CN117510333A - Method for preparing methyl propionate with high selectivity - Google Patents

Method for preparing methyl propionate with high selectivity Download PDF

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Publication number
CN117510333A
CN117510333A CN202311410735.7A CN202311410735A CN117510333A CN 117510333 A CN117510333 A CN 117510333A CN 202311410735 A CN202311410735 A CN 202311410735A CN 117510333 A CN117510333 A CN 117510333A
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catalyst
gold
methyl propionate
propionaldehyde
metal
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黄家辉
张军营
谢妍
龙化云
苏鑫
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a method for preparing methyl propionate with high selectivity, and belongs to the technical field of oxidative esterification. The method utilizes cheap metal to modify nano gold to obtain a bimetallic catalyst, and can convert the propionaldehyde into methyl propionate with high selectivity through oxidation esterification reaction. Compared with a pure nano gold catalyst, the addition of the cheap metal can adjust the dispersity and the surface electronic property of gold, thereby greatly reducing the generation of propionic acid as a byproduct in the reaction process. The catalyst shows remarkable reaction activity on a synthetic route for preparing methyl propionate by oxidizing and esterifying propionaldehyde, and the preparation method of the catalyst is simple, the reaction flow is short, the reaction condition is mild, and the catalyst is suitable for industrial amplification. In the reaction of preparing methyl propionate by using propionaldehyde as a raw material, the conversion rate of the propionaldehyde can reach 60 percent, and the selectivity of the methyl propionate can reach 95 percent.

Description

Method for preparing methyl propionate with high selectivity
Technical Field
The invention belongs to the technical field of oxidative esterification reaction, and particularly relates to a method for preparing methyl propionate by using an oxide supported bimetallic catalyst and using methanol and propionaldehyde as raw materials.
Background
Methyl propionate is mainly used as a solvent for nitrocellulose, nitrolacquers, paints, varnishes and the like, and also as a solvent for perfumes and flavors, and also as an organic synthesis intermediate. Methyl propionate can be used for synthesizing Methyl Methacrylate (MMA) and is widely applied to the fields of glass, medical equipment and the like.
Methyl propionate can be obtained by esterifying propionic acid with methanol, for example, CN104761451B discloses that propionic acid and monohydric alcohol are subjected to esterification reaction under the action of a gel-type strongly acidic ion exchange resin catalyst to generate propionate, and the purity of the product is improved by effectively adsorbing reaction impurities by adopting the catalyst. In addition, methyl propionate can be prepared from ethylene, CO and methanol through a carbonylation-esterification process, and Co, fe, ru and other metal ions have obvious effect on catalyzing ethylene methoxycarbonylation to obtain methyl propionate (J.Organomet.Chem., 2016,691,921;CN 108993602A;CN 107497494A;CN 107497493A). Although some methods for preparing methyl propionate are disclosed in the prior art, the problems of low conversion rate, low selectivity of methyl propionate and the like still exist, and further research and development of a new process route for preparing methyl propionate with high selectivity are particularly important.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing methyl propionate with high selectivity, which uses an oxide-supported bimetallic catalyst to catalyze methanol and propionaldehyde to prepare methyl propionate, wherein the bimetallic catalyst has the following functions: (1) The addition of the second metal can adjust the dispersity and the surface electronic property of gold, so as to regulate and control the activity of the catalyst and the selectivity of the catalyst to the product; (2) The bimetallic can further reduce the cost of the catalyst; (3) The bimetallic can further modulate the interfacial length and interfacial properties between the supported metal and the support, thereby further modulating the performance of the catalyst. The advantages of the process route described in the present invention over other routes for the preparation of methyl propionate are: the preparation method has the advantages of short propionaldehyde oxidation and esterification flow, mild reaction conditions in the process, high raw material conversion rate and high product selectivity.
The invention aims at realizing the following steps:
the invention provides a method for preparing methyl propionate with high selectivity, which comprises the following steps:
(1) Dissolving a gold precursor into water, adding a protective agent with the molar quantity of 2-100 times of gold to obtain a first solution, dissolving a second metal precursor into water, wherein the molar ratio of the second metal to gold is 1:1-1:1000, and adding a second protective agent with the molar quantity of 2-100 times of that of the second metal to obtain a second solution; uniformly mixing the first solution and the second solution, adding excessive reducing agent for reduction, adding an oxide carrier, continuously stirring for 1-5h, filtering, washing, drying and roasting to obtain a catalyst;
(2) Adding the catalyst obtained in the step (1) into a reaction kettle of a mixed solution of methanol and propionaldehyde, regulating the pressure of the reaction kettle to 0.5-5MPa by utilizing an atmosphere containing oxygen, and reacting for 0.5-10h at 30-120 ℃ to obtain the catalyst.
