Solid beta-h elimination promoter of sodium sulfamate salt and its preparation method and application
By preparing solid sodium aminosulfonate as a β-H elimination promoter, the problems of low metal salt content, weak alkalinity, and difficult separation in the existing technology have been solved, realizing a highly efficient carbon dioxide carboxylation reaction with broad industrial application prospects.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-12-09
- Publication Date
- 2026-06-09
AI Technical Summary
Existing β-H elimination promoters suffer from problems such as low metal salt content, weak alkalinity, difficulty in separation, and high cost. Furthermore, the use of tert-butanol metal salts leads to a large amount of waste liquid and high separation energy consumption.
Using solid sodium aminosulfonate as a β-H elimination promoter, sodium aminosulfonate is generated by the reaction of diethylenetriamine with chlorosulfonic acid. Combined with nickel compounds and phosphine ligand catalysts, it is then used to carry out the carboxylation reaction of carbon dioxide and ethylene to produce acrylic acid.
It increases the metal salt content, enhances alkalinity, simplifies the separation process, reduces separation energy consumption, and solid sodium aminosulfonate has good stability, a wide range of applications, and is suitable for high-temperature reactions.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of β-H elimination promoter technology, specifically to a solid sodium aminosulfonate β-H elimination promoter, its preparation method, and its application. Background Technology
[0002] In the 1980s, Burkhart first reported the carboxylation reaction of carbon dioxide with alkenes. Using carbon dioxide and styrene as raw materials, he demonstrated that carbon dioxide could be activated to generate nickel propionate lactone intermediates under the action of a nickel complex. By controlling the reaction temperature, phenylpropionic acid or cinnamic acid products could be generated. Building on this, more and more researchers have studied the catalytic carboxylation of unsaturated hydrocarbons with carbon dioxide. Carbon dioxide carboxylation reactions can be widely used to prepare bulk and fine chemicals, as well as intermediates in organic synthesis. In recent years, palladium and nickel-catalyzed reactions of alkenes and alkynes with carbon dioxide have received considerable attention among different catalytically active metals. Some reactions have been used to prepare a series of important industrial products. For example, valuable α,β-unsaturated carboxylic acids and their derivatives can be directly obtained via carbon dioxide carboxylation reactions. The carboxylation reaction of carbon dioxide with ethylene can directly synthesize acrylic acid, which can then be further processed through esterification to obtain various acrylate compounds.
[0003] The carboxylation reaction of carbon dioxide with ethylene is a direct reaction between ethylene and carbon dioxide catalyzed by a metal catalyst. The reaction mechanism is that after the metal catalyst activates carbon dioxide, it reacts with ethylene to generate a metal lactone ring intermediate of propionate. This intermediate can be hydrolyzed or undergo β-H elimination reaction under heating or acid-base conditions. At the same time, the metal catalyst leaves and re-enters the next catalytic cycle, finally yielding acrylic acid or propionic acid compounds.
[0004] From a reaction mechanism perspective, the promoter in the β-H elimination step plays a crucial role in the reaction process. Currently, most β-H elimination promoters are metal salts of acids or alcohols. When using tert-butanol metal salts as β-H elimination promoters for carbon dioxide carboxylation reactions, the reaction yield can reach over 70%. However, the amount of potassium tert-butoxide added is usually 200-1000 times that of the catalyst, generating a large amount of waste liquid. Furthermore, the unreacted tert-butanol metal salt and potassium acrylate product are difficult to separate, leading to increased separation energy consumption. Chevron Philips Chemicals has developed sulfur-oxyacid-substituted polyaromatic resins and phosphorus-oxyacid-substituted polyaromatic resin metal salts (CN110799480A) as supported β-H elimination promoters to replace tert-butanol metal salts in the carboxylation reaction of carbon dioxide and ethylene. Although these supported β-H elimination promoters are easy to separate, these aromatic resin β-H elimination promoters have low metal salt content and weak basicity, resulting in lower reaction efficiency.
