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CN-122006788-A - Multifunctional catalyst and CO/CO thereof2Application of co-hydrogenation in preparation of methyl acetate

CN122006788ACN 122006788 ACN122006788 ACN 122006788ACN-122006788-A

Abstract

The invention relates to a multifunctional catalyst and application thereof in preparing methyl acetate by CO/CO 2 CO-hydrogenation, wherein the multifunctional catalyst consists of spinel catalyst CuGa 2 O 4 , mordenite and polymer, wherein the spinel catalyst CuGa 2 O 4 is prepared by adding Ga salt and Cu salt into water, uniformly mixing, adding a precipitant, regulating pH value, performing CO-precipitation reaction, standing, filtering, washing and drying solids, and roasting; according to the invention, a synergistic catalytic system is constructed by compounding the catalyst CuGa 2 O 4 with the dimethyl ether synthesizing function, the mordenite with the carbonylation function and the polymer with the hydrophobic function, the inhibition effect of water on the active sites of the mordenite is relieved in the CO/CO 2 CO-hydrogenation reaction process, and the direct synthesis of methyl acetate is realized, so that the reaction flow is shortened, the equipment investment and the operation energy consumption are reduced, and the utilization of blast furnace gas resources and the carbon emission reduction are facilitated.

Inventors

  • ZHENG YANE
  • LI HUAN
  • WANG HUA
  • WANG YUHAO
  • Du Lunren

Assignees

  • 昆明理工大学

Dates

Publication Date
20260512
Application Date
20260202

Claims (5)

  1. 1. A multifunctional catalyst is characterized by comprising a spinel type catalyst CuGa 2 O 4 , mordenite and a polymer, wherein the spinel type catalyst CuGa 2 O 4 is prepared by adding Ga salt and Cu salt into water, uniformly mixing, adding a precipitant, adjusting the pH value to 8.0-10.0, performing coprecipitation reaction under stirring at 20-30 ℃, standing, filtering, washing and drying solids, and roasting.
  2. 2. The multifunctional catalyst according to claim 1, wherein the precipitant is one or more of ammonia water, ammonium carbonate, sodium hydroxide, sodium carbonate and sodium bicarbonate, and the molar ratio of Ga salt to Cu salt is 1:1-4:1.
  3. 3. The multifunctional catalyst according to claim 2, wherein the mass ratio of the mordenite to the polymer is 1 (0.1-4.0), and the mixture of the mordenite and the polymer is prepared by mixing, grinding, tabletting and re-granulating.
  4. 4. Use of a multifunctional catalyst according to any of claims 1-3 for CO/CO 2 CO-hydrogenation to prepare methyl acetate.
  5. 5. The method of claim 4, wherein the upper layer of the high-pressure fixed bed reactor is filled with a catalyst CuGa 2 O 4 , the lower layer of the high-pressure fixed bed reactor is provided with a mixture of mordenite and polymer, then mixed gas of CO and CO 2 、H 2 is introduced, and the reaction is carried out at a space velocity of 1000-12000 mL g -1 ·h -1 , a temperature of 100-600 ℃ and a pressure of 0.1-8.0 MPa to prepare methyl acetate.

Description

Multifunctional catalyst and application thereof in CO/CO 2 CO-hydrogenation preparation of methyl acetate Technical Field The invention belongs to a synthesis method of methyl acetate, and particularly relates to a multifunctional catalyst and application thereof in CO/CO 2 CO-hydrogenation to prepare methyl acetate. Background The conversion of synthesis gas to C 2+ oxygenates has attracted considerable attention in the catalytic field, providing a technological route to the potential of an implement for the production of fuels and chemicals from non-petroleum resources such as coal, natural gas and biomass. Methyl acetate is used as one of important C 2+ oxygen-containing compounds, has excellent solubility, can replace acetone to be used for products such as resin, paint, ink, paint, adhesive, leather and the like, is also an important raw material for pharmaceutical industry and organic synthesis, can be used as an important intermediate for producing ethanol, and has wide market prospect. At present, methyl acetate is mainly prepared by dimethyl ether carbonylation reaction, and dimethyl ether is usually obtained by synthesizing synthesis gas through methanol and further dehydrating, so that the process flow is longer, and the required equipment investment is larger. In addition, with the increasingly prominent global climate change problem, the reduction of greenhouse gas emission has become a major problem to be solved, and the steel industry is one of main carbon emission sources in China, and faces a larger emission reduction challenge in the process of achieving the double-carbon target. The method for searching carbon emission reduction measures for the steel industry has important significance for promoting China to realize the strategic targets of carbon peak and carbon neutralization. The blast furnace gas is used as one of main byproduct gases generated in the production process of the steel industry, contains a large amount of CO 2 (20-35%) and CO (20-30%), and has important significance for green low-carbon transformation of the steel industry if the high-efficiency recycling of the furnace gas can be realized. However, no report on CO/CO 2 CO-hydrogenation in blast furnace gas to prepare methyl acetate exists at present, if a corresponding catalytic system and a corresponding reaction process can be developed, the method is expected to obviously shorten the reaction flow and reduce the production cost, and helps to reduce the emission of greenhouse gases while realizing high-value utilization of carbon resources, so that the method has important industrial application value and social significance. In the above reaction system, water is inevitably generated during the series reaction, and it has been shown that the presence of water significantly inhibits the carbonylation activity of the mordenite catalyst, mainly because water interferes with the adsorption of dimethyl ether and the subsequent CO insertion process, thereby inhibiting the carbonylation activity. Therefore, the hydrophobic modification of the catalyst is considered as an effective regulation means, which can weaken the covering effect of water on the catalytic active sites and promote the desorption and diffusion of surface water, thereby improving the reaction performance. Disclosure of Invention Aiming at the problems that the existing synthesis gas is complex in process of preparing methyl acetate through multi-step conversion, water is used for inhibiting carbonylation reaction activity and the like, the invention provides a multifunctional catalyst which is composed of a spinel type catalyst CuGa 2O4, mordenite and a polymer, wherein the catalyst CuGa 2O4 is prepared by adding Ga salt and Cu salt into water, uniformly mixing, adding a precipitator, adjusting the pH value to 8.0-10.0, performing coprecipitation reaction under the conditions of 20-30 ℃ and stirring, standing, filtering, washing and drying solids, and roasting. The mordenite is firstly mixed with polymer according to the mass ratio of 1 (0.1-4.0), ground for 10-15 minutes, pressed into tablets under 10-40 megapascals, and then granulated to obtain the mixture. The invention further aims to apply the multifunctional catalyst in the CO/CO 2 CO-hydrogenation to prepare methyl acetate, specifically, the upper layer is filled with a catalyst CuGa 2O4 in a high-pressure fixed bed reactor, the lower layer is filled with a mixture of mordenite and a polymer, then mixed gas of CO and CO 2、H2 is introduced, and the methyl acetate is prepared by reacting at a temperature of 100-600 ℃ and a pressure of 0.1-8.0 MPa at a space velocity of 1000-12000 mL-g -1·h-1, wherein the volume ratio of H 2:(CO+CO2) is 0.5-6:1, and CO: CO 2 =1-5:1. The invention uses CO and CO 2、H2 as reaction raw materials, and carries out continuous relay catalytic reaction on a multifunctional catalyst to realize CO/CO 2 CO-hydrogenation to prepare methyl acetate. In the process, CO and CO 2、H2