Based on the technical scheme, further, the gold loading amount in the catalyst obtained in the step (1) is 0.1-3wt%
Based on the technical scheme, the gold precursor in the step (1) further comprises chloroauric acid, potassium chloroaurate, ammonium tetrachloroaurate (III), sodium chloroaurate and triphenylphosphine gold chloride.
Based on the above technical scheme, further, the protective agent in the step (1) is an organic ligand, and includes at least one of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), ethylenediamine tetraacetic acid (EDTA), citric acid, and ethylenediamine glycine.
Based on the above technical solution, further, in the step (1), the second metal is at least one of Cu, ni, ag, ru, and the second metal precursor includes one of nitrate, sulfate, hydrochloride, phosphate, and acetate of the above metal.
Based on the above technical scheme, further, the second protective agent in the step (1) is at least one of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), ethylenediamine tetraacetic acid (EDTA), citric acid, and ethylenediamine glycine.
Based on the above technical scheme, further, the reducing agent in the step (1) comprises sodium borohydride and borane tert-butylamine complex.
Based on the technical scheme, further, the oxide carrier in the step (1) is MgO and TiO 2 、CeO 2 、Al 2 O 3 、Fe 2 O 3 One of CoO and ZnO.
Based on the technical scheme, the drying temperature in the step (1) is 40-90 ℃ and the roasting temperature is 300-600 ℃.
Based on the technical scheme, further, the molar ratio of the methanol to the propionaldehyde in the step (2) is in the range of 1000:1 to 5:1, preferably 100:1 to 10:1; the molar ratio of propanal to gold is between 5000 and 100, preferably 2000 to 500.
Based on the technical scheme, the atmosphere containing oxygen in the step (2) is air or mixed gas of oxygen and nitrogen with the volume percentage of 10-50%.
Based on the technical scheme, the catalyst in the step (2) is further added in an amount of 0.01-0.5g/mL.
Based on the technical scheme, further, the reaction pressure in the step (2) is 1-5MPa, and the reaction temperature is 30-100 ℃.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the oxide supported bimetallic catalyst is used for catalyzing methanol and propionaldehyde to prepare methyl propionate, one metal in the bimetallic catalyst is gold, the other metal in the bimetallic catalyst is Cu, ni, ag, ru, the electronic distribution of gold is regulated and controlled by the second metal, the activity of the catalyst can be further improved, the catalyst activity is higher, methyl propionate is prepared by catalyzing methanol and propionaldehyde in an intermittent reaction kettle at a lower temperature, the reaction temperature is mild, the conversion rate and selectivity of a product are higher, the conversion rate of propionaldehyde can reach 60%, the selectivity of methyl propionate can reach 95%, and the catalyst is easy to amplify and synthesize and is more suitable for industrialization.
Detailed Description
The following detailed description of the invention is provided in connection with examples, but the implementation of the invention is not limited thereto, and it is obvious that the examples described below are only some examples of the invention, and that it is within the scope of protection of the invention to those skilled in the art to obtain other similar examples without inventive faculty.
Comparative example 1: preparation of 1% Au/MgO
Gold catalyst preparation: dissolving 0.1g of chloroauric acid into 150mL of water, then adding a certain amount of PVA, wherein the mole number of the PVA is 10 times of that of gold, uniformly mixing, adding excessive sodium borohydride for reduction, continuously stirring for 30min, adding a 5.0 magnesium oxide carrier, and continuously stirring for 1h. After filtration and washing, the catalyst was dried at 80℃and then calcined at 500℃under an air atmosphere for 2 hours, giving a catalyst designated 1% Au/MgO.
Comparative example 2:1% Au/TiO 2 Is prepared from
Comparative example 2 is a modification of the support of comparative example 1 to TiO 2 Catalyst 1% Au/TiO was prepared by the same method as in comparative example 1 2 。
Comparative example 3:1% Au/Al 2 O 3 Is prepared from
Comparative example 3 is a modification of the support of comparative example 1 to Al 2 O 3 Catalyst 1% Au/Al was prepared by the same method as in comparative example 1 2 O 3 。
Example 1: preparation of 1% Au0.1% Ni/MgO
Preparation of a supported catalyst: 0.1g of chloroauric acid was dissolved in 150mL of water, followed by addition of an amount of PVA, 10 times the moles of PVA as many as gold. Dissolving 0.03g of nickel nitrate in 50mL of ultrapure water to make the molar ratio of gold to nickel in the solution be 10:1, then adding a certain amount of PVP, wherein the molar number of PVP is 10 times that of nickel, heating the solution to 50 ℃ after uniformly mixing the two solutions, quickly adding excessive sodium borohydride for reduction, continuously stirring for 5min, adding a 5.0 magnesium oxide carrier to make the theoretical loading of gold on the oxide be 1%, and the theoretical loading of nickel on the oxide be 0.1%, and continuously stirring for 1h. After filtration washing, it was dried at 80℃and then calcined at 500℃under an air atmosphere for 2 hours, the resulting catalyst was designated as 1% Au0.1% Ni/MgO.
