High-temperature-resistant desulfurization catalyst and preparation method thereof

Abstract

The invention provides a high-temperature-resistant desulfurization catalyst and a preparation method thereof, and relates to the technical field of catalysis, and the high-temperature-resistant desulfurization catalyst comprises the following components in percentage by weight: 30-35% of cobalt phthalocyanine, 10-15% of Fe-PBTCA-EDTMP, 10-15% of manganese sulfate monohydrate, 10-15% of 2, 3, 4-trimethyl-1, 3-pentanediol monoisobutyrate, 10-15% of 2, 3, 4-trimethyl-1, 3 The cleaning agent is prepared from 5-10% of 1, 4-dinitrophenol, 15-20% of tannin extract, 8-10% of sodium metavanadate, 8-10% of ammonium phosphate and 4-8% of ammonia-ammonium chloride solution. The high-temperature-resistant desulfurization catalyst disclosed by the invention has the advantages of being small in dosage, small in waste liquid discharge, good in regeneration effect, low in corrosion rate, low in operation cost, not easy to block a tower, capable of overcoming hydrogen cyanide poisoning, high-temperature-resistant and not easy to inactivate. In a wet oxidation desulfurization system, the high-temperature-resistant desulfurization catalyst provided by the invention overcomes the defects that a PDS desulfurization catalyst, an MSQ desulfurization catalyst, a vanadium pentoxide + tannin extract catalyst and an ADA catalyst are easy to inactivate and secondary salts in a desulfurization solution are increased quickly when the desulfurization solution is at a high temperature of 70 DEG C. In addition, the high-temperature-resistant desulfurization catalyst overcomes the defects that a complex iron catalyst is high in corrosivity, large in usage amount, prone to tower blockage and the like.

Description

Technical Field

[0001] The present invention relates to the field of catalytic technology, and in particular to a high temperature resistant desulfurization catalyst and a preparation method thereof. The catalyst is a liquid phase oxidation catalyst, which is suitable for the purification of coal gas, natural gas, semi-water gas, synthetic ammonia raw gas, biogas, coke oven gas and gasoline, etc., which need to remove inorganic sulfur and organic sulfur. Background Art

[0002] When dealing with high concentrations of H2S, wet oxidation desulfurization is generally used in industry. There are sulfonated cobalt phthalocyanine catalysts, complex iron catalysts, ADA catalysts, tannin extract catalysts, MSQ catalysts, etc. on the market for wet oxidation desulfurization. Among them, sulfonated cobalt phthalocyanine catalysts have the advantages of small usage, good regeneration effect, not easy to plug the tower, and overcome hydrogen cyanide poisoning. However, sulfonated cobalt phthalocyanine catalysts have the disadvantages of large waste liquid discharge and deactivation of desulfurization liquid above 45°C; complex iron catalysts have the advantages of high hydrogen sulfide removal effect and less waste liquid discharge, but complex iron catalysts have the disadvantages of high corrosion, large catalyst usage, and easy tower plugging. The addition of complex iron catalyst in coking plants will cause excessive iron ions in the sulfuric acid production process of desulfurization waste liquid, affecting the quality of sulfuric acid; ADA catalyst has the advantages of less equipment corrosion and good chemical stability, but ADA catalyst has the disadvantages of low hydrogen cyanide removal efficiency, large investment, and high operating cost; tannin extract catalyst and MSQ catalyst are mostly used in the process of treating semi-water gas, but they are not effective in treating blast furnace gas or high-concentration H2S and are deactivated when the desulfurization liquid temperature exceeds 45°C. The above catalysts have shortcomings in practical applications, and the desulfurization effect is not ideal. Therefore, it is urgent to develop a high-temperature desulfurization catalyst with low dosage, less waste liquid discharge, good regeneration effect, low corrosion rate, low operating cost, not easy to cause tower blockage, overcome hydrogen cyanide poisoning, high temperature resistance, and not easy to deactivate. Summary of the invention

[0003] The purpose of the present invention is to provide a high temperature resistant desulfurization catalyst, which can not only overcome the disadvantages of PDS desulfurization catalyst, MSQ desulfurization catalyst, vanadium pentoxide + tannin catalyst and ADA catalyst being deactivated when the desulfurization liquid is at a high temperature of 70°C in a wet oxidation desulfurization system, but also slow down the growth of secondary salts in the desulfurization liquid.

