Beta zeolite-containing ultradeep hydrodesulfurization catalyst and preparation method thereof

A desulfurization catalyst and deep hydrogenation technology, applied in the direction of catalyst activation/preparation, molecular sieve catalysts, chemical instruments and methods, etc., can solve the problems of difficult access to active centers, difficult removal, and decreased reaction rate, so as to reduce production costs, Improve the effect of pore structure and pore diameter enlargement

Active Publication Date: 2011-05-11
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

4,6-Dimethyldibenzothiophene sulfide is usually the most difficult type of sulfide to remove, because the methyl group next to the sulfur atom creates steric hindrance between the sulfur atom and the active center of the catalyst, Sulfur atoms are not easy to access the active center of the reaction, which leads to a significant decrease in the reaction rate
In the prior art, only emphasis is placed on the type

Method used

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  • Beta zeolite-containing ultradeep hydrodesulfurization catalyst and preparation method thereof
  • Beta zeolite-containing ultradeep hydrodesulfurization catalyst and preparation method thereof
  • Beta zeolite-containing ultradeep hydrodesulfurization catalyst and preparation method thereof

Examples

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Effect test

Embodiment 1

[0031] 1000 mL of water was added to the dissolving tank, followed by adding 43 g of nickel chloride to dissolve, 36.5 g of ammonium metatungstate to dissolve, and 357 ml of aluminum chloride solution, and uniformly stirred to prepare a 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 precipitant 10% ammonia water were simultaneously added into the reaction tank equipped with purified water to form a gel. After gel formation, 10 grams of beta zeolite slurry was added and aged for 2 hours. After aging, filter, add 600ml of purified water and 8.4g of molybdenum trioxide to the filter cake, beat and stir evenly, filter, the obtained filter cake is dried at 80 ℃ for 5 hours, and then extruded into strips, washed 3 times with pure water, and the wet strips are dried at 120 After drying at ℃ for 5 hours, and calcining at 500 ℃ for 4 hours, the final...

Embodiment 2

[0033] According to the method of Example 1, according to the component content ratio of catalyst B in Table 2, aluminum chloride, nickel chloride, sodium tungstate and water glass were added into the dissolving tank, and the solution was made after uniform stirring. Take 100g of ammonium bicarbonate to prepare a solution with a molar concentration of 2.0mol / l. Then the mixed solution, the aqueous ammonium bicarbonate solution and the precipitant 9% ammonia water were simultaneously added to the reaction tank equipped with purified water to form gelatinization, the gelation pH value was 10, and the gelation temperature was 80°C. After gel formation, add 14 grams of beta zeolite slurry, age for 3 hours, filter after aging, add 600 ml of purified water and 7.2 g of molybdenum trioxide to the filter cake, beat and stir evenly, filter, and dry the obtained filter cake at 70 ° C for 7 hours, Then extruded, washed twice with clean water, dried at 100°C for 6 hours, and calcined at 5...

Embodiment 3

[0035] According to the method of Example 1, add nickel nitrate, ammonium metatungstate, aluminum chloride, phosphoric acid, and zirconium oxychloride into the dissolving tank according to the component content ratio of catalyst C in Table 1, and make a solution after uniform stirring. . Take 120 g of ammonium oxalate to prepare a solution with a molar concentration of 1.8 mol / l. Then the mixed solution, the ammonium oxalate aqueous solution and the precipitant 12% ammonia water were simultaneously added into the reaction tank equipped with purified water to form a gel. After gel formation, add 10 grams of beta zeolite slurry, age for 2 hours, filter after aging, add 600ml of purified water and 9.5g of molybdenum trioxide to the filter cake, beat and stir evenly, filter, and the obtained filter cake is dried at 120 ° C for 1 hour, Then, the strip was extruded, and the wet strip was dried at 130° C. for 3 hours and calcined at 600° C. for 3 hours to obtain the final catalyst C...

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Abstract

The invention discloses a bulk phase deep hydrodesulfurization catalyst and a preparation method thereof. The components of the catalyst comprise a composite oxide (NixWyO2), MoO3, aluminum oxide and beta zeolite. The method comprises: adding a proper amount of water soluble nitrogen compound in a precipitation process of Ni, W and Al, gelatinizing, adding beta zeolite size, aging, pulping with MoO3, forming and activating. The method improves the porous structure of the catalyst, makes more metal active spots exposed from the surface of the catalyst, improves the utilization rate of active metals, and makes beta zeolite and metal having hydrogenation activity uniformly and fully contacted and better cooperated to realize ultradeep hydrodesulfurization of diesel. In addition, the increase in the aperture and pore volume of the catalyst allows a Ni-W active center to be fully utilized and molecules with complex large structures to contact the active center more easily, and the effect is more obvious particularly when distillate with high-macromolecule content.

Description

technical field [0001] The invention relates to a distillate oil hydrodesulfurization catalyst and a preparation method thereof, in particular to a bulk-phase distillate oil deep hydrodesulfurization catalyst containing beta zeolite and a preparation method thereof. Background technique [0002] Since the combustion of sulfur-containing compounds in fuels will cause serious harm to the world's environment and society, the standards for clean fuels formulated by countries around the world have greatly increased the limit on sulfur content. The US Environmental Protection Agency has lowered the diesel sulfur content standard to 15ppm in June 2006. Among the various desulfurization technologies for diesel, the most mature is the hydrodesulfurization technology. Methods to achieve deep desulfurization include developing new reactors and new catalysts. Kinetic studies have shown that to reduce the sulfur content of diesel from 500 ppm to below 15 ppm, the reactor volume must be...

Claims

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Application Information

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IPC IPC(8): B01J29/78B01J35/10B01J37/00C10G45/12
Inventor 王海涛刘东香徐学军冯小萍王继锋
Owner CHINA PETROLEUM & CHEM CORP
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