Search

CN-122010680-A - Method for producing diol compounds by one-step synthesis gas

CN122010680ACN 122010680 ACN122010680 ACN 122010680ACN-122010680-A

Abstract

The application discloses a method for producing glycol compounds by a one-step method of synthesis gas, belonging to the technical field of catalytic chemistry. The method comprises the steps of contacting raw material gas containing water, carbon monoxide and hydrogen with a catalyst to react to obtain glycol compounds, wherein the catalyst is at least one selected from mordenite, ZSM-5, ZSM-23, na-type Y molecular sieve and H-type Y molecular sieve. In the method, the one-step continuous production of the diol compound can be realized by taking the synthesis gas and the water as raw materials in the fixed bed reactor, and the conversion rate of carbon monoxide and the selectivity of the diol compound can be effectively improved by adjusting the proportion of the synthesis gas and the water, the catalyst activation condition and the catalytic reaction condition, so that the continuous production of one or more diol compounds including methyl glycol, ethylene glycol and 1, 4-butanediol and one or more alcohol products including methanol and ethanol can be realized, and the method has high selectivity.

Inventors

  • LIU SHUXIN
  • Zong Xiaotong
  • PEI RENYAN
  • WANG GUOJIAN
  • WANG HUI

Assignees

  • 延长中科（大连）能源科技股份有限公司

Dates

Publication Date
20260512
Application Date
20260121

Claims (10)

  1. 1. A process for producing glycol compounds from synthesis gas in a one-step process comprising: The method comprises the steps of (1) contacting raw material gas containing water, carbon monoxide and hydrogen with a catalyst, and reacting to obtain glycol compounds; Wherein, the water is heated and vaporized and then mixed with carbon monoxide and hydrogen to form the feed gas; The catalyst is at least one selected from mordenite, ZSM-5, ZSM-23, na-type Y molecular sieve and H-type Y molecular sieve.
  2. 2. The method according to claim 1, wherein the molar ratio of carbon monoxide, hydrogen and water in the raw material gas is (1-400): 1; preferably, the molar ratio of carbon monoxide to water in the raw material gas is 20-100:1; Preferably, the molar ratio of the hydrogen to the water in the raw material gas is 20-100:1.
  3. 3. The method of claim 1, wherein the catalyst has a silicon to aluminum ratio of 20-100:1.
  4. 4. The method according to claim 1, wherein the temperature of the reaction is 100-400 ℃; preferably, the temperature of the reaction is 150-300 ℃.
  5. 5. The method according to claim 1, wherein the pressure of the reaction is 0.5-10.0 MPa; Preferably, the pressure of the reaction is 0.5-6.0 MPa.
  6. 6. The method according to claim 1, wherein the total space velocity of the raw materials is 3-15 h -1 ; Preferably, the total airspeed of the raw materials is 5-10 h -1 .
  7. 7. The method of claim 1, further comprising activating the catalyst prior to contacting the feedstock comprising water, carbon monoxide and hydrogen with the catalyst; The activating step comprises the step of sequentially carrying out reducing gas purging and carrier gas purging on the catalyst at the activating temperature.
  8. 8. The method of claim 7, wherein the reducing gas is selected from at least one of hydrogen, carbon monoxide, pyridine; The carrier gas is selected from at least one of nitrogen, helium and argon; Preferably, the reducing gas is hydrogen and/or carbon monoxide.
  9. 9. The method of claim 7, wherein the activation temperature is 100-400 ℃ and the activation time is 2-48 hours; preferably, the activation temperature is 150-250 ℃.
  10. 10. The process of claim 1, wherein the apparatus used for the reaction is a fixed bed reactor or a tank reactor.

Description

Method for producing diol compounds by one-step synthesis gas Technical Field The application relates to a method for producing glycol compounds by a one-step method of synthesis gas, belonging to the technical field of catalytic chemistry. Background The diol compound is an organic compound containing two hydroxyl groups, is widely applied to the fields of polyester synthesis, antifreeze, medical intermediates, cosmetics and the like, and mainly comprises ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and the like. At present, the production of glycol compounds is mainly carried out by taking low-carbon olefin represented by ethylene and propylene as raw materials and oxidizing and hydrating the low-carbon olefin. However, with the increasing lack of global petroleum resources and the influence of long-term high-order operation of crude oil prices, the preparation cost of glycol compounds by using olefins as raw materials is higher and higher, and with the increasing demand of the market for glycol compounds today, it is very necessary to find a method for preparing glycol compounds from cheap raw materials. Under the natural condition of rich coal and natural gas resources in China, the synthesis gas becomes an ideal industrial synthesis raw material. And researchers have found that synthesis gas has the feasibility and potential of producing glycol compounds at a theoretical level. For example, a technical method for preparing dimethyl oxalate from synthesis gas and preparing ethylene glycol by hydrogenation of dimethyl oxalate is disclosed in the prior art. However, this process has a number of disadvantages, including the purity of the intermediates and the production of byproducts during the multi-step reaction, which can severely affect the difficulty in separating and purity of the ethylene glycol product. Meanwhile, some of the work about the one-step process for preparing glycol compounds from synthesis gas is reported, but all the work needs to be performed under the homogeneous reaction condition of high pressure (100-1700 atm) by using a system of combining a transition metal carbonyl compound with a ligand, so that the process can only be performed at the laboratory level and cannot realize industrial application. The existing production methods of glycol compounds are step-by-step production processes, so that the problems of influence of reaction intermediates and byproducts on the purity of the products, raw material loss in each step and the like almost exist in the production process. Disclosure of Invention In order to solve at least one problem of difficult industrialization, high cost and complex flow caused by depending on noble metal, high-pressure harsh conditions or multi-step reaction in the prior art of diol compounds, the application provides a technical scheme for producing the diol compounds by a one-step synthesis gas method by taking water as a raw material. The method is used in the reaction process of producing the diol compound by the synthesis gas one-step method, and has the advantages of high carbon monoxide conversion rate, strong diol compound selectivity and the like. The application adopts the following technical scheme: according to a first aspect of the present application there is provided a process for the one-step production of a glycol compound from synthesis gas comprising: The method comprises the steps of (1) contacting raw material gas containing water, carbon monoxide and hydrogen with a catalyst, and reacting to obtain glycol compounds; The catalyst is at least one selected from mordenite, ZSM-5, ZSM-23, na-type Y molecular sieve and H-type Y molecular sieve. Wherein the water is heated and vaporized and then mixed with carbon monoxide and hydrogen to form the feed gas. The glycol compound product contains methyl glycol, ethylene glycol and 1, 4-butanediol, and also contains other alcohol products including methanol and ethanol. Optionally, the molar ratio of carbon monoxide, hydrogen and water in the raw material gas is (1-400): 1. Optionally, the molar ratio of carbon monoxide to water in the raw material is 20-100:1. Optionally, the molar ratio of hydrogen to water in the raw material is 20-100:1. Optionally, the silicon-aluminum ratio of the catalyst is 20-100:1. Optionally, the temperature of the reaction is 100-400 ℃. Optionally, the reaction temperature is 150-300 ℃. Optionally, the pressure of the reaction is 0.5-10.0 MPa. Optionally, the pressure of the reaction is 0.5-6.0 MPa. Optionally, the total airspeed of the raw material is 3-8 h -1. Optionally, the total airspeed of the raw material is 3-6 h -1. Optionally, prior to contacting the feedstock containing water, carbon monoxide and hydrogen with the catalyst, further comprising activating the catalyst; The activating step comprises the step of sequentially carrying out reducing gas purging and carrier gas purging on the catalyst at the activating temperature. Optionally, the reduci