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Copper-based catalyst for preparing ethylene glycol and ethylene glycol monomethyl ether by hydrogenation of dimethyl oxalate and preparation method thereof

A technology of ethylene glycol monomethyl ether and dimethyl oxalate, which is applied to the preparation of hydroxyl compounds, dehydration of hydroxyl-containing compounds to prepare ethers, ether preparations, etc., can solve the problems of not being able to directly obtain ethylene glycol monomethyl ether, and achieve excellent Hydrogenation activity and selectivity of ethylene glycol monomethyl ether, enhanced activity and stability, effect of high specific surface area

Inactive Publication Date: 2015-12-02
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The present invention solves the technical problem that ethylene glycol monomethyl ether cannot be directly obtained from dimethyl oxalate through continuous hydrogenation and one-step method in the original system, and provides a method to obtain ethylene glycol by catalytic hydrogenation of dimethyl oxalate in one step Novel catalyst for monomethyl ether and its preparation method

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Zirconia preparation: Dissolve 1.80g of zirconium oxychloride in an appropriate amount of ethanol. After fully dissolving, add 1.00g of hexagonal mesoporous molecular sieve HMS. After fully grinding in an agate mortar, add 150mL of ethanol, place in a round bottom flask and heat to reflux for 24 hours. After filtration, wash, dry at 100°C, gradually raise the temperature to 650°C at 2°C / min, and bake at this temperature for 20 hours. The carrier containing the template agent obtained in the previous step was dissolved in 2M NaOH solution to remove the silicon template, and dried to obtain zirconia.

[0024] Carrier modification and metal loading: 50ml of 0.02M H 2 SO 4 Aqueous solution, add dropwise to 50ml aqueous solution containing 2g zirconia at a constant speed, stir at 20°C for 4h, raise the temperature to 90°C and continue stirring until the solvent evaporates completely, bake at 120°C for 12h, heat up to 300°C in a muffle furnace at 5°C / min Keep at ℃ for 4h...

Embodiment 2

[0027] The preparation of zirconia is the same as in Example 1.

[0028] Carrier modification and metal loading:50ml of 0.08M H 2 SO 4 Aqueous solution, add dropwise to 50ml aqueous solution containing 2g zirconia at a constant speed, stir at 40°C for 4h, raise the temperature to 90°C and continue stirring until the solvent evaporates completely, bake at 110°C for 12h, heat up to 400°C in a muffle furnace at 5°C / min Keep at ℃ for 4h to get the carrier, denoted as S-ZrO 2 -2#. 12.08gCu(NO 3 ) 2· 3H 2 O, 7.53gMn(NO 3 ) 2 4H 2 O dissolved in 100ml H 2 O is made into a metal ion solution, the pH of the suspension is adjusted to 11~12 with ammonia water, stirred and reacted in a water bath at 40°C for 5 hours, and the solution containing S-ZrO is added dropwise at a uniform speed. 2 -Aqueous solution of 2# carrier. Continue to stir for 4 hours after the dropwise addition, increase the temperature of the water bath, and continue to stir and react at 80°C until the pH ...

Embodiment 3

[0031] The preparation of zirconia is the same as in Example 1.

[0032] Carrier modification and metal loading: 50ml of 0.20M H 2 SO 4 Aqueous solution, add dropwise to 50ml aqueous solution containing 2g zirconia at a constant speed, stir at 40°C for 3h, raise the temperature to 80°C and continue stirring until the solvent evaporates completely, bake at 140°C for 14h, heat up to 500°C at 10°C / min in the muffle furnace Keep at ℃ for 4h to get the carrier, denoted as S-ZrO 2 -3#. 9.66gCu(NO 3 ) 2· 3H 2 O, 5.02gMn(NO 3 ) 2 4H 2 O dissolved in 100ml H 2 O is made into a metal ion solution, the pH of the suspension is adjusted to 10~11 with ammonia water, stirred and reacted in a water bath at 45°C for 5 hours, and the solution containing S-ZrO is added dropwise at a uniform speed. 2 -Aqueous solution of 3# carrier. Continue to stir for 6 hours after the dropwise addition, increase the temperature of the water bath, and continue to stir the reaction at 80°C until t...

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Abstract

The invention belongs to the technical field of chemical industry, in particular to a copper-based catalyst used for gas-phase catalytic hydrogenation of dimethyl oxalate to synthesize ethylene glycol and ethylene glycol monomethyl ether and a preparation method thereof. The catalyst uses modified zirconia as a carrier, and is loaded with copper and other additive metals. The preparation method is as follows: firstly adopt the improved hard template method to prepare zirconia; carry out acidification modification treatment on zirconia; add soluble copper salt and soluble additive metal salt to the above suspension, and use the ammonia distillation method to carry out metal loading. Stop the reaction when the pH of the suspension is 6-10; filter the above suspension, wash the filter cake, dry, and roast to obtain a powder catalyst for gas-phase catalytic hydrogenation of dimethyl oxalate. The advantage of the invention is that the yield of ethylene glycol monomethyl ether can reach 80% under the condition of lower liquid hourly space velocity, and the yield of ethylene glycol can reach 90% under the condition of higher liquid hourly space velocity; the preparation method of the catalyst is simple, Good stability and good industrial application prospect.

Description

technical field [0001] The invention belongs to the technical field of chemical industry, and in particular relates to a high-efficiency copper-based catalyst for preparing ethylene glycol and ethylene glycol monomethyl ether by gas-phase catalytic hydrogenation of dimethyl oxalate and a preparation method thereof. Background technique [0002] Ethylene glycol, also known as glycol, is an important organic chemical raw material. Ethylene glycol is widely used in the synthesis of polyester polyester, polyester resin, hygroscopic agent, plasticizer, surfactant, etc. Ethylene glycol is an important raw material for the synthesis of polyethylene terephthalate (PET). Fiber-grade PET, namely polyester fiber, is widely used in the manufacture of clothing fabrics and industrial products; bottle-grade PET is widely used in the packaging industry, electronics Electrical appliances, medical and health care, construction, automobiles and other fields. In addition, ethylene glycol can ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/889B01J23/80B01J23/745B01J23/75B01J23/72B01J35/10C07C31/20C07C29/149C07C43/13C07C41/09
CPCY02P20/52
Inventor 戴维林崔园园温超
Owner FUDAN UNIV