Superdeep hydrodesulfurization catalyst and preparation method thereof

A desulfurization catalyst, deep hydrogenation technology, applied in molecular sieve catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc. problems, to increase the pore size and pore volume, to avoid uneven distribution of molecular sieves, and to improve the effect of pore structure

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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  • Superdeep hydrodesulfurization catalyst and preparation method thereof
  • Superdeep hydrodesulfurization catalyst and preparation method thereof
  • Superdeep hydrodesulfurization catalyst and preparation method thereof

Examples

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[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 st...

Example Embodiment

[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 tri...

Example Embodiment

[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 eve...

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Abstract

The invention discloses a bulk phase superdeep hydrodesulfurization catalyst and a preparation method thereof. The catalyst comprises NixWyOz which is a composite oxide, MoO3 and aluminum oxide and microporous and mesoporous composite molecular sieves. The method comprises the following steps of: adding proper quantity of water-solubility nitrogenous compounds in the precipitation process of Ni, W and Al, gelatinating, adding serous fluid of the composite molecular sieves, aging, beating the mixture with the MoO3, and forming and activating to prepare the bulk phase superdeep hydrodesulfurization catalyst. By the method, a pore structure of the catalyst is improved, so that more metal active sites are exposed from the surface of the catalyst to improve the utilization rate of active metal, and the composite molecular sieves contact the hydrogenated active metal uniformly and better coordinate with the hydrogenated active metal to produce the performance of the composite molecular sieves fully and achieve the effect of superdeep desulfuration of diesel oil, and particularly, the effect of processing macromolecular distillate with more content is more obvious.

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 a composite 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...

Claims

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Application Information

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IPC IPC(8): B01J29/80B01J29/85B01J23/888B01J35/10C10G45/12
Inventor 王海涛徐学军刘东香冯小萍王继锋
Owner CHINA PETROLEUM & CHEM CORP
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