[0005] In summary, to solve the above problems, it is of great significance to develop novel β-H elimination promoters for olefin carboxylation reactions that have high metal salt content, strong basicity, are easy to separate, and have simple preparation methods and low cost. Summary of the Invention
[0006] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a solid sodium aminosulfonate β-H elimination promoter, its preparation method and application. The prepared solid sodium aminosulfonate β-H elimination promoter has advantages such as high metal salt content, strong alkalinity and easy separation, and is an additive with great prospects for industrial application.
[0007] The technical solution of this invention is as follows:
[0008] In a first aspect, the present invention provides a method for preparing a solid sodium aminosulfonate β-H elimination promoter, comprising the following steps:
[0009] S1 dissolves diethylenetriamine in an organic solvent;
[0010] S2. Chlorosulfonic acid organic solution is added dropwise to diethylenetriamine organic solution prepared in step S1 at 0-10℃ to carry out the reaction. After the addition is completed, the temperature is raised to continue the reaction.
[0011] S3. The solid generated in step S2 is filtered and washed with chloroform and ethanol respectively. The washed solid is poured into anhydrous methanol and dispersed evenly. The reaction temperature is lowered to 0°C, sodium hydroxide is added for neutralization, the solvent is removed by vacuum distillation, and the obtained solid is washed with ethanol and finally dried to obtain solid sodium aminosulfonate β-H elimination promoter.
[0012] Preferably, in steps S1 and S2, the organic solvent is chloroform or dichloromethane.
[0013] Preferably, in step S2, the molar ratio of diethylenetriamine to chlorosulfonic acid is 1:(3-5); preferably, the molar ratio of diethylenetriamine to chlorosulfonic acid is 1:(3-4); and the concentration of the chlorosulfonic acid organic solution is 2-4 mol / L.
[0014] Preferably, in step S2, the temperature is raised to 50-70℃ and the reaction continues for 7-10 hours; preferably, in step S2, the temperature is raised to 50-60℃ and the reaction continues for 7-9 hours.
[0015] Preferably, in step S3, the molar ratio of sodium hydroxide to diethylenetriaminosulfonic acid is (3-5):1.
[0016] Preferably, in step S3, the stirring time during sodium hydroxide neutralization is 2-4 hours; preferably, in step S3, the stirring time during sodium hydroxide neutralization is 2-3 hours; the drying temperature is 60-90℃, and the drying time is 5-8 hours.
[0017] Secondly, the present invention provides a solid sodium aminosulfonate β-H elimination promoter prepared by the above preparation method, with the following structural formula:
[0018]
[0019] Thirdly, the present invention provides the application of the above-mentioned solid sodium aminosulfonate β-H elimination promoter, in which ethylene and carbon dioxide react to form acrylic acid under the catalytic action of a catalyst composed of nickel compound, phosphine ligand and solid sodium aminosulfonate β-H elimination promoter.
[0020] Preferably, nickel compounds, phosphine ligands, and solid sodium aminosulfonate β-H elimination promoters are added to a reaction vessel, sealed, and then an appropriate amount of carbon dioxide with a mass purity of 90-100% is introduced. Then, the reaction vessel is charged to a specified pressure with ethylene, wherein the mass purity of ethylene is 90-100%. This reaction is a heterogeneous reaction carried out in a batch reactor.
[0021] Preferably, the nickel compound is bis-(1,5-cyclooctadiene)nickel; the phosphine ligand is a bidentate phosphine ligand, preferably, the phosphine ligand is 1,2-bis(dicyclohexylphosphine)ethane or 1,4-bis(dicyclohexylphosphine)butane; the molar ratio of the nickel compound, the phosphine ligand (in molar amounts of P) to the solid sodium aminosulfonate β-H elimination promoter is 1:(1-2.5):(300-900).
[0022] Preferably, the reaction temperature is 140-160℃ and the reaction time is 8-24h; preferably, the reaction temperature is 140-150℃ and the reaction time is 8-14h.
[0023] In this invention, the TON of the carbon dioxide carboxylation reaction is calculated as: the number of moles of sodium acrylate produced by the reaction / the number of moles of catalyst (i.e., nickel compound and phosphine ligand) added.