[0004] The invention provides a high temperature resistant desulfurization catalyst, the components and weight percentage of which are: 30-35% of cobalt phthalocyanine, 10-15% of Fe-PBTCA-EDTMP, 10-15% of manganese sulfate monohydrate, 5-10% of 2,4-dinitrophenol, 15-20% of tannin extract, 4-10% of sodium metavanadate, 4-10% of ammonium phosphate and 4-8% of ammonia-ammonium chloride solution.

[0005] The present invention also provides a method for preparing a high temperature resistant desulfurization catalyst, comprising the following steps:

[0006] (1) adding cobalt phthalocyanine, Fe-PBTCA-EDTMP, manganese sulfate monohydrate, 2,4-dinitrophenol, tannin extract, sodium metavanadate, ammonium phosphate, and ammonia-ammonium chloride solution into a reaction kettle equipped with a stirring device, mixing and stirring uniformly;

[0007] (2) When the pH of the reactor is less than 10, add ammonia-ammonium chloride solution to control the pH of the reactor between 10 and 11;

[0008] (3) The mixture obtained in step (2) is placed in an electric heating box for heating to 150° C. for 3 hours to obtain a fluffy, porous, gray-black, high-temperature resistant desulfurization catalyst with a brownish red color. After drying and crushing, 80# powder is obtained, which is packaged using a vacuum packaging machine.

[0009] Preferably, the preparation of cobalt phthalocyanine comprises the following steps:

[0010] (1) Put 50% fuming sulfuric acid and phthalic anhydride in a 1:1 ratio (weight ratio) into a sulfonation reaction kettle, add anhydrous sodium sulfate and stir, gradually raise the temperature to 255°C, react for 24 hours until the sulfonation mixture is completely dissolved in water, cool, remove excess sulfuric acid with lime milk to a pH of ≥3, neutralize with ammonium carbonate to neutrality, filter out calcium carbonate precipitate, heat the solution to evaporate and crystallize, and stop heating after obtaining a brown sulfonated material;

[0011] (2) The sulfonated material obtained in step (1), disodium pyromellitic acid, industrial urea, cobalt chloride hexahydrate, and ammonium molybdate are uniformly mixed in a weight ratio of 100:10:90:217:2 and placed in a reaction kettle, heated to 250° C., and reacted for 2 hours to obtain crisp, porous blue-purple cobalt phthalocyanine.

[0012] Preferably, the preparation of the Fe-PBTCA-EDTMP comprises the following steps:

[0013] (1) Select PBTCA and EDTMP water treatment agents, and prepare a mixed solution according to PBTCA:EDTMP=1:1 (molar ratio) with a total content of PBTCA and EDTMP of 0.0576 mol / L;

[0014] (2) adding sodium carbonate to the solution obtained in step (1) to make the concentration of the sodium carbonate solution reach 0.2 mol / L;

[0015] (3) Select ferric chloride hexahydrate and ferrous sulfate heptahydrate, according to Fe 3+ :Fe 2+ =9:1 (molar ratio), total Fe is 0.036 mol / L to prepare a mixed solution;

[0016] (4) The solution obtained in step (2) is heated to 50° C., and the solution obtained in step (3) is slowly poured in, the reaction temperature is maintained at 50° C., stirring is continued for 2 hours, and sodium carbonate solution (0.2 mol / L) is continuously added dropwise to the solution until the pH reaches 11. The obtained product is the Fe-PBTCA-EDTMP.

[0017] Preferably, the ammonia-ammonium chloride solution is 54 g of ammonium chloride dissolved in water (distilled water), 350 ml of ammonia water (25%) is added, and the resulting solution is diluted to 1000 ml with distilled water.

[0018] Preferably, the 2,4-dinitrophenol, the sodium metavanadate, and the ammonium phosphate are all analytically pure, the manganese sulfate monohydrate is industrial grade, and the tannin extract is tannin extract.

