A copper-silicon catalyst modified by silanization of a tertiary amino-containing silane coupling agent and its preparation method and application

A technology of tertiary amino silane coupling agent silane and tertiary amino silane coupling agent, which is applied in the field of copper-silicon catalyst and its preparation, gas-phase ester hydrogenation catalyst, and can solve the problem of separation cost and energy consumption increase, copper species Catalyst deactivation, catalyst coking deactivation and other problems, to achieve the effect of reducing the selectivity of by-products, improving stability and conversion frequency, and promoting desorption

Active Publication Date: 2021-06-01
TIANJIN UNIV
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  • Application Information

AI Technical Summary

Problems solved by technology

One is that the silanol on the surface of the copper-silicon catalyst has a certain degree of alkalescence, and the side reaction Guerbet reaction generates alcohols containing three or four carbon atoms as a by-product (hereinafter also used C 3,4 -OH), such as 1,2-butanediol and 1,2-propanediol, the reaction by-products 1,2-butanediol and ethylene glycol have close boiling points, resulting in a significant increase in separation costs and energy consumption; the second is the initial hydrogenation product Methyl glycolate is easy to adsorb and polymerize on the isolated silanol on the surface of the catalyst, resulting in coking and deactivation of the catalyst, and the silanol on the surface of the catalyst may also react with the product methanol to form tetramethoxysilane. Long-term use of the catalyst silica carrier will gradually Corroded, resulting in agglomeration of copper species and catalyst deactivation
In addition, the conversion frequency of the hydrogenation of dimethyl oxalate to ethylene glycol needs to be further improved

Method used

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  • A copper-silicon catalyst modified by silanization of a tertiary amino-containing silane coupling agent and its preparation method and application
  • A copper-silicon catalyst modified by silanization of a tertiary amino-containing silane coupling agent and its preparation method and application
  • A copper-silicon catalyst modified by silanization of a tertiary amino-containing silane coupling agent and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-3

[0041] Example 1-3: 10Cu / SiO 2 -0.93N, 20Cu / SiO 2 -0.93N, 30Cu / SiO 2 -0.93N

[0042] Embodiment 1-3 is 10Cu / SiO 2 -0.93N, 20Cu / SiO 2 -0.93N, 30Cu / SiO 2 - Preparation of 0.93N with 10Cu / SiO 2 -0.93N means that the copper metal loading in the ammonia-distilled copper-silicon catalyst is 10wt.%, the nitrogen element accounts for 0.93wt.% of the catalyst weight, and the modified group includes a tertiary amino group, 20Cu / SiO 2 -0.93N, 30Cu / SiO 2 -0.93N and 10Cu / SiO 2 -0.93N differs only in copper loading. The active species copper loading and nitrogen element content in the catalyst of the present invention are respectively characterized by an inductively coupled plasma emission spectrometer and an elemental analyzer.

[0043] The specific preparation method is as follows: Weigh 1g 10Cu / SiO 2 , 20Cu / SiO 2 and 30Cu / SiO 2 Dissolve in 125mL of anhydrous methanol, add 0.0867g of N,N-diethylaminopropyltrimethoxysilane dropwise at 30°C, raise the temperature to 80°C after t...

Embodiment 4-5

[0044] Example 4-5: 20Cu / SiO 2 -1.41NH, 20Cu / SiO 2 -0.95NH 2

[0045] Embodiment 4-5 is 20Cu / SiO 2 -1.41NH, 20Cu / SiO 2 -0.95NH 2 Preparation, where 20Cu / SiO 2 -1.41NH means that the copper loading in ammonia-distilled copper-silicon catalyst is 20wt.%, the nitrogen element accounts for 1.41wt.% of the catalyst weight, and the modification group does not contain tertiary amino groups but contains secondary amino groups. 20Cu / SiO 2 -0.95NH 2 The modifying group only contains primary amino groups, the copper metal loading in the ammonia-distilled copper-silicon catalyst is 20wt.%, and the nitrogen element accounts for 0.95wt.% of the weight of the catalyst.

