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CN-121988308-A - Method for synthesizing glycerol carbonate from carbon dioxide, glycerol and propylene oxide

CN121988308ACN 121988308 ACN121988308 ACN 121988308ACN-121988308-A

Abstract

An Mg-M bimetallic oxide catalyst for synthesizing glycerin carbonate by a one-pot method of carbon dioxide, glycerin and propylene oxide. When the amount ratio of Mg to M substances is in a certain range, the catalyst has higher strong alkaline site and oxygen vacancy content, has stronger CO 2 adsorption activation capacity, and improves the reaction efficiency and the yield of the glycerin carbonate. The method for synthesizing the glycerin carbonate by adopting the one-pot method of the catalyst comprises the steps of mixing glycerin and propylene oxide, adding CO 2 for coupling reaction, wherein the reaction temperature is 100-160 ℃, the operating pressure is 1-4MPa CO 2 , and the reaction time is 1-4 hours. The process is simple, low in energy consumption and high in selectivity of corresponding glycerin carbonate.

Inventors

  • LIU YIBIN
  • SHEN QI
  • XU PEIPEI
  • YAN HAO
  • CHEN XIAOBO
  • YANG CHAOHE

Assignees

  • 中国石油大学(华东)

Dates

Publication Date
20260508
Application Date
20241104

Claims (10)

  1. 1. The catalyst for synthesizing the glycerin carbonate comprises an active component comprising Mg element and a second metal element, wherein the second metal element comprises one or a mixture of more than two of Ni, al, mn, co, sn, zr, cu, ca, li elements; Preferably, the second metal comprises one or a mixture of more than two of Al, ni, zr, li elements; More preferably, the second metal is an Al element.
  2. 2. The catalyst according to claim 1, wherein in the catalyst, the ratio of Mg to the amount of the substance of the second metal element is 1 (0.2-5) based on the amount of the substance of the metal element; Preferably, the ratio of the amount of the substance of Mg element to the second metal element is 1 (1-5).
  3. 3. The catalyst according to claim 1, wherein in the catalyst, the ratio of the amount of the substance of Mg element to the amount of the substance of Al element is 1 (2.0-3.5), Preferably, the ratio of the amounts of substances of Mg element and Al element is 1:3.
  4. 4. A process for preparing the catalyst of any one of claims 1 to 3, comprising: mixing soluble salt containing Mg element, soluble salt containing second metal element and sodium bicarbonate in a solution, adding a template agent, mixing to obtain a mixture A, crystallizing, centrifuging, drying and roasting the mixture A to obtain a catalyst; preferably, the template agent comprises P123 or tetrapropylammonium hydroxide; Preferably, the ratio of the amount of the substance of the template agent to the sum of the amounts of the substance of the Mg element and the second metal element is (0.004-0.012): 1; more preferably, the second metal element is Al, and the ratio of the amount of the template agent substance to the sum of the amounts of Mg and Al substances is (0.004-0.012): 1.
  5. 5. The process according to claim 4, wherein the ratio of the amounts of active metal and sodium bicarbonate is 1:1 to 1:4, preferably 1:3.
  6. 6. The method according to claim 4 or 5, wherein crystallization is carried out at 100 ℃ to 140 ℃ prior to the drying step; Preferably, the crystallization time is 10-20 hours.
  7. 7. The method according to any one of claims 4 to 6, wherein the firing temperature is controlled to 350 to 650 ℃; Preferably, the roasting temperature is controlled between 450 and 650 ℃; Preferably, the temperature rising speed is controlled to be 2.5-4 ℃ per minute in the roasting process.
  8. 8. A method for preparing glycerol carbonate, comprising: reacting glycerol, propylene oxide and carbon dioxide under the action of the catalyst of any one of claims 1-3 to obtain glycerol carbonate, wherein the reaction temperature is 100-160 ℃; Preferably, the reaction temperature is 120-140 ℃. At this range of temperatures; preferably, the reaction time is 1 to 4 hours.
  9. 9. The method of claim 8, wherein the mass ratio of glycerin to propylene oxide is from 1:1 to 1:10; Preferably, the ratio of the amount of glycerol to the amount of propylene oxide is from 1:2 to 1:6.
  10. 10. The method according to claim 8 or 9, characterized in that the ratio of the amount of catalyst to the substance of the substrate glycerol is 1:50 to 1:2000; Preferably, the ratio of the amount of material of the catalyst to the amount of material of the reactants is from 1:100 to 1:1000.

