High-activity propylene gas-phase epoxidation catalyst and preparation method thereof

A catalyst, epoxidation reaction technology, applied in physical/chemical process catalysts, molecular sieve catalysts, chemical instruments and methods, etc., can solve the problems of ineffective decomposition of hydrogen peroxide, limit the number of TS-1 molecular sieve Ti active sites, etc., to improve the load efficiency and stability, reducing synthesis costs, and reducing the effect of ineffective decomposition

Inactive Publication Date: 2021-06-01
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The research results show that in order to obtain highly active Au species and as many epoxidized Ti centers as possible, and in order to get closer to the reactants, most of the existing technologies use titanium-silicon molecular sieves to be synthesized and then modified, thus exposing More Ti active sites and generate more defect sites for Au loading, and amorphous Ti species can lead to ineffective decomposition of hydrogen peroxide
[0004] The existing technology shows that the theoretical limit of the framework titanium content in the titanium-silicon molecular sieve is 2.5%, that is, the silicon-titanium ratio is 40:1. This result limits the number of Ti active sites in the TS-1 molecular sieve
Some researchers have achieved the purpose of increasing the framework titanium by reducing the ratio of silicon to titanium, but at the same time it will also bring about a large number of amorphous titanium species.

Method used

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  • High-activity propylene gas-phase epoxidation catalyst and preparation method thereof
  • High-activity propylene gas-phase epoxidation catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] 45gSiO 2 Add 30% silica sol into a jacketed three-necked flask, add 0.05g soluble starch, 44g 25wt% TPAOH aqueous solution and 38g water, and hydrolyze at 40°C for 2h to obtain a silicon source hydrolysis mixture; 3.8g tetrabutyl titanate Dissolve in 18.7g of isopropanol, then stir for 30min to obtain the titanium source hydrolysis mixture; mix the titanium source and the silicon source hydrolysis mixture, remove the alcohol at 80°C for 1.5h, replenish 50.2g of water and stir for 30min, and the obtained Put the transparent glue into a crystallization kettle to crystallize, and crystallize at 170°C for 36 hours. After washing and drying, the crystallized product is washed with 1M HCl aqueous solution (the liquid-solid ratio is 50ml g -1 ), calcined in air at 550°C for 6h, and obtained a TS-1 sample with a Si / Ti ratio of 31.8 after XRF testing. Repeat the Au loading process in Comparative Example 1 to obtain a catalyst of 0.38% Au / TS-1-D.

Embodiment 2

[0044] Repeat Example 1, replace the soluble starch in the defect site auxiliary agent in the preparation process of TS-1 with sodium carboxymethylcellulose, polyacrylamide, polyethyleneimine, the amount of the component substances remains unchanged, after crystallization, Adopt 1M HCl aqueous solution washing after drying (liquid-solid ratio is 50ml g -1 ), calcined in air at 550°C for 6h, and obtained TS-1 samples with Si / Ti ratios of 31.7, 31.9, and 31.8 after XRF testing.

[0045] The loading process of Au in Comparative Example 1 was repeated to obtain catalysts of 0.38% Au / TS-1-E, 0.38% Au / TS-1-F, and 0.38% Au / TS-1-G.

Embodiment 3

[0047] Repeat Example 1, the tetraethyl orthosilicate in the TS-1 preparation process is replaced by tetramethyl orthosilicate, tetrapropyl orthosilicate, the amount of tetrabutyl orthosilicate component material remains unchanged, After crystallization, adopt 1M HCl aqueous solution washing after drying (liquid-solid ratio is 50ml g -1 ), calcined in air at 550°C for 6h, and obtained TS-1 samples with Si / Ti ratios of 32.1, 31.9, and 32.0 through XRF testing.

[0048] The Au loading process in Comparative Example 1 was repeated to obtain catalysts of 0.38% Au / TS-1-H, 0.38% Au / TS-1-I, and 0.38% Au / TS-1-J.

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PUM

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Abstract

The invention discloses a high-activity propylene gas-phase epoxidation catalyst and a preparation method thereof. In the preparation process of the catalyst, a defect site auxiliary agent and an S auxiliary agent are added, a large number of defect sites which are rich in titanium and suitable for Au loading are obtained, amorphous species on the catalyst are stabilized by S, the high-activity propylene gas-phase epoxidation catalyst is obtained, and the conversion rate of propylene, the selectivity of PO and the hydrogen efficiency are greatly improved.

Description

technical field [0001] The invention belongs to the technical field of catalytic synthesis, and in particular relates to a preparation method for a propylene gas-phase epoxidation catalyst. Background technique [0002] At present, the production units of the liquid-phase HPPO process all use methanol as the solvent. However, the methanol solvent also brings a lot of trouble to the HPPO process. First, methanol is prone to solvolysis side reactions with propylene oxide products to generate high-boiling point propylene glycol monomethyl ether and other by-products. These by-products not only seriously reduce the selectivity of propylene oxide, but also increase the difficulty of wastewater treatment. Secondly, methanol solvent must be recycled, and complex refining treatment (including hydrogenation, rectification and resin adsorption) is required before recycling, which leads to complex HPPO process and high investment and energy consumption. What's worse, the circulating...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/89C07D301/12C07D303/04
CPCB01J29/89B01J2229/18C07D301/12C07D303/04Y02P20/52
Inventor 黄家辉贾玉华吕强龙化云
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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