[0019] Beneficial Effects

[0020] (1) The high temperature resistant desulfurization catalyst of the present invention is applicable to different desulfurization processes and can remove both inorganic sulfur and organic sulfur. The inorganic sulfur removal efficiency is above 98% and the organic sulfur removal rate is above 50%.

[0021] (2) The high temperature resistant desulfurization catalyst of the present invention does not deactivate at a high temperature of 70°C in the desulfurization liquid.

[0022] (3) When the temperature of the desulfurization liquid is 30-40°C, the amount of foam generated by the high temperature resistant desulfurization catalyst of the present invention is 2-3 times that of the PDS desulfurization catalyst, MSQ desulfurization catalyst, vanadium pentoxide + tannin catalyst, and ADA catalyst.

[0023] (4) The high temperature resistant desulfurization catalyst of the present invention has a low rate of secondary salt generation and a small amount of waste liquid discharged.

[0024] (5) The high temperature resistant desulfurization catalyst described in the present invention is prepared using water treatment agents and has a low corrosion rate to carbon steel. DETAILED DESCRIPTION

[0025] The following is a clear and complete description of the technical solutions specifically implemented in the present invention, and the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. It should be noted that the embodiments are provided to enable those skilled in the art to more thoroughly understand the preparation method of the present invention, and should not be limited by the embodiments described herein.

[0026] The invention provides a high temperature resistant desulfurization catalyst, the components and weight percentage of which are: 30-35% of cobalt phthalocyanine, 10-15% of Fe-PBTCA-EDTMP, 10-15% of manganese sulfate monohydrate, 5-10% of 2,4-dinitrophenol, 15-20% of tannin extract, 4-10% of sodium metavanadate, 4-10% of ammonium phosphate and 4-8% of ammonia-ammonium chloride solution.

[0027] The present invention also provides a method for preparing a high temperature resistant desulfurization catalyst, comprising the following steps:

[0028] (1) adding cobalt phthalocyanine, Fe-PBTCA-EDTMP, manganese sulfate monohydrate, 2,4-dinitrophenol, tannin extract, sodium metavanadate, ammonium phosphate, and ammonia-ammonium chloride solution into a reaction kettle equipped with a stirring device, mixing and stirring uniformly;

[0029] (2) When the pH of the reactor is less than 10, add ammonia-ammonium chloride solution to control the pH of the reactor between 10 and 11;

[0030] (3) The mixture obtained in step (2) is placed in an electric heating box for heating to 150° C. for 3 hours to obtain a fluffy, porous, gray-black, high-temperature resistant desulfurization catalyst with a brownish red color. After drying and crushing, 80# powder is obtained, which is packaged using a vacuum packaging machine.

[0031] Preferably, the preparation of cobalt phthalocyanine comprises the following steps:

[0032] (1) Put 50% fuming sulfuric acid and phthalic anhydride in a 1:1 ratio (weight ratio) into a sulfonation reaction kettle, add anhydrous sodium sulfate and stir, gradually raise the temperature to 255°C, react for 24 hours until the sulfonation mixture is completely dissolved in water, cool, remove excess sulfuric acid with lime milk to a pH of ≥3, neutralize with ammonium carbonate to neutrality, filter out calcium carbonate precipitate, heat the solution to evaporate and crystallize, and stop heating after obtaining a brown sulfonated material;

[0033] (2) The sulfonated material obtained in step (1), disodium pyromellitic acid, industrial urea, cobalt chloride hexahydrate, and ammonium molybdate are uniformly mixed in a weight ratio of 100:10:90:217:2 and placed in a reaction kettle, heated to 250° C., and reacted for 2 hours to obtain crisp, porous blue-purple cobalt phthalocyanine.

