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Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier

A compound molecular sieve and hydrodesulfurization technology, which is applied in molecular sieve catalysts, physical/chemical process catalysts, refined hydrocarbon oils, etc., can solve the problems of application limitations, unsatisfactory effects, and high diffusivity, etc., to achieve interaction improvement, Good metal dispersibility, effect of improving metal dispersibility

Active Publication Date: 2016-01-20
CHINA UNIV OF PETROLEUM (BEIJING)
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the desulfurization rate of CoMo / ZK-1 catalyst prepared by the above method to dibenzothiophene and 4,6-dimethyldibenzothiophene is higher than that of conventional CoMo / γ-Al under the same conditions 2 o 3 catalyst, but the effect achieved is still not ideal, so that its application in actual production is limited
For the above situation, the main reason is that the pore structure of the carrier mesoporous composite molecular sieve ZK-1 used in the catalyst still cannot meet the high diffusivity requirements required for the reaction.

Method used

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  • Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier
  • Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier
  • Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0054] The present embodiment provides a kind of Beta-FDU-12 composite molecular sieve, and its preparation process comprises the following steps:

[0055] 1. Preparation of Beta zeolite precursor emulsion

[0056] Prepare raw materials, the amount of TEOS is SiO 2 Gauge, NaAlO 2 The dosage is Al 2 o 3 In terms of, the amount of NaOH is Na 2 In terms of O, the molar ratio of the amount of each raw material is SiO 2 :Al 2 o 3 : Na 2 O:TEAOH:H 2 O=60:1.0:1.4:14:360. TEAOH directly uses a solution with a mass percent content of 25 wt%, and obtains the amount of the solution after conversion. The specific preparation process is:

[0057] Step 1: take a part of TEAOH (25wt%) and record it as solution (1), add TEOS into solution (1), and stir evenly for a period of time to form a slightly opaque sol, which is recorded as solution (2);

[0058] Step 2: NaOH, NaAlO 2 Mix with the remaining TEAOH (25wt%), then add deionized water and stir until dissolved, which is referred...

Embodiment 2

[0069]This embodiment provides a hydrodesulfurization catalyst, and the preparation method of the catalyst comprises the following steps:

[0070] 1. Preparation of H-type Beta-FDU-12 composite molecular sieve carrier after ion exchange treatment

[0071] The Beta-FDU-12 composite molecular sieve carrier that embodiment 1 makes and the NH of 1mol / L 4 Cl solution corresponds to 10ml NH per 1g carrier 4 Proportion of Cl solution: Stir for 2 hours in a water bath at 80°C for ammonium exchange, filter, wash, and dry, and then perform the second ammonium exchange in the same steps to obtain the H-type Beta-FDU-12 composite molecular sieve carrier.

[0072] 2. Preparation of mixed carrier

[0073] The above-mentioned H-type Beta-FDU-12 composite molecular sieve carrier and γ-Al were mixed by mechanical mixing method. 2 o 3 Beta-FDU-12-γ-Al was prepared by mixing at a mass ratio of 1:4 2 o 3 Mixed carrier (denoted as ABF).

[0074] 3. Preparation of Hydrodesulfurization Cataly...

Embodiment 3

[0079] This embodiment provides a hydrodesulfurization catalyst treated with an organic complexing agent, and the preparation method of the catalyst comprises the following steps:

[0080] 1. Dissolve 1.6g of CA in 10.6g of ammonia solution with a pH of 9 to obtain solution a;

[0081] 2. Use solution a to impregnate the Cat-ABF prepared in Example 2, and then dry it at 120° C. for 4 hours. The treated catalyst is designated as Cat-L1.

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Abstract

The invention provides a composite molecular sieve and a hydrodesulfurization catalyst prepared with the composite molecular sieve as a carrier. According to the composite molecular sieve and the hydrodesulfurization catalyst, the Beta-FDU-12 composite molecular sieve is of a bimodal porous structure, namely a Beta micropore and an FDU-12 mesoporous, the superficial area of the composite molecular sieve is 800-1000m<2>.g<-1>, the pore diameter is 14-25 nm, and the pore volume is 0.4-0.9 cm<3>.g<-1>.The hydrodesulfurization catalyst prepared with the Beta-FDU-12 composite molecular sieve as the carrier is outstanding in performance, the yield of FCC diesel oil can be higher than 99%, the denitrification percent can be higher than 98%, and the sulphur content is lower than 10 ppm.

Description

technical field [0001] The invention belongs to the field of petroleum refining, and in particular relates to a composite molecular sieve and a hydrogenation desulfurization catalyst made of the composite molecular sieve as a carrier. Background technique [0002] In recent years, the exhaust emissions caused by the combustion of vehicle fuels have led to increasingly serious air pollution. According to the survey results of relevant foreign institutions, during the nearly 15 years from 2001 to 2014, the global growth rate of diesel vehicles reached 97%, much higher than the 23% growth rate of gasoline vehicles. Therefore, providing clean and environment-friendly vehicle diesel oil has become an urgent task for the oil refining industry. SO formed by the combustion of sulfur and nitrogen compounds in diesel X , NO X It is one of the main vehicle exhaust pollutants. From January 1, 2017, the national V emission standards will be fully implemented for motor vehicles. Compa...

Claims

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Application Information

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IPC IPC(8): B01J29/70B01J35/10C10G45/12
Inventor 段爱军杜鹏赵震苑少军吴晶晶陈新国姜桂元刘坚
Owner CHINA UNIV OF PETROLEUM (BEIJING)
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