[0024] Compared with the prior art, the present invention has the following advantages:
[0025] 1. The method for preparing the β-H elimination promoter of the present invention has the advantages of mild reaction conditions, wide range of applicable raw materials, and high product selectivity. Compared with the current carbon dioxide carboxylation reaction, the solid sodium sulfonate β-H elimination promoter of the present invention has the advantages of high metal salt content, strong alkalinity, and easy separation, and is an auxiliary agent with great prospects for industrial application.
[0026] 2. Using the solid sodium sulfonate of the present invention as a β-H elimination promoter has high safety and good stability; it is insoluble in organic solvents and water, which is beneficial for separation from reactants and products, and reduces separation energy consumption; the solid sodium sulfonate β-H elimination promoter of the present invention has a high metal salt content, an exchange capacity of 7.35 mmol / g, and requires a small amount to reduce waste liquid generation; moreover, the solid sodium sulfonate β-H elimination promoter has high temperature resistance and can be used at reaction temperatures above 140°C. Detailed Implementation
[0027] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention.
[0028] Example 1
[0029] In a 250 mL round-bottom flask, 20 mmol of diethylenetriamine and 100 mL of chloroform were added sequentially, and the mixture was stirred thoroughly for 2 h until completely dissolved. The round-bottom flask was then placed in an ice-water bath at 0 °C, and a chloroform solution of chlorosulfonic acid (2 mol / L, 30 mL) was slowly added dropwise to the reaction system using a constant-pressure dropping funnel. After the addition was complete, the mixture was heated to 50 °C and the reaction was continued for 7 h. After the reaction was complete, the resulting white solid was filtered and washed with chloroform and ethanol, respectively. The washed white solid was poured into anhydrous methanol and stirred thoroughly to disperse it evenly. The reaction temperature was lowered to 0 °C, and then 60 mmol of sodium hydroxide solid was added. After the addition was complete, the mixture was stirred at room temperature for 2 h. The solvent was then removed by vacuum distillation, and the resulting pale yellow solid was washed with ethanol. Finally, the solid was dried in a vacuum drying oven at 60 °C for 8 h to obtain a solid sodium aminosulfonate β-H elimination promoter with a yield of 86%.
[0030] Example 2
[0031] In a 250 mL round-bottom flask, 20 mmol of diethylenetriamine and 100 mL of chloroform were added sequentially, and the mixture was stirred thoroughly for 2 h until completely dissolved. The round-bottom flask was then placed in an ice-water bath at 10 °C, and a chloroform solution of chlorosulfonic acid (2 mol / L, 40 mL) was slowly added dropwise to the reaction system using a constant-pressure dropping funnel. After the addition was complete, the mixture was heated to 50 °C and the reaction was continued for 7 h. After the reaction was complete, the resulting white solid was filtered and washed with chloroform and ethanol, respectively. The washed white solid was poured into anhydrous methanol and stirred thoroughly to disperse it evenly. The reaction temperature was lowered to 0 °C, and then 60 mmol of sodium hydroxide solid was added. After the addition was complete, the mixture was stirred at room temperature for 2 h. The solvent was then removed by vacuum distillation, and the resulting pale yellow solid was washed with ethanol. Finally, the solid was dried in a vacuum drying oven at 60 °C for 8 h to obtain a solid sodium aminosulfonate β-H elimination promoter with a yield of 90%.
[0032] Example 3
[0033] In a 250 mL round-bottom flask, 20 mmol of diethylenetriamine and 100 mL of chloroform were added sequentially, and the mixture was stirred thoroughly for 2 h until completely dissolved. The round-bottom flask was then placed in an ice-water bath at 0 °C, and a chloroform solution of chlorosulfonic acid (2 mol / L, 30 mL) was slowly added dropwise to the reaction system using a constant-pressure dropping funnel. After the addition was complete, the mixture was heated to 60 °C and the reaction was continued for 9 h. After the reaction was complete, the resulting white solid was filtered and washed with chloroform and ethanol, respectively. The washed white solid was poured into anhydrous methanol and stirred thoroughly to disperse it evenly. The reaction temperature was lowered to 0 °C, and then 60 mmol of sodium hydroxide solid was added. After the addition was complete, the mixture was stirred at room temperature for 2 h. The solvent was then removed by vacuum distillation, and the resulting pale yellow solid was washed with ethanol. Finally, the solid was dried in a vacuum drying oven at 90 °C for 5 h to obtain a solid sodium aminosulfonate β-H elimination promoter with a yield of 91%.