Description

Method for synthesizing glycerol carbonate from carbon dioxide, glycerol and propylene oxide Technical Field The invention relates to a preparation method of glycerin carbonate, in particular to a method for preparing amino acid by carbon dioxide, glycerin and epoxypropane through a one-pot method. Background At normal temperature and pressure, the glycerol carbonate is colorless liquid, and the purity of products produced by partial factories is low and is light yellow. The organic solvent has the advantages of high boiling point, nonflammability, no toxicity and pollution, easy dissolution in water, biodegradability and the like, can be used as a good green organic solvent and is widely applied to the fields of medical treatment, lubrication and the like. In addition, the glycerol carbonate has a double functional group structure, and carbonyl groups and hydroxyl groups on the glycerol carbonate can further carry out various reactions such as substitution, polymerization and the like to generate ester derivatives such as polyurethane, polycarbonate and the like or polyester. Therefore, the glycerol carbonate can also be used as a good chemical process intermediate or raw material. Meanwhile, the glycerol carbonate with a very high dielectric constant has good solubility on lithium-containing inorganic salts, and can be used as an electrolyte solution of a lithium battery. The existing preparation process of the glycerin carbonate comprises a transesterification method, a urea alcoholysis method, a CO oxidation and carbonylation method and a CO 2 carbonylation method, and has the defects of serious environmental pollution, high separation cost, low product quality and the like. Among them, the CO 2 carbonylation method has received a lot of attention because of its advantages of low cost, high atomic utilization, safety and environmental protection. However, due to the inertness of CO 2, there is a thermodynamic limitation on the reaction, which results in very low yields of glycerol carbonate. Although there has been no breakthrough in the production of glycerol carbonate by the carbonylation of glycerol and CO 2, the simultaneous use of the reaction of the industrial by-product glycerol and the greenhouse gas CO 2 has been still attractive. Past studies have shown that the cycloaddition of epoxide and CO 2 to synthesize cyclic carbonate and the transesterification of glycerol and carbonate to synthesize glycerol carbonate are both thermodynamically favourable. When propylene oxide is added as a coupling agent to CO 2 and glycerol, the carbonylation reaction is split into two steps, cycloaddition and transesterification. The coupling reaction has the advantages of (1) greatly improving the yield of the glycerol carbonate while maintaining the advantages of the carbonylation reaction, (2) having economic benefits of by-products of propylene carbonate and 1, 2-propylene glycol, being widely applied chemicals, and (3) avoiding separation and purification of an intermediate product of propylene carbonate and simplifying experimental steps. To date, research into coupling reaction catalysts has been directed to halogen-containing catalysts, which generally have superior catalytic properties. However, the toxicity and corrosiveness of halogens may limit their industrial application, and thus, there is a need to develop environmentally friendly halogen-free heterogeneous catalysts for coupling reactions to glycerol carbonate. Disclosure of Invention The invention aims to provide a catalyst for synthesizing glycerol carbonate by a one-pot method of carbon dioxide, glycerol and epoxypropane, which has strong CO 2 adsorption activation capability and high yield of the glycerol carbonate. The invention also aims at a method for preparing the glycerol carbonate by using carbon dioxide, glycerol and propylene oxide through a one-pot method, so that the efficient synthesis of the glycerol carbonate on the halogen-free heterogeneous catalyst is realized. A catalyst for synthesizing glycerol carbonate comprises an active component comprising Mg element and a second metal element, wherein the second metal element comprises one or a mixture of more than two of Ni, al, mn, co, sn, zr, cu, ca, li elements. The catalyst is used for preparing the glycerin carbonate by a one-pot method, and improves the yield of the glycerin carbonate. The preparation method of the glycerol carbonate comprises the step of synthesizing the glycerol carbonate under the action of the catalyst, wherein the reaction temperature is 100-160 ℃. That is, glycerin, propylene oxide and carbon dioxide are used as raw materials, cycloaddition reaction and transesterification reaction are not needed to be carried out step by step under the action of a catalyst, and the raw materials can be used for obtaining the product glycerin carbonate by a one-pot method. Not only simplifying the preparation process, but also improving the yield of the glycerol carbonate