[0046] The specific preparation method is as follows: 1g 20Cu / SiO 2 Dissolve in 125mL of anhydrous methanol, add 0.368mmol nitrogen-containing silane coupling agent dropwise at 30°C, that is, add 0.0819g N-(2-aminoethyl)-3-aminopropyltrimethoxy dropwise Silane or 0.0660g of 3-aminopropyltrimethoxysilane, after the d...

Embodiment 6-7

[0047] Example 6-7: 20Cu / SiO 2 -0.27N, 20Cu / SiO 2 -1.65N

[0048] Embodiment 6-7 is 20Cu / SiO 2 -0.27N, 20Cu / SiO 2 - Preparation of 1.65N with 20Cu / SiO 2 -0.27N means that the copper metal loading in the ammonia-distilled copper-silicon catalyst is 20wt.%, the nitrogen element accounts for 0.27wt.% of the catalyst weight, and the modified group includes a tertiary amino group, 20Cu / SiO 2 -Nitrogen in 1.65N accounts for 1.65wt.% of catalyst weight, others are the same as 20Cu / SiO 2 -0.27N is the same.

[0049] The specific preparation method is as follows: 1g 20Cu / SiO 2 Dissolve in 125mL of anhydrous methanol, add 0.0095g and 0.1844g of N,N-diethylaminopropyltrimethoxysilane dropwise at 30°C respectively, raise the temperature to 80°C after the dropwise addition, and stir at reflux for 6h. The cooled solution was centrifugally washed and dried overnight at 80° C. to obtain a copper-silicon catalyst modified with a tertiary amino silane coupling agent. The catalyst is pre...

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Abstract

The invention discloses a copper-silicon catalyst modified by silylation of a tertiary amino group-containing silane coupling agent, which comprises copper species, silica and silica modified by silylation of a tertiary amino group-containing silane coupling agent; The copper species accounts for 10-30wt.% of the copper-silicon catalyst, and the silica accounts for 60-85wt.% of the copper-silicon catalyst. 0.1-2 wt.% of the copper-silicon catalyst weight. The invention also discloses a preparation method of the catalyst and its use in hydrogenation of dimethyl oxalate to produce ethylene glycol. After the copper-silicon catalyst of the invention is modified by the tertiary amino silylation coupling agent, the catalytic activity and stability are improved, and at the same time, the basicity of the catalyst is weakened, and the generation of by-products is suppressed. When the copper-silicon catalyst modified by silanization of the tertiary amino group-containing silane coupling agent is used for the hydrogenation of dimethyl oxalate to produce ethylene glycol, the conversion frequency is obviously higher than that of the tertiary amino group-containing and secondary amino group-containing copper-silicon catalysts. Silane coupling agent silanization modified copper-silicon catalyst.

Description

technical field [0001] The invention belongs to the technical field of catalysts, and relates to a gas-phase ester hydrogenation catalyst, in particular to a copper-silicon catalyst modified by silanization with a tertiary amino-containing silane coupling agent, and a preparation method and application thereof. Background technique [0002] Ethylene Glycol (EG) is an essential chemical product widely used as a solvent, antifreeze, PET raw material, etc. Compared with the petroleum-derived route, the process of producing MEG from coal has become more and more attractive. The process consists of three steps: pressurized gasification of coal to generate syngas, carbon monoxide obtained by catalytic coupling reaction Dimethyl oxalate (DMO), and hydrogenation of dimethyl oxalate to ethylene glycol. Due to the abundance of syngas resources, short process flow and low cost, this process has become one of the main development directions of my country's coal chemical industry. As a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/72B01J31/02B01J35/02B01J35/10C07C29/149C07C31/20
CPCB01J23/72B01J31/0274B01J31/0275B01J35/023B01J35/1019B01J35/1038B01J35/1042B01J35/1061B01J2231/641C07C29/149C07C31/202Y02P20/52
Inventor 王悦马新宾王美琳吕静黄守莹赵玉军王胜平
Owner TIANJIN UNIV
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