Method for synthesizing methyl 3-hydroxypropionate by forming guanidine-carbonyl cobalt catalyst in situ and catalyzing ethylene oxide hydromethyl esterification reaction
The in situ formation of guanidine-cobalt catalysts addresses the instability and cost issues of existing catalysts by enabling efficient and cost-effective production of 3-hydroxypropionic acid methyl ester through ethylene oxide hydrocarbonylation, suitable for industrial applications.
Patent Information
- Application Number
- CN202510468399.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-15
- Publication Date
- 2025-07-15
AI Technical Summary
In the prior art, the catalyst for preparing methyl 3-hydroxypropionate by hydrogen methylation of ethylene oxide is prone to decomposition and unstable, and is expensive and difficult to industrially apply, and lacks a cheap and stable catalytic system.
The guanidine-carbonyl cobalt catalyst is formed in situ under the carbon monoxide atmosphere by cobalt salt, reducing agent and alkylguanidine hydrochloride, and the guanidine hydromethylation reaction is catalyzed to form methyl 3-hydroxypropionate.
It realizes efficient and inexpensive preparation of methyl 3-hydroxypropionate, the catalyst can be reused, the reaction conditions are mild, and it is suitable for large-scale industrial production.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the field of fine chemicals, and particularly relates to a method for in-situ forming a guanidine-carbonyl cobalt catalyst and catalyzing the hydroformylation reaction of ethylene oxide to synthesize methyl 3-hydroxypropionate. Background Art
[0002] Methyl 3-hydroxypropionate is an important type of fine chemical, which can be used as a solvent, resin or organic synthesis intermediate, and has important application prospects in the field of fine chemicals. 1,3-Propanediol is an important chemical raw material and intermediate, and its main use is as a polymerization monomer for synthesizing polytrimethylene terephthalate (PTT). Therefore, in recent years, the process of preparing methyl 3-hydroxypropionate by the hydroformylation of ethylene oxide and then hydrogenating it to prepare 1,3-propanediol has attracted much attention.
[0003] Currently, the production modes of 1,3-propanediol worldwide show a diverse situation, and each country and enterprise has adopted different production methods to meet market demands: the hydroformylation method of ethylene oxide by Shell, the hydration and hydrogenation method of acrolein by Degussa, the biological fermentation method by Dupont, and the glycerol hydrogenolysis method by Daicel Corporation of Japan.
[0004] Among them, the oxirane hydroformylation method initially uses oxirane and carbon monoxide as raw materials to first prepare 3-hydroxypropanal, and then hydrogenate it to obtain 1,3-propanediol. However, 3-hydroxypropanal is not a stable intermediate and is prone to polycondensation, which is not conducive to the subsequent steps. Around the early 21st century, Shell and Samsung companies improved the oxirane hydroformylation method. The improved method is as follows: Using oxirane, carbon monoxide and methanol as raw materials, and homogeneous cobalt carbonyl as a catalyst, the stable product methyl 3-hydroxypropionate is obtained, and then hydrogenated to obtain the final product 1,3-propanediol. This method is an efficient and potentially developing industrial production route. The key to the efficient progress of the reaction is to use a high-performance catalytic system. In recent years, researchers have developed some catalytic systems with high activity and selectivity for this reaction, such as the catalytic system of Co2(CO)8 and pyridine ligands (Lee B.N., Yang D.J., Byun Y.H. et al. Process for preparing 1,3-alkanediol from epoxide derivative. US6348632-B1[P], 2000.2), supported cobalt catalytic system (Zeng B, Chen L, Zhu G, et al. Nitrogen-doped cobalt nanocatalysts for carbonylation of propylene oxide[J]. Molecular Catalysis, 2020, 494:111109.), etc. Different catalytic systems show different advantages in the oxirane hydroformylation reaction. For example, the catalytic system of cobalt carbonyl and pyridine ligand is known for its high selectivity and mild reaction conditions, and the supported cobalt catalytic system is significantly advantageous for its recyclability. Dicobalt octacarbonyl, as a highly active homogeneous catalyst, is widely used in the preparation of methyl 3-hydroxypropionate by oxirane hydroformylation. However, due to its easy decomposition at room temperature, instability in air, toxicity and high price, it is difficult to be applied in industrial production. Therefore, it is necessary to develop a stable and inexpensive catalyst system.
