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Solid heterogeneous catalyst used for preparation method using ethylene oxide, carbon dioxide and methanol to prepare dimethyl carbonate and ethylene glycol and preparation method of solid heterogeneous catalyst

A heterogeneous catalyst, the technology of dimethyl carbonate, is applied in the preparation of carbon dioxide or inorganic carbonate, the preparation of oxygenated compounds, chemical instruments and methods, etc. Problems such as poor product selectivity, to achieve the effects of high conversion rate and product selectivity, high product quality, and short reaction process

Inactive Publication Date: 2017-11-21
SHAANXI COAL & CHEM TECH INST
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  • Abstract
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  • Claims
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Problems solved by technology

However, the above-mentioned catalysts are all homogeneous systems, and there are many deficiencies in separation and service life, and catalyst residues have a great impact on product quality
[0006] The use of solid heterogeneous catalysts is the best way to solve the above problems. However, the heterogeneous catalysts reported so far have low activity or poor product selectivity without the use of homogeneous co-catalysts.
Arai et al. tested the reactivity of metal oxides such as magnesium oxide, zinc oxide, lanthanum oxide, and cerium oxide in the reaction of ethylene oxide, carbon dioxide, and methanol: at 150°C and 8 MPa, reacted for 15 hours, and ethylene oxide Transformation efficiency 96.1%, dimethyl carbonate selectivity 28%, ethylene glycol selectivity 26.3% (Applied Catalysis A: General, 2001, 219: 259), product selectivity is higher, but the reaction time is longer, catalyst activity is not high
In this reaction, Dai et al. tested the catalytic activity of metal oxides such as magnesium oxide and zinc oxide and ion exchange resins such as Lewatit MP500 and Amberlyst A21. They reacted at 120°C and 5-15MPa for 3-10h, and the conversion rate of ethylene oxide was 11.9 -37.2%, dimethyl carbonate selectivity 4.3-30.2%, ethylene glycol selectivity 4.5-30.5% (Industrial&Engineering Chemistry Research, 2003,42: 3865), product selectivity is higher, but oxirane conversion rate is lower low catalyst activity
Other studies have shown that solid heterogeneous catalysts with high activity are less selective to the product in this reaction

Method used

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preparation example Construction

[0034] The present invention is used for the preparation method of the solid heterogeneous catalyst of ethylene oxide, carbon dioxide and methyl alcohol preparation dimethyl carbonate and ethylene glycol, comprises the steps:

[0035] Step 1. Carrier pretreatment

[0036] The carrier material, that is, the modified resin material (chlorinated polyethylene, chlorinated polypropylene or chloromethylated polystyrene) is vacuum-dried at 20-200°C for 0.5-48h.

[0037] Step 2, active component 1 is immobilized

[0038] Mix the carrier obtained in step 1 and the active component imidazole at a mass ratio of 1.0:(0.1-0.7), react at 20-200°C for 0.5-48h, filter, wash and dry.

[0039] Step 3, active component 2 is immobilized

[0040] Mix the solid and active component 2 halogen-containing organic matter (2-bromoethanol or 1,2-dibromoethane) obtained in step 2 at a mass ratio of 1.0: (0.5-1.5), and react at 20-200°C for 0.5 -48h, the obtained solid is filtered, washed with ethyl ace...

Embodiment 1

[0044] Step 1. Carrier chloromethylated polystyrene is vacuum-dried at 80° C. for 12 hours;

[0045] Step 2. Take 10 g of the solid obtained in step 1, mix it with 3.6 g of imidazole and react at 80°C for 8 hours;

[0046] Step 3, the solid obtained in step 2 is filtered, washed with ethyl acetate, water, and methanol, and then vacuum-dried at 80°C;

[0047] Step 4, reacting 10 g of the solid obtained in step 3 and 7 g of 2-bromoethanol at 80° C. for 8 h;

[0048] Step 5. The solid obtained in Step 4 is filtered, washed with ethyl acetate and methanol, and then vacuum-dried at 80° C. to obtain a solid heterogeneous catalyst.

