Method for preparing methyl propionate through carbonylation of ethylene and carbon monoxide

Abstract

The invention provides a method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide, which is characterized in that ethylene, carbon monoxide and methanol are used as raw materials and react under the catalysis of a catalytic system to directly prepare methyl propionate, and the catalytic system comprises a divalent cobalt catalyst and an organic phosphine oxide; the reaction temperature is 60-160 DEG C, and the reaction pressure is 0.5-8 Mpa. According to the method, an active species is generated through coordination of divalent cobalt and organic secondary phosphine oxide or tertiary phosphine oxide, and the species have high catalytic activity on the carbonylation reaction of ethylene. Compared with the prior art, the methyl propionate synthesis method has the advantages that carbonyl esterification of ethylene can be realized under relatively mild conditions without using noble metal, unreacted gas can be recycled, the catalyst can be recycled through rectification, and the methyl propionate synthesis method is green and economical.

Description

Technical field:

[0001] The invention belongs to the technical field of organic chemical industry, and particularly relates to a method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide. Background technology:

[0002] Methyl propionate (MP) is an important organic compound with a wide range of applications. It serves as a crucial intermediate in the synthesis of numerous high-value-added fine chemicals, playing a key role in the preparation of pharmaceuticals, pesticides, fragrances, and polymers. Furthermore, due to its excellent solubility and volatility, MP is also playing a crucial role in coatings, detergents, and industrial solvents. Therefore, with the continuous expansion of MP's applications and growing demand, the development of green and efficient catalytic systems has far-reaching practical significance.

[0003] Some preparation methods of methyl propionate have been disclosed in existing literature and patents. First, the most direct method is to use propionic acid as a raw material and esterify it with methanol in one step under acidic conditions to synthesize MP ( Figure 11 ), patents CN102320962A and CN102336661A reported homogeneous acid catalysis processes for this process, but these processes inevitably have problems such as high propionic acid raw material prices, multiple side reactions under acidic conditions, high equipment maintenance costs, and high waste liquid treatment costs. To address these issues, patent CN105478147A reported a method of replacing traditional homogeneous acids with solid heterogeneous acids. Although this method avoids equipment corrosion, it suffers from the problem of acid sites being easily deactivated, making catalyst recycling difficult.

[0004] Second, replacing propionic acid with propionaldehyde to optimize reaction conditions and reduce production costs has become a new idea ( Figure 12 Patent CN117510333A reports a bimetallic catalytic system with gold as the core. Although it has high MP selectivity, the conversion rate is limited and an organic ligand is required to protect the precious metal, which is not conducive to industrial scale-up. The paper Journal of the Japan Petroleum Institute, 2011, 54(6):380-384 reports a method for synthesizing MP by oxidative esterification in one pot using propionaldehyde, oxygen and methanol as raw materials. Although this route directly avoids the use of acidic auxiliary agents and has a yield of at least 60%, it requires the use of additional DMF as a solvent and requires expensive palladium (Pd) as a catalyst. In addition, the catalyst life reported in the document is difficult to meet the requirements of industrial application, thus limiting the further development of this process.

[0005] Third, in addition to the traditional esterification method, patents CN111054390A and CN112916022A reported a new method for synthesizing MP by direct hydrogenation using methyl acrylate and hydrogen as raw materials ( Figure 13 ), a method with high atomic utilization efficiency that conforms to the basic principles of green chemistry. However, the catalysts reported in both patents are based on precious metals such as rhodium, platinum, palladium, and ruthenium, modified with cheaper metals such as cobalt and nickel. This still carries high production costs, and also faces challenges such as expensive raw materials and high storage costs (methyl acrylate is prone to self-polymerization and deterioration).

[0006] Fourth, considering the economic efficiency of the reaction and the growing popularity of the concept of green chemistry, the method of synthesizing MP by one-step carbonylation of ethylene with carbon monoxide is the most widely used reaction pathway in the catalytic industry. Figure 14 ), which has the advantages of mild reaction conditions, recyclable feed gas, and no need for additional solvents. It is highly consistent with the principles of green chemistry and has important theoretical and practical value. Among them, CN119191979A, CN118878581A, CN117986119A, CN116854921A, CN119488952A, CN119488948A, CN115870007A, CN115819234A and other patents report catalytic systems based on precious metals such as palladium, rhodium, and ruthenium. However, the use of precious metals always leads to high costs and difficult recycling. In particular, Pd-based catalysts, which have the highest activity, are easily reduced by CO to catalytically inactive palladium black, resulting in system deactivation, further increasing production costs and separation and recovery costs.

