High-stability copper-based catalyst for preparing ethylene glycol by hydrogenating dimethyl oxalate and preparation method of high-stability copper-based catalyst

Abstract

The invention discloses a high-stability copper-based catalyst for preparing ethylene glycol by hydrogenating dimethyl oxalate and a preparation method of the high-stability copper-based catalyst. Thecatalyst is prepared from the following components by weight percent: 10 to 50 percent of metal copper, 38 to 89.8 percent of carrier, 0.1 to 2 percent of additives, and 0.1 to 10 percent of hydrophobic groups. The catalyst is designed according to the characteristic of the dimethyl oxalate raw material containing trace water, an inorganic oxide is used as a catalyst carrier, and the non-modifiedcopper-based catalyst is prepared according to a conventional catalyst preparation method; and the hydrophobic groups are grafted onto the surface of the non-modified copper-based catalyst by adopting a heating refluxing method, an ultrasonic method or a fumigation method, thereby preparing the hydrophobic modified copper-based catalyst. By virtue of the hydrophobic treatment on the surface of the catalyst, a hydrophobic micro environment is built on the surface of the catalyst, so that the absorption of impurities such as trace water on the surface of the catalyst is selectively reduced, thewater resistance and acid resistance of the catalyst can be effectively improved, and the stability of the catalyst is greatly improved on the premise of not influencing the reaction activity of thecatalyst.

Description

technical field [0001] The invention belongs to the technical field of catalysts and their preparation, and in particular relates to a highly stable copper-based catalyst for hydrogenating dimethyl oxalate to prepare ethylene glycol and a preparation method thereof. Background technique [0002] Vigorously develop the synthesis technology of coal-based bulk chemicals, which is in line with the major strategic needs of national development. Coal-to-ethylene glycol, as an important way of coal-based synthesis of bulk chemicals, has attracted wide attention in recent years. Hydrogenation of dimethyl oxalate to ethylene glycol The stability of copper-based catalysts is generally considered to be one of the biggest difficulties in the industry. The literature (Industrial Catalysis, 2015, 23(2): 98-102) analyzes the deactivation reasons of copper-based catalysts for this reaction, focusing on catalyst sintering, carbon deposition, poisoning, solvents, reaction atmosphere and physi...

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Problems solved by technology

[0003] Dimethyl oxalate contains a small amount of water in the feed component of dimethyl oxalate hydrogenation in the industry. In the actual production process, the water content in the dimethyl oxalate solution is required to be less than 0.1%. High water content will cause dimethyl oxalate to be hydrolyzed into oxalic acid. , oxalic acid reacts with copper, the active component of the hydrogenation catalyst, to form copper oxalate, which changes the structure of the catalyst, causing catalyst pulverization and resulting in a decrease in stability (Henan Chemical Industry, 2017, 34(4):44-46)

In order to improve the stability of copper-based catalysts, generally by adding additives or changing the carrier (Petrochemical Industry, 2014, 43 (9): 985-994), starting from the situation that the industrial feed contains a small amount of water, the copper-based catalyst surface Hydrophobic treatment to improve the stability of the catalyst has not been reported

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