[0034] Preferably, the preparation of the Fe-PBTCA-EDTMP comprises the following steps:

[0035] (1) Select PBTCA and EDTMP water treatment agents, and prepare a mixed solution according to PBTCA:EDTMP=1:1 (molar ratio) with a total content of PBTCA and EDTMP of 0.0576 mol / L;

[0036] (2) adding sodium carbonate to the solution obtained in step (1) to make the concentration of the sodium carbonate solution reach 0.2 mol / L;

[0037] (3) Select ferric chloride hexahydrate and ferrous sulfate heptahydrate, according to Fe 3+ :Fe 2+=9:1 (molar ratio), total Fe is 0.036 mol / L to prepare a mixed solution;

[0038] (4) The solution obtained in step (2) is heated to 50° C., and the solution obtained in step (3) is slowly poured in, the reaction temperature is maintained at 50° C., stirring is continued for 2 hours, and sodium carbonate solution (0.2 mol / L) is continuously added dropwise to the solution until the pH reaches 11. The obtained product is the Fe-PBTCA-EDTMP.

[0039] Preferably, the ammonia-ammonium chloride solution is 54 g of ammonium chloride dissolved in water (distilled water), 350 ml of ammonia water (25%) is added, and the resulting solution is diluted to 1000 ml with distilled water.

[0040] Preferably, the 2,4-dinitrophenol, the sodium metavanadate, and the ammonium phosphate are all analytically pure, the manganese sulfate monohydrate is industrial grade, and the tannin extract is tannin extract.

[0041] (1) Preparation Example of Cobalt Phthalocyanine

[0042] a. Put 50% fuming sulfuric acid (40kg) and phthalic anhydride (40kg) into a sulfonation reaction kettle, add anhydrous sodium sulfate (500g) and stir, gradually raise the temperature to 255°C, react for 24 hours, until the sulfonation mixture is completely dissolved in water, cool, remove excess sulfuric acid with lime milk to pH ≥ 3, then neutralize with ammonium carbonate to neutrality, filter out calcium carbonate precipitate, heat the solution to evaporate and crystallize, and stop heating after obtaining a brown sulfonated material.

[0043] b. Weigh the sulfonated material (30 kg), disodium pyromellitic acid (3 kg), industrial urea (27 kg), cobalt chloride hexahydrate (65.1 kg), and ammonium molybdate (0.6 kg), mix them evenly and put them into a reaction kettle, heat to 250° C., react for 2 hours, and obtain crisp, porous cobalt phthalocyanine (120 kg).

[0044] (2) Preparation Example of Fe-PBTCA-EDTMP

[0045] a. Take ferric chloride hexahydrate (4378.698 g) and ferrous sulfate heptahydrate (500.418 g), put them into a container with a stirring device, add 500 L of distilled water, mix and stir evenly.

[0046] b. Take 50% PBTCA (7.78 kg), solid EDTMP (6.28 kg), and sodium carbonate (10.6 kg), add them into a reactor with a stirring device, then add 500 L of distilled water, mix and stir evenly, and then heat to 50°C.

[0047] c. The solution obtained in a was pumped into the solution obtained in b, and stirring was continued for 2 hours. Sodium carbonate solution (0.2 mol / L) was continuously added dropwise to the solution until the pH reached 11. The obtained product was Fe-PBTCA-EDTMP.

[0048] (3) Ammonia-ammonium chloride solution preparation example

[0049] Take 27 kg of ammonium chloride, add 200 L of distilled water, stir until the ammonium chloride is completely dissolved, then add 350 ml of ammonia water (25%), and finally add 300 L of distilled water, mix and stir evenly.

[0050] Example 1

[0051] Add cobalt phthalocyanine (70kg), Fe-PBTCA-EDTMP (20kg), manganese sulfate monohydrate (30kg), 2,4-dinitrophenol (10kg), cloud crown tannin extract (30kg), sodium metavanadate (16kg), ammonium phosphate (16kg), and ammonia-ammonium chloride solution (8kg) into a reactor with a stirring device, mix and stir evenly. When the pH of the reactor is less than 10, add ammonia-ammonium chloride solution to control the pH of the reactor between 10-11. Then take it out and put it into an electric heating box for heating, heating to 150℃ for 3 hours to obtain a fluffy, porous, brown-red gray-black high-temperature resistant desulfurization catalyst A (160kg). After drying and crushing, 80# powder is obtained and packaged with a vacuum packaging machine.

