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Catalyst for preparing glycol through oxalate hydrogenation and preparation and application thereof

A catalyst, oxalate technology, applied in the preparation of hydroxyl compounds, metal/metal oxide/metal hydroxide catalysts, preparation of organic compounds, etc., can solve the problems of high impurity content, small liquid hourly space velocity, etc. Low temperature, stable reaction, and the effect of reducing separation equipment and processes

Active Publication Date: 2013-01-16
SHANGHAI HUAYI ENERGY CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The technical problem to be solved by the present invention is to overcome the defects in previous literatures, such as high hydrogen-ester ratio, small liquid hourly space velocity, and high content of impurities in the product, and provide a high-activity, high-selectivity gas-solid phase reaction catalyst. It is suitable for the hydrogenation of oxalate ester to ethylene glycol. It has the characteristics of low reaction temperature, high activity, wide activity temperature range, low hydrogen-ester ratio, high liquid hourly space velocity, and low content of impurities in the product. It reduces energy consumption and improves space-time Yield, reduce production cost

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0028] Catalyst preparation method:

[0029] Dissolve the silicate in ethanol, add deionized water, adjust the pH value between 0.1 and 5.0 with acidic substances, and then stir for 30 to 120 minutes at a temperature of 40 to 120 °C and a stirring speed of 50 to 500 rpm; Nitrates, sulfates, oxalates, acetates or halides are formulated into aqueous solutions with a concentration of 0.001-2.0M; the precipitants are formulated into aqueous solutions with a concentration of 0.001-8.0M, and the above-prepared solutions Mix with this aqueous solution to prepare a mixed solution; mix the above prepared several solutions evenly, then stir for 10-48 hours at a temperature of 40-120 °C and a stirring speed of 50-500 rpm; generate precipitates, filter and wash with deionized water , drying at 90-120° C. for 4-12 hours, calcining at 300-600° C. for 2-10 hours and molding to obtain the catalyst of the present invention.

Embodiment 1

[0033]Weigh 100g of tetraethoxysilane, dissolve it in 100mL of absolute ethanol, add 200mL of deionized water, adjust the pH value to 3.0 with nitric acid, stir at a temperature of 70°C and a stirring speed of 350rpm for 60min; weigh 70g of urea, dissolve in 150mL of deionized water; select copper nitrate to prepare 500mL of 1.0M aqueous solution; mix the above-mentioned solutions evenly, stir at a reaction temperature of 95°C and a stirring speed of 400rpm for 24 hours to form a precipitate, filter while hot and repeatedly wash and filter with deionized water The cake was obtained as a catalyst filter cake, which was dried at 95° C. for 4 hours, and baked at 400° C. for 4 hours after molding to obtain the catalyst Cu / SiO2 (A). The weight content of copper element in the catalyst was 40w%. Catalyst Cu / SiO2(A) was crushed and screened to 40-60 meshes, activated by reduction with pure hydrogen at 330°C for 6 hours, and then adjusted to the reaction process conditions for reaction...

Embodiment 2

[0035] Weigh 100g of tetramethoxysilane, add 200mL of deionized water, adjust the pH value to 1.0 with nitric acid, stir for 120min at a temperature of 70°C and a stirring speed of 350rpm; weigh (NH 4 ) 2 CO 3 144g, dissolved in 200mL deionized water; select copper acetate to prepare 800mL 0.5M aqueous solution; mix the above solutions evenly, stir at a reaction temperature of 110°C and a stirring speed of 450rpm for 18 hours to form a precipitate, filter and deionize while hot Wash the filter cake with water repeatedly to obtain a catalyst filter cake, dry it at 120°C for 4 hours, and bake it at 450°C for 4 hours after molding to obtain the catalyst Cu / SiO2 (B). The weight content of copper in the catalyst is 30w%. Catalyst Cu / SiO2 (B) was crushed and screened to 20-40 meshes; activated by reduction with pure hydrogen at 300°C for 6 hours, then adjusted to the reaction process conditions for reaction.

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Abstract

The invention relates to a catalyst for preparing glycol through oxalate hydrogenation and the preparation and the application thereof. The catalyst is a silica carrier which is prepared with copper oxide as the active component and silicon ester as the carrier. The catalyst is prepared through a sol-gel method and a coprecipitation method, and can be used for preparing polylol with polybasic ester as the reaction raw material. Experiments show that the catalyst has very high reactivity and glycol selectivity in glycol synthesis through oxalic ester and hydrogen, long service and stable reaction.

Description

technical field [0001] The invention relates to a catalyst for synthesizing ethylene glycol by vapor-phase hydrogenation of oxalic acid ester, its preparation and application. Background technique [0002] Ethylene glycol is an important organic chemical raw material, mainly used in the manufacture of polyester fibers, antifreeze, non-ionic surfactants, ethanolamine and explosives, and is also used to prepare low freezing point coolant (for engines), and can also be directly Used as a solvent. In addition, it is also widely used in the tobacco industry, textile industry and cosmetic industry. [0003] Most of the existing production processes of ethylene glycol adopt the petroleum route, that is, the direct oxidation method is used to produce ethylene oxide, and then ethylene glycol is produced through liquid phase catalysis or non-catalytic hydration. Such as Chinese patent 02112038.2, US patent 5874653, and Japanese patent 82106631 all disclose this route. In this metho...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/72C07C29/149C07C31/18C07C31/20
Inventor 唐大川吴良泉周亚明李永刚戴成勇王东辉肖本端施春辉
Owner SHANGHAI HUAYI ENERGY CHEM