[0005] In order to efficiently prepare methyl 3-hydroxypropionate and realize the reuse of the catalyst, the present invention aims to prepare a highly efficient, stable and recyclable catalytic system to realize the oxirane hydroformylation reaction to prepare methyl 3-hydroxypropionate under relatively mild conditions. Summary of the Invention
[0006] The purpose of the present invention is to provide a method for in-situ forming a guanidine-cobalt carbonyl catalyst and catalyzing the oxirane hydroformylation reaction to synthesize methyl 3-hydroxypropionate.
[0007] The technical solution of the present invention:
[0008] A method for in-situ forming a guanidine-carbonyl cobalt catalyst and catalyzing the hydroformylation of ethylene oxide to synthesize methyl 3-hydroxypropionate is as follows: A cobalt salt, a reducing agent, and an alkylguanidine hydrochloride are used to in-situ catalyze the hydroformylation of ethylene oxide to generate methyl 3-hydroxypropionate under a carbon monoxide atmosphere at a certain pressure.
[0009] Preferably, the cobalt salt is selected from one of cobalt chloride, cobalt bromide, cobalt acetate, and cobalt carbonate;
[0010] Preferably, the reducing agent is selected from one of Mn and Zn;
[0011] Preferably, the alkylguanidine hydrochloride is selected from one of 1,1,3,3-tetramethylguanidine hydrochloride, 1,1-diethyl-3,3-dimethylguanidine hydrochloride, and 1,1-din-butyl-3,3-dimethylguanidine hydrochloride;
[0012] Preferably, the molar ratio of the cobalt salt to ethylene oxide is 3:100 to 1:100; the molar ratio of the reducing agent to ethylene oxide is 20:100 to 1:100; the molar ratio of the alkylguanidine hydrochloride to ethylene oxide is 3:100 to 1:100; and the concentration of ethylene oxide in methanol is 2.0 mol / L.
[0013] Preferably, the reaction temperature is 25 to 100 °C; the carbon monoxide pressure is 0.5 to 4.0 MPa; and the reaction time is 12 to 48 h.
[0014] Advantages of the present invention:
[0015] 1. The present invention does not require the synthesis of a catalyst. Only a cheap cobalt salt, a reducing agent, and an alkylguanidine hydrochloride are used to in-situ generate an active species for catalyzing the hydroformylation of ethylene oxide, and the efficient preparation of methyl 3-hydroxypropionate can be achieved;
[0016] 2. The reaction raw materials and catalytic system of the present invention are widely sourced and cheaply available. The product methyl 3-hydroxypropionate has a high added value and can be applied to the large-scale production of 1,3-propanediol;
[0017] 3. The method for preparing methyl 3-hydroxypropionate by the hydroformylation of ethylene oxide according to the present invention has high atom economy, relatively mild reaction conditions, meets the requirements of green chemistry, and has a simple process, is easy to operate, has low equipment requirements, and is suitable for large-scale industrial production. Description of the Drawings
[0018] Figure 1 1H NMR spectrum of methyl 3-hydroxypropionate for Example 1.
[0019] Figure 2Gas chromatogram for quantitative analysis of methyl 3-hydroxypropionate in Example 1. Detailed implementation manners
[0020] The following details the specific implementation manners of the present invention in combination with the technical solutions and the figures.
[0021] Example 1
[0022] First, add 0.09 mmol of cobalt chloride, 0.09 mmol of 1,1,3,3-tetramethylguanidine hydrochloride, and 0.6 mmol of Mn powder into a 20 mL high-pressure reactor. Then add 1.5 ml of methanol and 3 mmol of EO. Seal the reactor and displace the atmosphere in the reactor with CO for 3 times. Fill in CO gas, adjust the pressure to 4.0 MPa, place the high-pressure reactor in an oil bath at 70 °C and set the stirrer speed to 400 rpm, and stir and react for 24 h. After the reaction is completed, wait for the reactor to cool down to room temperature, carefully release the remaining CO in the reactor, and then perform GC and GC-MS analyses on the reaction stock solution using dodecane as the internal standard to investigate the reaction situation of the hydroformylation reaction of ethylene oxide. The yield of methyl 3-hydroxypropionate obtained by quantitative analysis of GC testing is 64%, and the results are recorded in Table 1.