[0007] Therefore, in response to the above problems, the development of a new green and recyclable catalytic system with cheap transition metals as the core is of great practical production value. Summary of the invention:

[0008] The present invention aims to address the deficiencies of the prior art and to provide a method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide. The method comprises inexpensive and readily available materials, mild reaction conditions, no need for the addition of additional solvents and acidic additives, and the catalyst after the reaction can be recycled by simple distillation.

[0009] In order to achieve the above object, the present invention adopts the following technical solutions:

[0010] The invention provides a method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide. The method uses ethylene, carbon monoxide and methanol as raw materials, and reacts to prepare methyl propionate under the catalysis of a catalytic system; the catalytic system comprises a divalent cobalt catalyst and an organic phosphine oxide, wherein the divalent cobalt is the main catalyst and the organic phosphine oxide is the ligand.

[0011] As a further preferred embodiment of the present invention, the following feature is also included: the divalent cobalt catalyst is a combination of one or more of cobalt acetate tetrahydrate, cobalt propionate, cobalt carbonate, cobalt hydroxide, cobalt iodide, cobalt tetrafluoroborate and cobalt phosphate.

[0012] As a further preferred embodiment of the present invention, the following features are also included: the organic phosphine oxide is one or a combination of organic tertiary phosphine oxide and organic secondary phosphine oxide; the structural formulas of the organic tertiary phosphine oxide and the organic secondary phosphine oxide are Formula 1 and Formula 2, respectively:

[0013]

[0014] Among them, R 1 、R 2 、R 3 It is one of aryl, pyridyl, alkyl, alkoxy and aryloxy.

[0015] As a further preferred embodiment of the present invention, the following features are also included: the reaction temperature is 60 to 160° C., and the reaction time is 10 to 20 hours.

[0016] As a further preferred embodiment of the present invention, the following features are also included: the reaction temperature is 140-160° C., and the reaction time is 16 hours.

[0017] As a further preferred embodiment of the present invention, the following feature is also included: the reaction pressure is 0.5 to 8 MPa.

[0018] As a further preferred embodiment of the present invention, the following feature is also included: the reaction pressure is 2 to 6 MPa.

[0019] As a further preferred embodiment of the present invention, the following feature is also included: in the catalytic system, the molar ratio of the divalent cobalt catalyst to the organic phosphine oxide is 1:0.5-10.

[0020] As a further preferred embodiment of the present invention, the following feature is also included: the molar ratio of the divalent cobalt catalyst to ethylene is 1:20 to 80.

[0021] As a further preferred embodiment of the present invention, the following feature is also included: the molar ratio of methanol to ethylene is 4 to 20:1.

[0022] As a further preferred embodiment of the present invention, the following feature is also included: the molar ratio of ethylene to carbon monoxide is 1:10-20.

[0023] As a further preferred embodiment of the present invention, the following feature is also included: the molar ratio of ethylene to carbon monoxide is 1:16.

[0024] Beneficial effects of the present invention:

[0025] (1) In the present invention, the catalytic system includes a divalent cobalt catalyst and an organic phosphine oxide, wherein the divalent cobalt catalyst is the main catalyst and the organic phosphine oxide is the ligand, and no precious metal catalysis is required, the materials are readily available, and the cost is low;

[0026] (2) The present invention can directly prepare methyl propionate by catalyzing the liquid-phase carbonylation reaction of ethylene, carbon monoxide and methanol under relatively mild conditions (60-160° C., 0.5-8 MPa), without the need for any additional solvent or acidic additive, and has low equipment maintenance costs and waste liquid treatment costs. The catalyst after the reaction can be recycled by simple distillation. The liquid-phase by-product in the reaction process is a small amount of 3-pentanone, and the gas-phase by-product is a small amount of ethane and a trace amount of methane. Description of the drawings:

[0027] Figure 1 This is a gas chromatogram of the gas after the reaction in Example 2 of the present invention;

[0028] Figure 2 This is a gas chromatogram of the liquid after the reaction in Example 2 of the present invention;

[0029] Figure 3 The nuclear magnetic resonance of the self-synthesized ligand L2 before the reaction in Example 2 of the present invention 31 P spectrum;

[0030] Figure 4 The nuclear magnetic resonance of the self-synthesized ligand L2 after the reaction of Example 2 of the present invention 31 P spectrum;

[0031] Figure 5 The nuclear magnetic resonance of the self-synthesized ligand L12 of Example 12 of the present invention 31 P spectrum;

[0032] Figure 6 The nuclear magnetic resonance of the self-synthesized ligand L12 of Example 12 of the present invention 1 H spectrum;

[0033] Figure 7 The nuclear magnetic resonance of the self-synthesized ligand L12 of Example 12 of the present invention 12 C spectrum;