Example 2:1% Au0.1% Cu/TiO 2 Is prepared from
Preparation of a supported catalyst: 0.1g of chloroauric acid was dissolved in 150mL of water, followed by addition of an amount of PVA, 10 times the moles of PVA as many as gold. Dissolving 0.07g of copper nitrate in 50mL of ultrapure water to make the molar ratio of gold to copper in the solution be 10:1, then adding a certain amount of PVP with the molar number of PVP being 10 times of the molar number of copper ions, mixing the two solutions, quickly adding excessive sodium borohydride for reduction, continuously stirring for 5min, adding 5g of titanium oxide carrier to make the theoretical loading of gold on oxide be 1%, and the theoretical loading of copper on oxide be 0.1%, and continuously stirring for 1h. After filtration washing, it was dried at 80℃and then calcined at 500℃under an air atmosphere for 2 hours. The catalyst obtained was labeled with 1% Au0.1% Cu/TiO 2 。
Example 3:1% Au0.05% Ag/Al 2 O 3 Is prepared from
Preparation of a supported catalyst: after adding 100mL of ultrapure water to 0.1g of chloroauric acid, stirring and dissolving, a certain amount of PVA was added, the mole number of PVA being 10 times that of gold. 50mL of ultrapure water was taken to dissolve 0.01g of silver nitrate, followed by adding a certain amount of citric acid, the mole number of which is 2 times that of silver. After the two solutions are mixed, excessive sodium borohydride is rapidly added for reduction, after stirring is continued for 5min, 5g of alumina carrier is added, so that the theoretical load of gold on the oxide is 1%, the theoretical load of silver on the oxide is 0.05%, and stirring is continued for 1h. After filtration washing, it was dried at 80℃and then calcined at 500℃under an air atmosphere for 2 hours. The catalyst obtained was labeled with 1% Au0.05% Ag/Al 2 O 3 。
Example 4:1% Au0.05% Ag/CeO 2 Is prepared from
Preparation of a supported catalyst: after adding 100mL of ultrapure water to 0.1g of chloroauric acid, stirring and dissolving, a certain amount of PVA was added, the mole number of PVA being 2 times that of gold. 50mL of ultrapure water was taken to dissolve 0.01g of silver nitrate, followed by adding a certain amount of citric acid, the mole number of which is 2 times that of silver. After the two solutions are mixed, excessive sodium borohydride is rapidly added for reduction, after stirring is continued for 5min, 5g of cerium oxide carrier is added, so that the theoretical load of gold on the oxide is 1%, the theoretical load of silver on the oxide is 0.05%, and stirring is continued for 1h. After filtration washing, it was dried at 80℃and then calcined at 600℃under an air atmosphere for 2 hours. The catalyst obtained was labeled with 1% Au0.05% Ag/CeO 2 。
Example 5: preparation of 1% Au0.05% Ag/ZnO
Preparation of a supported catalyst: 0.1g of chloroauric acid was added to 100mL of ultrapure water and dissolved with stirring, followed by addition of a certain amount of PVP having a molar number 10 times that of gold. 50mL of ultrapure water was taken to dissolve 0.01g of silver nitrate, followed by adding a certain amount of citric acid, the mole number of which is 2 times that of silver. After the two solutions are mixed, excessive sodium borohydride is rapidly added for reduction, after stirring is continued for 5min, 5g of zinc oxide carrier is added, so that the theoretical load of gold on the oxide is 1%, the theoretical load of silver on the oxide is 0.05%, and stirring is continued for 1h. After filtration and washing, the mixture was dried at 80℃and then calcined at 500℃under a 50% oxygen/nitrogen mixture for 2 hours. The resulting catalyst was labeled with 1% Au0.05% Ag/ZnO.
