Supported catalyst using modified ZSM-5 molecular sieve as carrier and preparation method and application thereof

A technology of ZSM-5 and molecular sieve, which is applied in the direction of molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of low selectivity of a single product, high selectivity of methyl bromide to synthesize isobutene, etc. The method is simple, the reaction conditions are mild, and the product selectivity is high

Active Publication Date: 2016-11-23
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the technology with higher value-added low-carbon olefins as the target product, the selectivity of a single product is

Method used

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  • Supported catalyst using modified ZSM-5 molecular sieve as carrier and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Weigh an appropriate amount of hydrogen-type ZSM-5 molecular sieve (silicon-aluminum ratio 50) and place it in a tube-type high-temperature furnace. Mixed with nitrogen into the tube high temperature furnace. The amount of water introduced is based on the mass of the sample, and the space velocity is 8h -1 . The volume ratio of water and nitrogen in the mixed atmosphere is 1:3. Under the steam atmosphere, the heating rate was 15°C / min, calcined at 450°C for 4h, and then cooled to room temperature under the protection of nitrogen. The obtained steam-modified molecular sieve was impregnated with 1 mol / L citric acid solution at 50°C for 2h, and then calcined at 550°C for 6h to obtain the desired modified ZSM-5 molecular sieve.

[0030] Weigh an appropriate amount of zinc nitrate and zirconium nitrate and dissolve them in deionized water, and load them on the above-mentioned modified ZSM-5 molecular sieve (pore volume is 0.38ml / g, specific surface area is 407m 2 / g, str...

Embodiment 2

[0033] Weigh an appropriate amount of hydrogen-type ZSM-5 molecular sieve (silicon-aluminum ratio 100) and place it in a tube-type high-temperature furnace. Mixed with nitrogen into the tube high temperature furnace. The amount of water introduced is based on the mass of the sample, and the space velocity is 5h -1 . The volume ratio of water and nitrogen in the mixed atmosphere is 1:10. Under the steam atmosphere, the heating rate was 10°C / min, calcined at 400°C for 8h, and then cooled to room temperature under the protection of nitrogen. The obtained steam-modified molecular sieve was impregnated with 0.5mol / L citric acid solution at 30°C for 4h, and then calcined at 500°C for 8h to obtain the desired modified ZSM-5 molecular sieve.

[0034] Weigh an appropriate amount of zinc nitrate and zirconium nitrate and dissolve them in deionized water, and load them on the above-mentioned modified ZSM-5 molecular sieve (pore volume is 0.51ml / g, specific surface area is 436m 2 / g, ...

Embodiment 3

[0037] Weigh an appropriate amount of hydrogen-type ZSM-5 molecular sieve (silicon-aluminum ratio 150) and place it in a tube-type high-temperature furnace. Mixed with nitrogen into the tube high temperature furnace. The amount of water introduced is based on the mass of the sample, and the space velocity is 10h -1 . The volume ratio of water to nitrogen in the mixed atmosphere is 1:2. The heating rate was 20°C / min in a water vapor atmosphere, calcined at 500°C for 4h, and then cooled to room temperature under nitrogen protection. The obtained steam-modified molecular sieve was impregnated with 5 mol / L citric acid solution at 80° C. for 1 h, and then calcined at 650° C. for 3 h to obtain the desired modified ZSM-5 molecular sieve.

[0038] Weigh an appropriate amount of zinc nitrate and zirconium nitrate and dissolve them in deionized water, and load them on the above-mentioned modified ZSM-5 molecular sieve (pore volume is 0.55ml / g, specific surface area is 469m 2 / g, str...

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Abstract

The invention discloses a catalyst using a modified ZSM-5 molecular sieve as a carrier and a preparation method and application thereof. The preparation method of the catalyst includes the following steps that 1, a modified hydrogen type ZSM-5 molecular sieve carrier is obtained by using water vapor and an acid treated hydrogen type ZSM-5 molecular sieve having complexing properties; 2, zinc oxide and/or an additive oxide are introduced to the modified hydrogen type ZSM-5 molecular sieve carrier; 3, incomplete bromination treatment is conducted on the modified hydrogen type ZSM-5 molecular sieve carrier introduced with the zinc oxide. The catalyst prepared by adopting the method is used for methyl bromide to prepare isobutylene, and the selectivity of isobutene can be remarkably improved.

Description

technical field [0001] The invention relates to a supported catalyst with a modified ZSM-5 molecular sieve as a carrier, a preparation method and application thereof. Background technique [0002] Isobutene is an important basic organic chemical raw material. Its derivative products are numerous, the upstream and downstream industrial chains are complicated, and the consumption structure shows a trend of diversification. A variety of high value-added products can be prepared from isobutylene, such as: butyl rubber, polyisobutylene, methyl tert-butyl ether, isoprene and organic glass and other organic chemical raw materials and fine chemical products. As the market scale of isobutene downstream products continues to expand, the contradiction between supply and demand will gradually become prominent, especially in the context of the depletion of oil resources, the output of isobutene has become a key bottleneck restricting the development of downstream industries. Therefore, ...

Claims

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Application Information

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IPC IPC(8): B01J29/40C07C1/26C07C11/09
Inventor 孙晓丹张舒冬张信伟李杰倪向前张喜文刘继华
Owner CHINA PETROLEUM & CHEM CORP
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