[0034] Example 4
[0035] In a 250 mL round-bottom flask, 20 mmol of diethylenetriamine and 100 mL of dichloromethane were added sequentially, and the mixture was stirred thoroughly for 2 h until completely dissolved. Then, the round-bottom flask was placed in an ice-water bath at 5 °C, and a 2 mol / L, 30 mL solution of dichloromethane in chlorosulfonic acid was slowly added dropwise to the reaction system using a constant-pressure dropping funnel. After the addition was complete, the mixture was heated to 50 °C and the reaction was continued for 7 h. After the reaction was complete, the resulting white solid was filtered and washed with dichloromethane and ethanol, respectively. The washed white solid was poured into anhydrous methanol and stirred thoroughly to disperse it evenly. The reaction temperature was lowered to 0 °C, and then 60 mmol of sodium hydroxide solid was added. After the addition was complete, the mixture was stirred at room temperature for 3 h. The solvent was then removed by vacuum distillation, and the resulting pale yellow solid was washed with ethanol. Finally, the solid was dried in a vacuum drying oven at 70 °C for 7 h to obtain a solid sodium aminosulfonate β-H elimination promoter with a yield of 86%.
[0036] Examples 5-9
[0037] In a 150 mL high-pressure reactor, under nitrogen protection, 0.1 mmol of bis-(1,5-cyclooctadiene)nickel (Ni(COD)2), bisphosphine ligand, 30 mmol of β-H elimination promoter, and 60 mL of tetrahydrofuran (THF) were added sequentially. The reactor was sealed, and the gas inside was replaced with carbon dioxide three times. Carbon dioxide was then introduced until the reactor pressure reached 1 MPa, followed by the introduction of ethylene until the reactor pressure reached 5 MPa. The temperature was slowly increased to 140 °C under temperature control, and the reaction was carried out for 8 hours. After cooling to room temperature, the reactor was removed, the β-H elimination promoter was filtered, and the resulting liquid was analyzed. The raw materials and reaction parameters for Examples 5-9 are shown in Table 1.
[0038] Table 1. Raw materials and reaction-related parameters for Examples 5-9
[0039]
[0040] Examples 10-16
[0041] In a 150 mL high-pressure reactor, under nitrogen protection, 0.1 mmol of bis-(1,5-cyclooctadiene)nickel (Ni(COD)2), 0.15 mmol of 1,2-bis(dicyclohexylphosphine)ethane, a β-H elimination promoter, and 60 mL of tetrahydrofuran were added sequentially. The reactor was sealed, and the gas inside was replaced with carbon dioxide three times. Carbon dioxide was then introduced until the reactor pressure reached 1 MPa, followed by the introduction of ethylene until the reactor pressure reached 5 MPa. The temperature was slowly increased to the set temperature and reacted for the set time using a temperature controller. After cooling to room temperature, the reactor was removed, the β-H elimination promoter was filtered, and the resulting liquid was analyzed. The raw materials and reaction parameters for Examples 10-16 are shown in Table 2.
[0042] Table 2. Raw materials and reaction-related parameters for Examples 10-16
[0043]
[0044] Comparative Examples 1-3
[0045] In a 150 mL high-pressure reactor, under nitrogen protection, 0.1 mmol of bis-(1,5-cyclooctadiene)nickel (Ni(COD)2), 0.15 mmol of 1,2-bis(dicyclohexylphosphine)ethane, 30 mmol of β-H elimination promoter, and 60 mL of tetrahydrofuran were added sequentially. The reactor was sealed, and the gas inside was replaced with carbon dioxide three times. Carbon dioxide was then introduced until the reactor pressure reached 1 MPa, followed by the introduction of ethylene until the reactor pressure reached 5 MPa. The temperature was slowly increased to 140 °C under temperature control, and the reaction was carried out for 14 h. After cooling to room temperature, the reactor was removed, and the resulting liquid was analyzed. The raw materials and reaction parameters for Comparative Examples 1-3 are shown in Table 3.
