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Copper-based catalyst used in preparation of glycol by catalytic hydrogenation of oxalate ester and preparation method thereof

A copper-based catalyst, a technology for hydrogen production, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc., can solve the problem of poor catalyst stability, loss of activity, instability, etc. problem, to achieve the effect of large selectivity, high selectivity and high stability

Inactive Publication Date: 2013-04-10
河南能源集团研究总院有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The active site of the hydrogenation catalyst is Cu +1 , the main reason for the poor stability of the catalyst is the active site Cu +1 Unstable during the reaction, easily converted to Cu 0 , thereby inactivating the

Method used

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  • Copper-based catalyst used in preparation of glycol by catalytic hydrogenation of oxalate ester and preparation method thereof
  • Copper-based catalyst used in preparation of glycol by catalytic hydrogenation of oxalate ester and preparation method thereof
  • Copper-based catalyst used in preparation of glycol by catalytic hydrogenation of oxalate ester and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] Dissolve 1.13g of copper nitrate and 0.28g of polyvinylpyrrolidone 4000 in 500ml of absolute ethanol, transfer them to a Teflon-lined reactor, and react at 300°C for 4 hours. After cooling, transfer it to a beaker to obtain an ethanol suspension of copper oxide nanoparticles. Then add 800 ml of absolute ethanol, 1.0 L of deionized water, 50 ml of ammonia water, and 5 g of cetyltrimethylammonium bromide to the above suspension, stir evenly, and then add 10 ml of ethyl orthosilicate. Reacted for 12 hours, filtered, dried, and calcined at 500°C for 3 hours to obtain a copper-based catalyst with a core-shell structure, labeled as 10 wt.% Cu / SiO 2 .

[0017] The catalyst is granulated into 60-80 meshes, with 10% H 2 / N 2 Activity evaluation was carried out after in situ reduction, and the hydrogenation of oxalate to ethylene glycol was carried out. The results of selective hydrogenation are shown in Table 1.

[0018]

Embodiment 2

[0020] 3.82g of copper nitrate and 1.91g of polyvinylpyrrolidone 10000 were dissolved in 1000ml of absolute ethanol respectively, transferred to a Teflon-lined reactor, and reacted in a homogeneous reactor at 400°C for 5 hours. After cooling, transfer it to a beaker to obtain an ethanol suspension of copper oxide nanoparticles. Then add 1000ml of absolute ethanol, 1500ml of deionized water, 100ml of ammonia water, and 8g of cetyltrimethylammonium bromide to the above suspension, stir well and then add 15ml of ethyl orthosilicate. Reacted for 20 hours, filtered, dried, and calcined at 400°C for 4 hours to obtain a copper-based catalyst with a core-shell structure, marked as 20 wt.% Cu / SiO 2 .

[0021] The catalyst is granulated into 60-80 meshes, with 10% H 2 / N 2 Activity evaluation was carried out after in situ reduction, and the hydrogenation of oxalate to ethylene glycol was carried out. The results of selective hydrogenation are shown in Table 2.

[0022]

Embodiment 3

[0024] 8.73g of copper nitrate and 6.55g of polyvinylpyrrolidone 80000 were dissolved in 800ml of absolute ethanol respectively, transferred to a polytetrafluoroethylene-lined reactor, and reacted at 350°C for 4 hours. After cooling, transfer it to a beaker to obtain an ethanol suspension of copper oxide nanoparticles. Then add 2L of absolute ethanol, 1.6L of deionized water, 150ml of ammonia water, and 6g of cetyltrimethylammonium bromide to the above suspension, stir well and then add 10ml of ethyl orthosilicate. Reacted for 30 hours, filtered, dried, and calcined at 500°C for 6 hours to obtain a copper-based catalyst with a core-shell structure, marked as 30 wt.% Cu / SiO 2 .

[0025] The catalyst is granulated into 60-80 meshes, with 10% H 2 / N 2 Activity evaluation was carried out after in situ reduction, and the hydrogenation of oxalate to ethylene glycol was carried out. The results of selective hydrogenation are shown in Table 3.

[0026]

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Abstract

The invention provides a copper-based catalyst used in preparation of glycol by catalytic hydrogenation of oxalate ester and a preparation method thereof. The catalyst comprises 10 to 50 wt% of copper and 50 to 90 wt% of silica, and has a specific surface area of 200 to 1200 m<2> / g, a pore volume of 0.5 to 1.4 cm<3> / g, an average aperture of 1.5 to 15 nm and a particle size below 100 nm; copper oxide nanoparticles are cladded by a mesoporous silicon shell, and a core-shell structure is formed. The catalyst provided in the invention has the advantages of a small particle size, uniform particlesize distribution, good dispersibility, and high activity, high selectivity and a long life when used in preparation of glycol by catalytic hydrogenation of oxalate ester. The preparation method has the advantages of simple operation and high yield.

Description

technical field [0001] The invention relates to a catalyst and a preparation method thereof, in particular to a copper-based catalyst with a core-shell structure for oxalate hydrogenation to prepare ethylene glycol and a preparation method thereof. Background technique [0002] Catalytic hydrogenation of oxalate as raw material to prepare ethylene glycol can not only make full use of my country's relatively abundant coal resources and save seriously scarce oil resources, but also has the advantages of less environmental pollution, mild reaction conditions, continuous production, and high economic feasibility. The advantage is that it is an effective supplement for the preparation of ethylene glycol by the petroleum route. [0003] In the coal-to-ethylene glycol technology, the stability of the oxalate hydrogenation to ethylene glycol catalyst is generally considered to be the biggest difficulty in the industry. The copper-silicon system is the most common catalytic system. ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/72B01J35/02C07C31/20C07C29/149B01J35/00
CPCY02P20/52
Inventor 蒋元力尚如静穆仕芳王占修张秀全魏灵朝
Owner 河南能源集团研究总院有限公司
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