[0052] Example 2

[0053] Add cobalt phthalocyanine (60kg), Fe-PBTCA-EDTMP (30kg), manganese sulfate monohydrate (30kg), 2,4-dinitrophenol (10kg), cloud crown tannin extract (40kg), sodium metavanadate (10kg), ammonium phosphate (12kg), and ammonia-ammonium chloride solution (8kg) into a reactor with a stirring device, mix and stir evenly. When the pH of the reactor is less than 10, add ammonia-ammonium chloride solution to control the pH of the reactor between 10-11. Then take it out and put it into an electric heating box for heating, heating to 150℃ for 3 hours, and obtain fluffy, porous, gray-black, high-temperature resistant desulfurization catalyst B (160kg) with brownish red color. After drying and crushing, 80# powder is obtained, which is packaged with a vacuum packaging machine.

[0054] Example 3

[0055] Add cobalt phthalocyanine (70kg), Fe-PBTCA-EDTMP (30kg), manganese sulfate monohydrate (26kg), 2,4-dinitrophenol (20kg), cloud crown tannin extract (30kg), sodium metavanadate (8kg), ammonium phosphate (8kg), and ammonia-ammonium chloride solution (8kg) into a reactor with a stirring device, mix and stir evenly. When the pH of the reactor is less than 10, add ammonia-ammonium chloride solution to control the pH of the reactor between 10-11. Then take it out and put it into an electric heating box for heating, heating to 150℃ for 3 hours to obtain a fluffy, porous, brown-red gray-black high-temperature resistant desulfurization catalyst C (160kg). After drying and crushing, 80# powder is obtained and packaged with a vacuum packaging machine.

[0056] Example 4

[0057] Cobalt phthalocyanine (66kg), Fe-PBTCA-EDTMP (26kg), manganese sulfate monohydrate (20kg), 2,4-dinitrophenol (20kg), cloud crown tannin extract (40kg), sodium metavanadate (8kg), ammonium phosphate (12kg), ammonia-ammonium chloride solution (8kg) are added to a reactor with a stirring device, mixed and stirred evenly. When the pH of the reactor is less than 10, ammonia-ammonium chloride solution is added to control the pH of the reactor between 10-11. Then take it out and put it into an electric heating box for heating, heating to 150℃ for 3 hours to obtain a fluffy, porous, brown-red gray-black high-temperature resistant desulfurization catalyst D (160kg). After drying and crushing, 80# powder is obtained and packaged with a vacuum packaging machine.

[0058] In the wet oxidation desulfurization system, when the desulfurization liquid is 70°C, the desulfurization performance of the high temperature resistant desulfurization catalyst of the present invention is compared with that of the PDS desulfurization catalyst, the MSQ desulfurization catalyst, the vanadium pentoxide + tannin extract catalyst, and the ADA catalyst as shown in Table 1.

[0059] Table 1 Desulfurization performance comparison

[0060] Desulfurization effect Sulfur recovery rate Sub-salt production (g / L) High temperature resistant catalyst A of the present invention 82.1％ 75.8％ 192 High temperature resistant catalyst B of the present invention 72.4％ 64.5％ 223 The high temperature resistant catalyst C of the present invention 62.8％ 54.3％ 254 High temperature resistant catalyst D of the present invention 76.9％ 68.6％ 206 PDS Catalyst 39.3％ 27.7％ 301 Tannin extract + vanadium pentoxide 36.2％ 22.5％ 323 MSQ 35.7％ 21.8％ 357 ADA 35.3％ 20.6％ 368

[0061] It can be seen from the above data that the desulfurization performance of the high temperature resistant desulfurization catalyst of the present invention is significantly better than that of the PDS desulfurization catalyst, the MSQ desulfurization catalyst, the vanadium pentoxide + tannin extract catalyst, and the ADA catalyst. When the desulfurization liquid temperature is 70°C, when the desulfurization effect of other catalysts is very poor, the high temperature resistant desulfurization catalyst of the present invention can still ensure a higher desulfurization effect.

