Superdeep hydrodesulfurization catalyst and preparation method thereof

[0033] Example 1

[0034] Add 1000ml water to the dissolving tank and the concentration is 10.9g/cm 3 354 ml of aluminum chloride solution, 33 g of nickel chloride and 41.6 g of ammonium metatungstate were dissolved to prepare a mixed solution. Take 160 g of ammonium bicarbonate to prepare an aqueous solution with a molar concentration of 2.5 mol/l. Then the mixed solution, ammonium bicarbonate aqueous solution, and 10% ammonia water as a precipitating agent are simultaneously added into a reaction tank filled with purified water to form a gel, the gelation pH value is 8.0, and the gelation temperature is 60°C. After gelation is over, add 10 grams of ZSM-5/MCM-41 mixed molecular sieve slurry (the preparation method of ZSM-5/MCM-41 mixed molecular sieve is as in patent CN1393400A example 1, the ratio of microporous to mesoporous molecular sieve is 60:40), Aging for 2 hours. After aging, filter, add 600ml purified water and 7.2g molybdenum trioxide to the filter cake, beat and stir evenly, filter, the filter cake obtained is dried at 80℃ for 5 hours, then extruded, washed with pure water 3 times, the wet bar is at 120 After drying at ℃ for 5 hours and calcining at 500 ℃ for 4 hours, the final catalyst A was obtained. The composition and main properties are shown in Table 1, and the pore distribution is shown in Table 2.

[0035] Example 2

[0036] According to the method of Example 1, according to the composition ratio of the catalyst B in Table 2, aluminum chloride, nickel chloride, ammonium metatungstate, phosphoric acid, and water glass were added to the dissolution tank to prepare a mixed solution. Take 100 g of ammonium bicarbonate to prepare a solution with a molar concentration of 2.0 mol/l. Then, the mixed solution, ammonium bicarbonate aqueous solution, and 20% ammonia water as a precipitating agent were simultaneously added into a reaction tank filled with purified water to form a gel. The gelation pH was 9.0 and the gelation temperature was 70°C. After gelation is over, add 8 grams of Y/MCM-41 composite molecular sieve slurry (the preparation method of Y/MCM-41 composite molecular sieve is as in Example 2 of patent CN1393403A, the ratio of microporous to mesoporous molecular sieve is 50:50), aging for 3 hours, After aging, filter, add 600ml of purified water and 10.5g of molybdenum trioxide to the filter cake, beat and stir evenly, filter, the filter cake obtained is dried at 70 ℃ for 7 hours, then extruded, washed twice with pure water, the wet bar is at 100 It was dried at ℃ for 8 hours and calcined at 550 ℃ for 3 hours to obtain the final catalyst B. The composition and main properties are shown in Table 1, and the pore distribution is shown in Table 2.

[0037] Example 3

[0038] According to the method of Example 1, according to the composition ratio of the catalyst C in Table 1, nickel nitrate, ammonium metatungstate, aluminum chloride, and zirconium oxychloride were added to the reaction tank to prepare a mixed solution. Take 110 g of ammonium oxalate to prepare a solution with a molar concentration of 1.8 mol/l. Then the mixed solution, ammonium oxalate aqueous solution, and 12% ammonia water as a precipitant are simultaneously added into a reaction tank filled with purified water to form a gel. The gelation pH is 10.0 and the gelation temperature is 60°C. After gelation is over, add 11 grams of β/SAPO-5 mixed molecular sieve slurry (the preparation method of β/SAPO-5 mixed molecular sieve is as in patent CN1834013A example 1, the ratio of microporous to mesoporous molecular sieve is 55:45), and aging for 2 hours , Filter after aging, add 600ml purified water and 6.2g molybdenum trioxide to the filter cake, beat and stir evenly, filter, the filter cake obtained is dried at 120℃ for 1 hour, and then extruded into shape. The wet cake is dried at 130℃ for 3 hours. Calcined at 600°C for 4 hours to obtain the final catalyst C. The composition and main properties are shown in Table 1, and the pore distribution is shown in Table 2.