminum-containing compound B3 (alkaline metal sodium content of about 300 ppm) are similar to those of aluminum-containing compound B1, indicating that the alkali metal sodium content in different aluminum-containing compounds has little effect on the strength of the catalyst.

[0059] Comparative Example 3

[0060] This comparative example provides a method for preparing an efficient sulfur recovery organic sulfur hydrolysis catalyst, which comprises the following steps:

[0061] Weigh 13g of dry powder of aluminum-containing compound B3, 100g of titanic acid B, 5g of cement and 4g of sesbania dry powder and mix for 30 minutes, add 35g of 11% nitric acid, add 4g of VOSO4 to the nitric acid solution, knead twice, wherein the content of alkali metal impurity sodium in the aluminum-containing compound B3 is about 300ppm, use ф4mm perforated plate to extrude strips, dry in the shade (air purging) for 96 hours, then dry at 130℃ for 10 hours, and calcine at 520℃ for 3 hours to obtain catalyst E.

[0062] The specific surface area of ​​the catalyst E sample is 113 m 2 / g, bulk density is 0.74g / ml, and average crushing strength is 183N / cm.

[0063] Comparative Example 4

[0064] This comparative example provides a method for preparing an efficient sulfur recovery organic sulfur hydrolysis catalyst, which comprises the following steps:

[0065] Weigh 13g of dry powder of aluminum-containing compound B3, 100g of titanic acid B and 4g of sesbania dry powder and mix for 30 minutes, add 35g of 11% nitric acid, add 4g of VOSO4 and 4g of ethanol to the nitric acid solution, knead twice, the content of alkali metal impurity sodium in the aluminum-containing compound is about 300ppm, use ф4mm perforated plate to extrude strips, dry in the shade (air purging) for 96 hours, then dry at 130℃ for 10 hours, and calcine at 520℃ for 3 hours to obtain catalyst F.

[0066] The specific surface area of ​​the catalyst F sample is 1459 2 / g, bulk density is 0.73g / ml, and average crushing strength is 113N / cm.

[0067] Activity evaluation

[0068] 20 ml of each of the above catalyst samples crushed into 8-12 mesh sizes were respectively loaded into the reactor to evaluate the activity of the catalyst, wherein:

[0069] Reaction temperature: 320℃; inlet gas composition: H2S 6%, SO2 3%, COS 0.5%, H2O 30%, O2 0.3%, the rest is N2; gas volume space velocity: 10000h -1 ;

[0070] The claus conversion rate and organic sulfur hydrolysis activity of the catalyst were also investigated.

[0071] The claus conversion rate and COS hydrolysis rate of the catalyst were calculated according to the following formula, and the volume correction factor Kv was calculated according to formula (1):

[0072]

[0073] Where:

[0074] Kv——volume correction factor;

[0075] ——Hydrogen sulfide dry basis content in the raw gas, in %;

[0076] ——Sulfur dioxide content in the raw gas on a dry basis, in %;

[0077] ——Dry basis oxygen content in the raw gas, in %;

[0078] ——Hydrogen sulfide dry basis content in tail gas, in %;

[0079] ——Sulfur dioxide content in tail gas on a dry basis, in %;

[0080] ——Dry basis oxygen content in tail gas, in %.

[0081] Claus conversion η S Calculate according to formula (2):

[0082]

[0083] Where: η S is the Claus conversion rate, in %.

[0084] Organic sulfur hydrolysis rate (mainly COS hydrolysis rate) η O Calculate according to formula (3):

[0085]

[0086] Where: η O is the COS conversion rate, in %.

[0087] The strength, titanium oxide content and activity evaluation results of the above catalysts AF are shown in Table 1, wherein the activity evaluation data are data from 20 hours of continuous operation, and the specific activity evaluation method is as follows:

[0088] The catalyst AF was crushed into 8-12 meshes, and then 20 ml of the catalyst AF was respectively loaded into the reactor. The reaction temperature was 310-330°C, and the inlet gas composition was H2S 6.0%, SO2 3.0%, H2O 30%, COS 0.5%, O2 0.3%, and the rest was N2. The gas volume space velocity was 10000h -1; The activity of the catalyst was tested by continuous operation for 20 hours.