[0023] Example 2
[0024] Replace the cobalt chloride in Example 1 with cobalt bromide, and keep other operating conditions unchanged. The yield of methyl 3-hydroxypropionate obtained by quantitative analysis of GC testing is 59%, and the results are recorded in Table 1.
[0025] Example 3
[0026] Replace the cobalt chloride in Example 1 with cobalt acetate, and keep other operating conditions unchanged. The yield of methyl 3-hydroxypropionate obtained by quantitative analysis of GC testing is 55%, and the results are recorded in Table 1.
[0027] Example 4
[0028] Replace the cobalt chloride in Example 1 with cobalt carbonate, and keep other operating conditions unchanged. The yield of methyl 3-hydroxypropionate obtained by quantitative analysis of GC testing is 52%, and the results are recorded in Table 1.
[0029] Example 5
[0030] Replace the Mn powder in Example 1 with Zn powder, and keep other operating conditions unchanged. The yield of methyl 3-hydroxypropionate obtained by quantitative analysis of GC testing is 44%, and the results are recorded in Table 1.
[0031] Example 6
[0032] Replace the 1,1,3,3-tetramethylguanidine hydrochloride in Example 1 with 1,1-diethyl-3,3-dimethylguanidine hydrochloride, with other operating conditions remaining unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is 60%, and the results are recorded in Table 1.
[0033] Example 7
[0034] Replace the 1,1,3,3-tetramethylguanidine hydrochloride in Example 1 with 1,1-di-n-butyl-3,3-dimethylguanidine hydrochloride, with other operating conditions remaining unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is 55%, and the results are recorded in Table 1.
[0035] Comparative Example 1
[0036] Replace the Mn powder in Example 1 with Ni powder, with other operating conditions remaining unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is 3%, and the results are recorded in Table 1.
[0037] Comparative Example 2
[0038] Replace the Mn powder in Example 1 with Mg powder, with other operating conditions remaining unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is <1%, and the results are recorded in Table 1.
[0039] Table 1: Summary of catalytic results of Examples 1-7 and Comparative Examples 1-2 a
[0040]
[0041]
[0042] a Reaction conditions: 3 mmol EO, 1.5 ml MeOH, EO / cobalt salt / guanidine salt / reducing agent = 100 / 3 / 3 / 20, 4 MPa CO, 70 °C, 24 h.
[0043] b Quantitatively calculated by gas chromatography.
[0044] Example 8
[0045] Replace the 0.09 mmol cobalt chloride and 0.09 mmol 1,1,3,3-tetramethylguanidine hydrochloride in Example 1 with 0.06 mmol cobalt chloride and 0.06 mmol 1,1,3,3-tetramethylguanidine hydrochloride, with other operating conditions remaining unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is 60%, and the results are recorded in Table 2.
[0046] Example 9
[0047] Change 0.09 mmol of cobalt chloride and 0.09 mmol of 1,1,3,3-tetramethylguanidine hydrochloride in Example 1 to 0.03 mmol of cobalt chloride and 0.03 mmol of 1,1,3,3-tetramethylguanidine hydrochloride, and keep other operating conditions unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is 54%, and the results are recorded in Table 2.
[0048] Example 10
[0049] Change 0.6 mmol of Mn powder in Example 1 to 0.3 mmol of Mn powder, and keep other operating conditions unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is 54%, and the results are recorded in Table 2.
[0050] Example 11
[0051] Change 0.6 mmol of Mn powder in Example 1 to 0.15 mmol of Mn powder, and keep other operating conditions unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is 43%, and the results are recorded in Table 2.
[0052] Table 2: Summary of catalytic results of Examples 8 - 11 a
[0053]
[0054] a Reaction conditions: 3 mmol EO, 1.5 ml MeOH, 4 MPa CO, 70 °C, 24 h.
[0055] b Molar ratio.
[0056] c Quantitatively calculated by gas chromatography.
[0057] Example 12
[0058] On the basis of Example 1, change the reaction temperature of 70 °C to 30 °C, and keep other operating conditions unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is 70%, and the results are recorded in Table 3.