[0046] Table 3. Raw materials and reaction-related parameters for Comparative Examples 1-3
[0047]
[0048] Compared with the three β-H elimination promoters used in Comparative Examples 1-3, the solid sodium aminosulfonate β-H elimination promoter of the present invention has a higher sodium sulfonate content, with a sodium sulfonate content of 90 mmol when the addition amount is 30 mmol, which can effectively promote the β-H elimination reaction; after cooling, it has poor oil solubility and water solubility, is easy to separate, and can be separated from the product after filtration.
Claims
1. A method for preparing a solid sodium aminosulfonate β-H elimination promoter, characterized in that, Includes the following steps: S1 dissolves diethylenetriamine in an organic solvent; S2. Chlorosulfonic acid organic solution is added dropwise to diethylenetriamine organic solution prepared in step S1 at 0-10℃ to carry out the reaction. After the addition is completed, the temperature is raised to continue the reaction. S3. The solid generated in step S2 is filtered and washed with chloroform and ethanol respectively. The washed solid is poured into anhydrous methanol and dispersed evenly. The reaction temperature is lowered to 0°C, sodium hydroxide is added for neutralization, the solvent is removed by vacuum distillation, and the obtained solid is washed with ethanol and finally dried to obtain solid sodium aminosulfonate β-H elimination promoter.
2. The method for preparing the solid sodium aminosulfonate β-H elimination promoter as described in claim 1, characterized in that, In steps S1 and S2, the organic solvent is chloroform or dichloroform.
3. The method for preparing the solid sodium aminosulfonate β-H elimination promoter as described in claim 1, characterized in that, In step S2, the molar ratio of diethylenetriamine to chlorosulfonic acid is 1:(3-5); preferably, the molar ratio of diethylenetriamine to chlorosulfonic acid is 1:(3-4); and the concentration of the chlorosulfonic acid organic solution is 2-4 mol / L.
4. The method for preparing the solid sodium aminosulfonate β-H elimination promoter as described in claim 1, characterized in that, In step S2, the temperature is raised to 50-70℃ and the reaction continues for 7-10 hours; preferably, in step S2, the temperature is raised to 50-60℃ and the reaction continues for 7-9 hours.
5. The method for preparing the solid sodium aminosulfonate β-H elimination promoter as described in claim 1, characterized in that, In step S3, the molar ratio of sodium hydroxide to diethylenetriaminosulfonic acid is (3-5):
1.
6. The method for preparing the solid sodium aminosulfonate β-H elimination promoter as described in claim 1, characterized in that, In step S3, the stirring time during sodium hydroxide neutralization is 2-4 hours; preferably, the stirring time during sodium hydroxide neutralization in step S3 is 2-3 hours; the drying temperature is 60-90℃ and the drying time is 5-8 hours.
7. The solid sodium aminosulfonate β-H elimination promoter prepared by the preparation method according to any one of claims 1-6, characterized in that, The structure is as follows:
8. The application of the solid sodium aminosulfonate β-H elimination promoter as described in claim 7, characterized in that, Ethylene and carbon dioxide react to form acrylic acid under the catalysis of a catalyst composed of nickel compounds, phosphine ligands, and a solid sodium aminosulfonate β-H elimination promoter.
9. The application of the solid sodium aminosulfonate β-H elimination promoter as described in claim 8, characterized in that, The nickel compound is bis-(1,5-cyclooctadiene)nickel; the phosphine ligand is a bidentate phosphine ligand, preferably 1,2-bis(dicyclohexylphosphine)ethane or 1,4-bis(dicyclohexylphosphine)butane; the molar ratio of the nickel compound, the phosphine ligand and the solid sodium aminosulfonate β-H elimination promoter is 1:(1-2.5):(300-900).
10. The application of the solid sodium aminosulfonate β-H elimination promoter as described in claim 8, characterized in that, The reaction temperature is 140-160℃ and the reaction time is 8-24h; preferably, the reaction temperature is 140-150℃ and the reaction time is 8-14h.