[0089] Table 1 Activity comparison experimental data of different catalyst samples

[0090] Catalyst samples A B C D E F Strength, N / cm 152 176 170 172 183 113 Titanium oxide content, % 94.3 94.5 94.6 95.2 83.2 95.5 Claus conversion rate, % 68.1 68.1 69.2 72.0 66.9 71.8 COS hydrolysis rate, % 94.1 94.9 93.9 96.2 72.3 96.3

[0091] From Table 1 we can see that:

[0092] Catalyst F has the lowest strength, which shows that the addition of cement greatly improves the strength of the catalyst, which is more conducive to the industrial application of the catalyst;

[0093] Catalysts A to D have similar titanium oxide contents, but catalyst E has a lower titanium oxide content due to the lack of dispersant, which results in the lowest COS hydrolysis rate;

[0094] Catalysts A, B, and C are used as comparative samples of catalyst D. Under this condition, the Claus conversion rate and COS hydrolysis rate of catalysts A, B, and C are substantially equivalent, while the Claus conversion rate and COS hydrolysis rate of catalyst D of the present invention are the highest.

[0095] Due to the low strength and titanium oxide content of existing catalysts, the gas volume space velocity used is generally 5000 -1 Otherwise, the Claus conversion rate and the organic sulfur hydrolysis rate will be seriously reduced, and even the catalyst will be seriously damaged and the service life will be greatly shortened. -1 Under the conditions of high Claus conversion rate and organic sulfur hydrolysis rate, as well as ultra-long service life.

Claims

1. A method for preparing an efficient sulfur recovery organic sulfur hydrolysis catalyst, comprising the following steps: Mixing metatitanic acid with a high temperature resistant raw material and an extrusion aid, and then adding a modifier, a dispersant, and an active metal salt to knead to obtain a semi-finished product, wherein the mass ratio of the metatitanic acid, the high temperature resistant raw material, the modifier, the dispersant, and the active metal salt is 10-15:0.5-1:1-2:0.5-5:0.5-2; The semi-finished product is mixed with an aluminum-containing compound in a mass ratio of 4-8:1-2, and then kneaded, molded, dried, and calcined to obtain the catalyst; Wherein, the modifier is one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid and citric acid.

2. The preparation method according to claim 1, wherein The particle size of the metatitanic acid is 200-300 meshes.

3. The preparation method according to claim 1, wherein The modifier is nitric acid with a concentration of 2%-15%.

4. The preparation method according to claim 1, wherein The high temperature resistant raw material includes one or a combination of two or more of cement, polyurethane, methyl methacrylate resin and polypropylene.

5. The preparation method according to claim 1, wherein The dispersant includes one or a combination of two or more of ethanol, ethylenediamine, citric acid, polyethylene glycol, and polypropylene glycol.

6. The preparation method according to claim 1, wherein The active metal salt is a metal salt that does not decompose and can melt under the condition of 500-600°C, preferably one of TiOSO4, Ti(SO4)2, VOSO4 or a combination of two or more thereof.

7. The preparation method according to claim 1, wherein The aluminum-containing compound comprises aluminum xerogel, calcium oxide and silicon dioxide; Wherein, based on the mass of the aluminum-containing compound as 100%, the contents of the aluminum xerogel, calcium oxide, and silicon dioxide are 98%-99%, 0.5%-1%, and 0.5%-1%, respectively; The sodium content in the aluminum-containing compound is less than 300 ppm; Preferably, the particle size of the aluminum-containing compound is 200-300 mesh.

8. The preparation method according to claim 1, wherein An extrusion aid is added during the preparation of the semi-finished product. The amount of the extrusion aid is 5-10% of the total weight of the material. The extrusion aid includes one or a combination of two or more of sesbania powder, hydroxymethyl cellulose, hydroxyethyl cellulose, polyethylene oxide, and polyethylamide.

9. The preparation method according to claim 1, wherein The drying includes shade drying and drying in an oven. The shade drying takes 1 to 2 days. The drying temperature is 100 to 160° C. and the drying time is 5 to 10 hours.

10. The preparation method according to claim 1, wherein: The calcination temperature is 500-600° C. and the calcination time is 3-5 hours.

11. An efficient sulfur recovery organic sulfur hydrolysis catalyst, which is prepared by the preparation method according to any one of claims 1 to 10.

12. The catalyst according to claim 11, wherein The specific surface area of ​​the catalyst is 100-200m 2 / g, the average crushing strength is 150-230N / cm, the bulk density is 0.6-0.8g / ml, and the absolute content of titanium oxide in the catalyst body is 90-97%.

13. An organic sulfur recovery process, which is carried out using the high-efficiency sulfur recovery organic sulfur hydrolysis catalyst according to claim 11 or 12.

14. The organic sulfur recovery process according to claim 13, wherein: During the recovery process, the volume space velocity of the gas containing organic sulfur is 10000h -1 .