[0059] Example 13
[0060] On the basis of Example 1, change the reaction temperature of 70 °C to 40 °C, and keep other operating conditions unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis is 78%, and the results are recorded in Table 3.
[0061] Example 14
[0062] On the basis of Example 1, the reaction temperature was changed from 70 °C to 50 °C, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 74%, and the results were recorded in Table 3.
[0063] Example 15
[0064] On the basis of Example 1, the reaction temperature was changed from 70 °C to 60 °C, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 72%, and the results were recorded in Table 3.
[0065] Example 16
[0066] On the basis of Example 1, the reaction temperature was changed from 70 °C to 80 °C, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 60%, and the results were recorded in Table 3.
[0067] Example 17
[0068] On the basis of Example 1, the reaction temperature was changed from 70 °C to 90 °C, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 54%, and the results were recorded in Table 3.
[0069] Example 18
[0070] On the basis of Example 15, the CO pressure was changed from 4.0 MPa to 3.0 MPa, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 73%, and the results were recorded in Figure 2 .
[0071] Example 19
[0072] On the basis of Example 15, the CO pressure was changed from 4.0 MPa to 2.0 MPa, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 71%, and the results were recorded in Table 3.
[0073] Example 20
[0074] On the basis of Example 15, the CO pressure was changed from 4.0 MPa to 1.0 MPa, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 57%, and the results were recorded in Table 3.
[0075] Example 21
[0076] On the basis of Example 15, the CO pressure was changed from 4.0 MPa to 0.5 MPa, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 50%, and the results were recorded in Table 3.
[0077] Example 22
[0078] Based on Example 15, the reaction time was changed from 24 h to 48 h, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 80%, and the results were recorded in Table 3.
[0079] Example 23
[0080] Based on Example 15, the reaction time was changed from 24 h to 12 h, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 64%, and the results were recorded in Table 3.
[0081] Comparative Example 3
[0082] Based on Example 15, the reaction time was changed from 24 h to 4 h, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 20%, and the results were recorded in Table 3.
[0083] Comparative Example 4
[0084] Based on Example 15, the reaction time was changed from 24 h to 8 h, and other operating conditions remained unchanged. The yield of methyl 3-hydroxypropionate obtained by GC test quantitative analysis was 30%, and the results were recorded in Table 3.
[0085] Table 3: Summary of catalytic results of Examples 12 - 23 and Comparative Examples 1 - 2 a
[0086]
[0087]
[0088] a Reaction conditions: 3 mmol EO, 1.5 ml MeOH, EO / cobalt salt / guanidine salt / reducing agent = 100 / 3 / 3 / 20. b Quantitatively calculated by gas chromatography.
Claims
1. A method for in-situ forming a guanidine-carbonyl cobalt catalyst and catalyzing the hydroformylation of ethylene oxide to synthesize methyl 3-hydroxypropionate, characterized in that, Under a carbon monoxide atmosphere at a certain pressure, cobalt salt, reducing agent and alkylguanidine hydrochloride in-situ catalyze the hydroformylation reaction of ethylene oxide to produce methyl 3-hydroxypropionate.
2. The method according to claim 1, characterized in that, The molar ratio of the cobalt salt to ethylene oxide is 3:100 to 1:100; the molar ratio of the reducing agent to ethylene oxide is 20:100 to 1:100; the molar ratio of the alkylguanidine hydrochloride to ethylene oxide is 3:100 to 1:100; the concentration of ethylene oxide in methanol is 2.0 mol / L.
3. The method according to claim 1, wherein The reaction temperature is 25 to 100 °C; the carbon monoxide pressure is 0.5 to 4.0 MPa; the reaction time is 12 to 48 h.
4. The method according to claim 1, wherein The cobalt salt is selected from one of cobalt chloride, cobalt bromide, cobalt acetate and cobalt carbonate.
5. The method according to claim 1, wherein The reducing agent is selected from one of Mn and Zn.
6. The method according to claim 1, characterized in that, The alkylguanidine hydrochloride is selected from one of 1,1,3,3-tetramethylguanidine hydrochloride, 1,1-diethyl-3,3-dimethylguanidine hydrochloride and 1,1-din-butyl-3,3-dimethylguanidine hydrochloride.