[0034] Figure 8 The nuclear magnetic resonance of the self-synthesized ligand L4 of Example 4 of the present invention 31 P spectrum;

[0035] Figure 9 The nuclear magnetic resonance of the self-synthesized ligand L5 of Example 5 of the present invention 31 P spectrum;

[0036] Figure 10 The nuclear magnetic resonance of the self-synthesized ligand L7 of Example 7 of the present invention 31 P spectrum;

[0037] Figure 11 The reaction equation for synthesizing MP by one-step esterification of propionic acid and methanol in the prior art;

[0038] Figure 12 The reaction equation for synthesizing MP by oxidative esterification of propionaldehyde, oxygen and methanol in the prior art;

[0039] Figure 13 The reaction equation for synthesizing MP by hydrogenation of methyl propionate with hydrogen in the prior art is:

[0040] Figure 14 This is the reaction equation for the direct carbonylation of ethylene and carbon monoxide to synthesize MP in the prior art. Specific implementation method:

[0041] In order to make the purpose, technical solutions and advantages of this application more clearly understood, the present application is described and illustrated below in conjunction with the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely used to explain this application and are not intended to limit this application. Based on the embodiments provided in this application, all other embodiments obtained by those of ordinary skill in the art without making any creative efforts are within the scope of protection of this application.

[0042] Example 1

[0043] 125 mg of the catalyst Co(OAc)2·4H2O, 140 mg of triphenylphosphine oxide (L1), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of methyl propionate (MP) was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 32%.

[0044] The structural formula of triphenylphosphine oxide (L1) is:

[0045]

[0046] Example 2

[0047] 125 mg of the catalyst Co(OAc)2·4H2O, 139 mg of diphenyl-2-pyridylphosphine oxide (L2), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 83%.

[0048] The structural formula of diphenyl-2-pyridylphosphine oxide (L2) is:

[0049]

[0050] Figure 1 This is the gas chromatogram after the reaction in this embodiment. Figure 2 It is the liquid gas chromatogram after the reaction in this embodiment.

[0051] Figure 2 In the formula, the reference formula for the molar amount of the substance to be calibrated is: Where n is the molar amount of the substance to be calibrated, A is the peak area, m 内 is the mass of internal standard mesitylene, f n is the correction factor and M is the molecular weight.

[0052] In this embodiment, the molar amounts of methyl propionate and 3-pentanone in the reaction solution are:

[0053] n(methyl propionate)=[(12.476 / 4.466)×0.102×3.19] / 88.11=10.3 mmol;

[0054] n(3-pentanone)=[(1.558 / 4.466)×0.069×1.15] / 86.13=0.3 mmol.

[0055] Example 3

[0056] 125 mg of the catalyst Co(OAc)2·4H2O, 148 mg of tricyclohexylphosphine oxide (L3), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 43%.

[0057] The structural formula of tricyclohexylphosphine oxide (L3) is:

[0058]

[0059] Example 4

[0060] 125 mg of the catalyst Co(OAc)2·4H2O, 290 mg of 1,1'-bis(diphenylphosphine)ferrocene (L4), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 35%.

[0061] The structural formula of 1,1'-bis(diphenylphosphine) ferrocene (L4) is:

[0062]

[0063] Example 5

[0064] 125 mg of the catalyst Co(OAc)2·4H2O, 300 mg of the monophosphine oxide of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (L5), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 92%.

[0065] The structural formula of the monophosphine oxide of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (L5) is:

[0066]

[0067] Example 6

[0068] 125 mg of the catalyst Co(OAc)2·4H2O, 274 mg of tris(pentafluorophenyl)phosphine oxide (L6), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 81%.

[0069] The structural formula of tris(pentafluorophenyl)phosphine oxide (L6) is:

[0070]

[0071] Example 7

[0072] 125 mg of the catalyst Co(OAc)2·4H2O, 124 mg of tri(2-furyl)phosphine oxide (L7), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 24%.

[0073] The structural formula of tri(2-furyl)phosphine oxide (L7) is:

[0074]

[0075] Example 8

[0076] 125 mg of the catalyst Co(OAc)2·4H2O, 101 mg of diphenylphosphine oxide (L8), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 56%.

[0077] The structural formula of diphenylphosphine oxide (L8) is:

[0078]

[0079] Example 9

[0080] 125 mg of the catalyst Co(OAc)2·4H2O, 131 mg of bis(4-methylphenyl)phosphine oxide (L9), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 84%.

[0081] The structural formula of bis(4-methylphenyl)phosphine oxide (L9) is:

[0082]

[0083] Example 10

[0084] 125 mg of the catalyst Co(OAc)2·4H2O, 117 mg of diphenyl phosphate (L10), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 27%.