[0049] Put 0.5 g of the solid heterogeneous catalyst material obtained in step 5 into a 200 ml autoclave, and close the autoclave. Add 80g of ethylene oxide / methanol solution with a mixing ratio of 1:4 into the reactor, then fill it with 1MPa carbon dioxide, heat up to 170°C to start the reaction, and after 2 hours, the conversion rate of ethylene oxid...

Embodiment 2

[0051] Step 1. The carrier chlorinated polyethylene is vacuum-dried at 100° C. for 8 hours;

[0052] Step 2. Take 10g of the solid obtained in step 1, mix it with 7g of imidazole and react at 120°C for 6h;

[0053] Step 3, the solid obtained in step 2 is filtered, washed with ethyl acetate, water, and methanol, and then vacuum-dried at 80°C;

[0054] Step 4. React 10 g of the solid obtained in step 3 and 15 g of 2-bromoethanol at 120° C. for 6 h;

[0055] Step 5. The solid obtained in step 4 is filtered, washed with ethyl acetate and methanol, and then vacuum-dried at 120° C. to obtain a solid heterogeneous catalyst.

[0056] Put 0.5 g of the solid heterogeneous catalyst material obtained in step 5 into a 200 ml autoclave, and close the autoclave. Add 80g of ethylene oxide / methanol solution with a mixing ratio of 1:4 into the reactor, then fill it with 1MPa carbon dioxide, heat up to 170°C to start the reaction, and after 2 hours, the conversion rate of ethylene oxide is 100...

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Abstract

The invention discloses a solid heterogeneous catalyst used for a preparation method using ethylene oxide, carbon dioxide and methanol to prepare dimethyl carbonate and ethylene glycol. The solid heterogeneous catalyst comprises 1.0 part of carrier, 0.1-0.7 part of active component 1 and 0.5-1.5 parts of active component 2, wherein the carrier is modified resin material chlorinated polyethylene, chlorinated polypropylene or chloromethylated polystyrene; the active component 1 is imidazole; the active component 2 is a halogen-containing organic compound 2-bromoethanol or 1, 2-dibromoethane. A preparation method of the solid heterogeneous catalyst includes: preprocessing the carrier, and immobilizing the active component 1 and the active component 2 to obtain the solid heterogeneous catalyst. Compared with existing catalysts which are high in activity but low in product selectivity or high in product selectivity but low in activity, the solid heterogeneous catalyst is high in conversion rate and product selectivity.

Description

technical field [0001] The invention belongs to the technical field of chemical catalysts, in particular to a solid catalyst for cycloaddition and transesterification one-pot reaction, and more particularly to a one-pot method for preparing dimethyl carbonate and ethylene oxide from ethylene oxide, carbon dioxide and methanol Solid heterogeneous catalysts for diols and methods for their preparation. Background technique [0002] Dimethyl carbonate and ethylene glycol have important uses in the chemical industry. Among them, dimethyl carbonate can replace highly toxic methyl chloride, phosgene, dimethyl sulfate and other reagents for methylation, methoxylation, carbonylation and other reactions, and is widely used in medicine, synthetic materials, coatings, polymers, etc. Carbonate and other fields. Ethylene glycol is an important basic chemical raw material, mainly used in the production of polyester, and is the second most consumed alcohol after methanol. [0003] In my ...

Claims

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Application Information

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IPC IPC(8): B01J31/02C07C27/00C07C29/128C07C68/04C07C69/96C07C31/20
CPCB01J31/0231B01J31/0244B01J31/06B01J2231/49C07C29/128C07C68/04C07C69/96C07C31/202Y02P20/141Y02P20/52
Inventor 王一张国权李洪广张生军郑化安
Owner SHAANXI COAL & CHEM TECH INST