Claims

1. A high temperature resistant desulfurization catalyst, characterized in that: The invention comprises the following components in weight percentage: 30-35% of cobalt phthalocyanine, 10-15% of Fe-PBTCA-EDTMP, 10-15% of manganese sulfate monohydrate, 5-10% of 2,4-dinitrophenol, 15-20% of tannin extract, 4-10% of sodium metavanadate, 4-10% of ammonium phosphate and 4-8% of ammonia-ammonium chloride solution.

2. A method for preparing a high temperature resistant desulfurization catalyst, characterized in that: The following steps are involved: (1) adding cobalt phthalocyanine, Fe-PBTCA-EDTMP, manganese sulfate monohydrate, 2,4-dinitrophenol, tannin extract, sodium metavanadate, ammonium phosphate, and ammonia-ammonium chloride solution into a reaction kettle equipped with a stirring device, mixing and stirring uniformly; (2) When the pH of the reactor is less than 10, add ammonia-ammonium chloride solution to control the pH of the reactor between 10 and 11; (3) The mixture obtained in step (2) is placed in an electric heating box for heating to 150° C. for 3 hours to obtain a fluffy, porous, gray-black, high-temperature resistant desulfurization catalyst with a brownish red color. After drying and crushing, 80# powder is obtained, which is packaged using a vacuum packaging machine.

3. The method for preparing a high temperature resistant desulfurization catalyst according to claim 2, characterized in that: The preparation of the cobalt phthalocyanine comprises the following steps: (1) Put 50% fuming sulfuric acid and phthalic anhydride in a 1:1 ratio (weight ratio) into a sulfonation reaction kettle, add anhydrous sodium sulfate and stir, gradually raise the temperature to 255°C, react for 24 hours until the sulfonation mixture is completely dissolved in water, cool, remove excess sulfuric acid with lime milk to a pH of ≥3, neutralize with ammonium carbonate to neutrality, filter out calcium carbonate precipitate, heat the solution to evaporate and crystallize, and stop heating after obtaining a brown sulfonated material; (2) The sulfonated material obtained in step (1), disodium pyromellitic acid, industrial urea, cobalt chloride hexahydrate, and ammonium molybdate are uniformly mixed in a weight ratio of 100:10:90:217:2 and placed in a reaction kettle, heated to 250° C., and reacted for 2 hours to obtain crisp, porous blue-purple cobalt phthalocyanine.

4. The method for preparing a high temperature resistant desulfurization catalyst according to claim 2, characterized in that: The preparation of the Fe-PBTCA-EDTMP comprises the following steps: (1) Select PBTCA and EDTMP water treatment agents, and prepare a mixed solution according to PBTCA:EDTMP=1:1 (molar ratio) with a total content of PBTCA and EDTMP of 0.0576 mol / L; (2) adding sodium carbonate to the solution obtained in step (1) to make the concentration of the sodium carbonate solution reach 0.2 mol / L; (3) Select ferric chloride hexahydrate and ferrous sulfate heptahydrate, according to Fe 3+ :Fe 2+ =9:1 (molar ratio), total Fe is 0.036 mol / L to prepare a mixed solution; (4) The solution obtained in step (2) is heated to 50° C., and the solution obtained in step (3) is slowly poured in, the reaction temperature is maintained at 50° C., stirring is continued for 2 hours, and sodium carbonate solution (0.2 mol / L) is continuously added dropwise to the solution until the pH reaches 11. The obtained product is the Fe-PBTCA-EDTMP.

5. The method for preparing a high temperature resistant desulfurization catalyst according to claim 2, characterized in that: The ammonia-ammonium chloride solution is prepared by dissolving 54 g of ammonium chloride in water (distilled water), adding 350 ml of aqueous ammonia (25%), and diluting the solution to 1000 ml with distilled water.

6. The method for preparing a high temperature resistant desulfurization catalyst according to claim 2, characterized in that: The 2,4-dinitrophenol, the sodium metavanadate and the ammonium phosphate are all analytically pure, the manganese sulfate monohydrate is industrial grade, and the tannin extract is tannin extract.