Example 6:1% Au0.05% Ag/Fe 2 O 3 Is prepared from
Preparation of a supported catalyst: 0.1g of chloroauric acid was added to 100mL of ultrapure water and dissolved with stirring, followed by addition of a certain amount of PVP having 50 times the number of moles of PVP as compared with the number of moles of gold. 50mL of ultrapure water was taken to dissolve 0.01g of silver nitrate, followed by adding a certain amount of citric acid, the mole number of which is 2 times that of silver. Mixing the two solutions, quickly adding excessive sodium borohydride for reduction, stirring for 5min, and adding 5g of ferric oxide carrier to enable the theoretical load of gold on the oxide1% so that the theoretical loading of silver on the oxide is 0.05%, stirring is continued for 1h. After filtration and washing, the mixture was dried at 80℃and then calcined at 400℃under a 50% oxygen/nitrogen mixture for 2 hours. The catalyst obtained was labeled with 1% Au0.05% Ag/Fe 2 O 3 。
Example 7: preparation of 1% Au0.1% Ru/CoO
Preparation of a supported catalyst: after adding 100mL of ultrapure water to 0.1g of chloroauric acid, stirring and dissolving, a certain amount of PVA was added, the mole number of PVA being 10 times that of gold. 50mL of ultrapure water was taken to dissolve 0.02g of ruthenium nitrate, followed by addition of a certain amount of citric acid, the mole number of which was 5 times that of ruthenium. After mixing the two solutions, an excess of sodium borohydride was quickly added for reduction. After stirring for 5min, 5g of cobalt oxide carrier was added to give a theoretical loading of gold on the oxide of 1% and a theoretical loading of ruthenium on the oxide of 0.1%, and stirring was continued for 1h. After filtration washing, it was dried at 80℃and then calcined at 500℃under an air atmosphere for 2 hours. The resulting catalyst was labeled 1% Au0.1% Ru/CoO.
Example 8: catalytic reaction
10mL of a mixed solution of methanol and propionaldehyde in a molar ratio of 10:1 was placed in a reaction vessel, to which 0.5g of the catalysts of comparative examples 1-3 and examples 1-7, respectively, were added; the pressure of the reaction kettle is regulated to 3MPa by using the gas with the oxygen concentration of 20 percent, and the reaction is carried out for 1h after the reaction temperature is regulated to 60 ℃. After the reaction was completed, the product was analyzed by gas chromatography. The conversion of propanal and the selectivity of the product methyl propionate were calculated. Conversion = (initial propanal concentration-remaining propanal concentration) ×100/initial propanal concentration; selectivity = moles of methyl propionate 100/moles of propanal converted, the results are shown in table 1.
TABLE 1 catalytic reactivity of the catalysts of comparative examples 1-3 and examples 1-7 in the oxidative esterification of propionaldehyde
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. A method for preparing methyl propionate with high selectivity, which is characterized by comprising the following steps:
(1) Dissolving a gold precursor into water, adding a protective agent with the molar quantity of 2-100 times of gold to obtain a first solution, dissolving a second metal precursor into water, wherein the molar ratio of the second metal to gold is 1:1-1:1000, and adding a second protective agent with the molar quantity of 2-100 times of that of the second metal to obtain a second solution; uniformly mixing the first solution and the second solution, adding excessive reducing agent for reduction, adding an oxide carrier, continuously stirring for 1-5h, filtering, washing, drying and roasting to obtain a catalyst;
(2) Adding the catalyst obtained in the step (1) into a reaction kettle of a mixed solution of methanol and propionaldehyde, regulating the pressure of the reaction kettle to 0.5-5MPa by utilizing an atmosphere containing oxygen, and reacting for 0.5-10h at 30-120 ℃ to obtain the catalyst.
2. The process according to claim 1, wherein the gold loading in the catalyst obtained in step (1) is 0.1-3wt%.
3. The method of claim 1, wherein the gold precursor in step (1) comprises chloroauric acid, potassium chloroaurate, ammonium tetrachloroaurate (III), sodium chloroaurate, triphenylphosphine gold chloride; the protective agent is an organic ligand and comprises at least one of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), ethylenediamine tetraacetic acid (EDTA), citric acid and ethylenediamine glycine.
4. The method of claim 1, wherein the second metal in step (1) is at least one of Cu, ni, ag, ru and the second metal precursor comprises one of nitrate, sulfate, hydrochloride, phosphate, acetate of the metal; the second protective agent is at least one of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), ethylenediamine tetraacetic acid (EDTA), citric acid and ethylenediamine glycine.
5. The method of claim 1, wherein the reducing agent in step (1) comprises a complex of sodium borohydride and borane tert-butylamine.
6. The method according to claim 1, wherein the oxide support in step (1) is MgO, tiO 2 、CeO 2 、Al 2 O 3 、Fe 2 O 3 One of CoO and ZnO.
7. The method according to claim 1, wherein the drying temperature in step (1) is 40 to 90 ℃ and the firing temperature is 300 to 600 ℃.
8. Process according to claim 1, characterized in that the molar ratio of methanol to propionaldehyde in step (2) is in the range of 1000:1 to 5:1, preferably 100:1 to 10:1; the molar ratio of propanal to gold is between 5000 and 100, preferably 2000 to 500.
9. The method according to claim 1, wherein the atmosphere containing oxygen in the step (2) is air or a mixed gas of oxygen and nitrogen with an oxygen volume percentage of 10-50%.
10. The process according to claim 1, wherein the catalyst is added in step (2) in an amount of 0.01-0.5g/mL.
CN202311410735.7A 2023-10-28 2023-10-28 Method for preparing methyl propionate with high selectivity Pending CN117510333A (en)

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