Super deep hydrodesulfurization catalyst and preparation method thereof

A desulfurization catalyst and deep hydrogenation technology, applied in molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve problems such as difficult access to active centers, difficult removal, and reduced reaction rate, so as to avoid molecular sieve distribution Unevenness, improvement of pore structure, effect of reducing dosage

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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  • Super deep hydrodesulfurization catalyst and preparation method thereof
  • Super deep hydrodesulfurization catalyst and preparation method thereof
  • Super deep hydrodesulfurization catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Add 1000ml of water to the dissolution tank and the concentration is 10.9g / cm 3 376 ml of aluminum chloride solution, 39 g of nickel chloride and 36.5 g of ammonium metatungstate were dissolved to prepare a mixed solution. Get 160g ammonium bicarbonate and be made into the aqueous solution that molar concentration is 2.5mol / l. Then the mixed solution, ammonium bicarbonate aqueous solution, and 10% ammonia water as a precipitant are simultaneously and co-flowed into a reaction tank equipped with clean water to form a gel. The pH of the gel is 8.0, and the temperature of the gel is 60°C. After the gelation finishes, add 8 grams of Y-type molecular sieve slurry (the properties of Y-type molecular sieve are as follows: SiO 2 / Al 2 o 3 The molar ratio is 18, the unit cell parameter is 2.440nm, the infrared acidity is 0.35mmol), and the aging time is 2 hours. After aging, filter, add 600ml of clean water and 8.3g of molybdenum trioxide to the filter cake, beat and stir ev...

Embodiment 2

[0034] According to the method of Example 1, according to the component content ratio of catalyst B in Table 2, aluminum chloride, nickel chloride, ammonium metatungstate, phosphoric acid, water glass were added into the dissolution tank to prepare a mixed solution. Take 100g of ammonium bicarbonate to make a solution with a molar concentration of 2.0mol / l. Then the mixed solution, aqueous ammonium bicarbonate solution, and 20% ammonia water as a precipitating agent are simultaneously and co-flowed into a reaction tank equipped with clean water to form a gel. The pH of the gel is 9.0, and the temperature of the gel is 80°C. After gelling, add 5 grams of Y-type molecular sieve slurry (the same properties as in Example 1), age for 3 hours, filter after aging, add 600ml of clean water and 6.2g of molybdenum trioxide to the filter cake, beat and stir evenly, filter, and obtain the filter cake The cake was dried at 70°C for 7 hours, then extruded into strips, washed twice with clea...

Embodiment 3

[0036] According to the method of Example 1, according to the component content ratio of catalyst C in Table 1, nickel nitrate, ammonium metatungstate, aluminum chloride, zirconium oxychloride were added into the reaction tank to prepare a mixed solution. Get 120g ammonium oxalate to be made into the solution that molar concentration is 1.8mol / l. Then the mixed solution, ammonium oxalate aqueous solution, and 12% ammonia water as a precipitating agent are simultaneously and co-flowed into a reaction tank equipped with clean water to form a gel. The pH of the gel is 10.0, and the gelation temperature is 60°C. After gelling, add 10 grams of Y-type molecular sieve slurry, age for 2 hours, filter after aging, add 600ml of clean water and 6.2g of molybdenum trioxide to the filter cake, beat and stir evenly, filter, and dry the obtained filter cake at 120°C for 1 hour , and then extruded into strips. The wet strips were dried at 130°C for 3 hours and calcined at 600°C for 3 hours to...

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Abstract

The invention discloses a super deep hydrodesulfurization catalyst and a preparation method thereof. The catalyst comprises a composite oxide (NixWyOz), MoO3, aluminum oxide, a type-Y molecular sieve. The method comprises: adding a proper amount of water soluble nitride in a Ni, W and Al precipitation process; after gelatin is formed, adding type-Y molecular sieve slurry; aging and beating with MoO3; and forming and activating. When the method is used, the porous structure of the catalyst is improved, more metal active sites are exposed from the surface of the catalyst, the utilization rate of active metals is improved, the type-Y molecular sieve and metals having hydrogenation activity are uniformly and fully contacted and well combined, and the effect of super deep hydrodesulfurization of diesel is achieved. In addition, the aperture and pore capacity of the catalyst are increased, so a Ni-W high-activity center is fully used, it is easier for complex macromolecules to contact the active center, and the effect is more obvious particularly when the catalyst is used for processing distillates with high macromolecule content.

Description

technical field [0001] The invention relates to a hydrodesulfurization catalyst and a preparation method thereof, in particular to a distillate oil ultra-deep hydrodesulfurization catalyst containing Y molecular sieve and a preparation method thereof. Background technique [0002] Since the combustion of sulfur 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 restrictions on sulfur content. The U.S. Environmental Protection Agency has lowered the diesel sulfur content standard to 15ppm in June 2006. Among various desulfurization technologies for diesel, the most mature one is hydrodesulfurization technology. Ways to achieve deep desulfurization include the development of new reactors and new catalysts. Kinetic studies have shown that to reduce the sulfur content of diesel from 500ppm to below 15ppm, the reactor volume must be tripled, which is...

Claims

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Application Information

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IPC IPC(8): B01J29/16B01J35/10C10G45/12
Inventor 王海涛徐学军刘东香王继锋冯小萍
Owner CHINA PETROLEUM & CHEM CORP
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