[0085] The structural formula of diphenyl phosphate (L10) is:

[0086]

[0087] Example 11

[0088] 125 mg of the catalyst Co(OAc)2·4H2O, 151 mg of 2,2'-bis-(2-naphthyl)phosphine oxide (L11), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 90%.

[0089] The structural formula of 2,2'-bis-(2-naphthyl)phosphine oxide (L11) is:

[0090]

[0091] Example 12

[0092] 125 mg of the catalyst Co(OAc)2·4H2O, 127 mg of bis(4-vinylphenyl)phosphine oxide (L12), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 64%.

[0093] The structural formula of bis(4-vinylphenyl)phosphine oxide (L12) is:

[0094]

[0095] Example 13

[0096] 125 mg of the catalyst Co(OAc)2·4H2O, 107 mg of di(cyclohexyl)phosphine oxide (L13), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 62%.

[0097] The structural formula of di(cyclohexyl)phosphine oxide (L13) is:

[0098]

[0099] Example 14

[0100] 125 mg of the catalyst Co(OAc)2·4H2O, 190 mg of bis(pentafluorophenyl)phosphine oxide (L14), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 87%.

[0101] The structural formula of bis(pentafluorophenyl)phosphine oxide (L14) is:

[0102]

[0103] Example 15

[0104] 125 mg of the catalyst Co(OAc)2·4H2O, 119 mg of bis(4-trifluoromethylphenyl)phosphine oxide (L15), and 10 mL of methanol were sequentially added to a 50 mL autoclave. Ethylene (2.5 bar) and carbon monoxide (40 bar) were then introduced into the autoclave, and the reaction was carried out at 140°C for 16 hours. After the reaction, the autoclave was cooled to room temperature and the pressure was released. 0.12 g of mesitylene was added as an internal standard. 1.0 mL of the reaction solution was analyzed by gas chromatography, and the molar amount of MP was calculated based on the internal standard factor. Under these conditions, the yield of MP obtained was 80%.

[0105] The structural formula of bis(4-trifluoromethylphenyl)phosphine oxide (L15) is:

[0106]

[0107] The present invention provides a method for directly preparing methyl propionate by liquid-phase carbonylation reaction of ethylene, carbon monoxide and methanol using a catalyst system composed of a divalent cobalt salt and an organic phosphine oxide. Compared with traditional ethylene carbonylation methods, this method has the advantages of not requiring the use of precious metals and acidic additives, cheap and readily available ligands, a green and recyclable catalyst system, and mild reaction conditions. Therefore, this method is a green and economical method for synthesizing methyl propionate.

[0108] The above are only preferred embodiments of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the scope of protection of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications without departing from the principle of the present invention should be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide, characterized in that: The method uses ethylene, carbon monoxide and methanol as raw materials and reacts to prepare methyl propionate under the catalysis of a catalytic system; The catalytic system includes a divalent cobalt catalyst and an organic phosphine oxide.

2. The method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide according to claim 1, wherein: The divalent cobalt catalyst is a combination of one or more of cobalt acetate tetrahydrate, cobalt propionate, cobalt carbonate, cobalt hydroxide, cobalt iodide, cobalt tetrafluoroborate and cobalt phosphate.

3. The method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide according to claim 1, characterized in that: The organic phosphine oxide is one or a combination of organic tertiary phosphine oxide and organic secondary phosphine oxide; The structural formula of the organic tertiary phosphine oxide is: The structural formula of the organic secondary phosphine oxide is: Among them, R 1 、R 2 、R 3 It is one of aryl, pyridyl, alkyl, alkoxy and aryloxy.

4. The method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide according to claim 1, wherein: The reaction temperature is 60-160°C.

5. The method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide according to claim 1, characterized in that: The reaction pressure is 0.5-8 MPa.

6. The method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide according to claim 1, characterized in that: In the catalytic system, the molar ratio of the divalent cobalt catalyst to the organic phosphine oxide is 1:0.5-10.

7. The method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide according to claim 1, characterized in that: The molar ratio of the divalent cobalt catalyst to ethylene is 1:20-80.

8. The method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide according to claim 1, characterized in that: The molar ratio of methanol to ethylene is 4 to 20:

1.

9. The method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide according to claim 1, characterized in that: The molar ratio of ethylene to carbon monoxide is 1:10-20.

10. The method for preparing methyl propionate by carbonylation of ethylene and carbon monoxide according to claim 1, characterized in that: The reaction steps are: adding a divalent cobalt catalyst, an organic phosphine oxide and methanol in a reactor in sequence, then respectively introducing ethylene and carbon monoxide until the reaction pressure is reached, heating to the reaction temperature and reacting, and after the reaction is completed, obtaining a methanol solution of methyl propionate.

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