Synthesis method of 3-hydroxy propanesulfonic acid

Abstract

The invention discloses a method for preparing 3-hydroxypropanesulfonic acid by reacting 3-mercapto-1-propanol in air in the presence of a catalyst, wherein the catalyst is a Pd, La and Ru supported catalyst; compared with the existing production process, the method has the advantages of high route total yield, avoidance of the problem that waste sulfate is difficult to treat in the existing production process, high atom utilization rate and low environmental protection pressure.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical engineering, and particularly relates to a method for synthesizing propanesultone. Background Art

[0002] Lithium-ion batteries are widely used in electric bicycles, electric vehicles, and hybrid electric vehicles, and are considered to be the most promising power source in the electric vehicle scenario due to their high energy density, low self-discharge rate, and long cycle life. However, the electrolyte in lithium-ion batteries is thermodynamically unstable during the charging process. Under overcharge or overheat conditions, the electrolyte is easily oxidized at the positive electrode and reduced at the negative electrode surface. Usually, after the reduction reaction occurs on the negative electrode surface of the battery, a solid electrolyte interphase membrane (SEI) can be formed, thereby inhibiting the continuous decomposition of the electrolyte. 1,3-propanesultone (1,3-PS) can promote the formation of the SEI membrane, has a significant effect on inhibiting the reduction of the charge and discharge efficiency of lithium-ion secondary batteries, and has an obvious improvement effect on the high-temperature performance of the battery. It is an important additive for lithium-ion battery electrolytes.

[0003] Currently, there is only one industrial production route for 1,3-PS. This route uses allyl alcohol as the starting material, adds it with NaHSO3 to generate sodium 3-hydroxypropanesulfonate, and then acidifies it to obtain the intermediate 3-hydroxypropanesulfonic acid. Then, it is distilled under reduced pressure and dehydrated intramolecularly to obtain 1,3-propanesultone. The reaction route is shown as follows. The intermediate 3-hydroxypropanesulfonic acid is the key and difficult point of this process. The current preparation process has the following problems: 1) In the acidification step, sulfuric acid needs to be used for neutralization, and the waste sodium sulfate produced is difficult to treat due to its high organic matter content, with low atom utilization rate and great environmental protection pressure; 2) The total yield of 3-hydroxypropanesulfonic acid is only 70%.

[0004]

[0005] Therefore, it is of great significance to develop a synthesis method of 3-hydroxypropanesulfonic acid with high yield and less pollution of three wastes. Summary of the Invention

[0006] In order to overcome the deficiencies of the prior art, the present invention provides a new synthesis method of 3-hydroxypropanesulfonic acid. Using allyl alcohol as the raw material, it is added with hydrogen sulfide and oxidized by air to obtain 3-hydroxypropanesulfonic acid. This method is more environmentally friendly, less polluting, and has a high total yield.

[0007] To achieve the above object, the present invention adopts the following technical solutions:

[0008] A synthesis method of 3-hydroxypropanesulfonic acid, comprising the following steps: 3-mercapto-1-propanol reacts in the air in the presence of a catalyst to obtain 3-hydroxypropanesulfonic acid.

[0009] Preferably, the catalyst is a Pd, La, Ru supported catalyst.

[0010] Preferably, the mass ratio of Pd, La, Ru is: 100:1.3 - 2.2:0.3 - 0.7, and the carrier is preferably activated carbon, and the mass ratio of Pd to the carrier is 1 - 3:100.

[0011] Preferably, the preparation method of the catalyst is: dissolving the salts of metals Pd, La, Ru in hydrochloric acid solution, then adding this solution to the aqueous suspension of activated carbon, stirring for 1.5 - 2.5 hours, and then adding an alkali solution to adjust the pH = 13.5 - 14. Then adding an aldehyde solution for reduction, and then heating the solution to 75 - 85 °C for reaction, cooling, filtering, and washing the filter cake with deionized water.

[0012] Preferably, the salts of metals Pd, La, Ru can be soluble salts such as hydrochlorides, nitrates, sulfates, etc.

[0013] Preferably, the mass ratio of metals Pd, La, Ru in the salts of metals Pd, La, Ru is 100:1.3 - 2.2:0.3 - 0.7, and the mass ratio of Pd to activated carbon is 1 - 3:100.

[0014] Preferably, the hydrochloric acid has a mass fraction of 5 - 20%, and the dosage is about 20 - 50 times the mass of the metal salt; the aldehyde solution has a mass fraction of 2 - 10%, and the dosage is about 3 - 10 times the mass of the metal salt;

[0015] Preferably, the aldehyde solution is formaldehyde or acetaldehyde solution;

[0016] The alkali solution is preferably an aqueous solution of alkali metal hydroxide, such as sodium hydroxide, potassium hydroxide solution.

[0017] Preferably, the 3 - mercapto - 1 - propanol can be directly purchased or synthesized by oneself, and the synthesis method of the 3 - mercapto - 1 - propanol is: adding allyl alcohol and a radical initiator to an alcohol solvent and mixing evenly, and then introducing hydrogen sulfide gas for reaction to obtain 3 - mercapto - 1 - propanol;

[0018] Preferably, the synthesis reaction equation of 3 - mercapto - 1 - propanol is as follows:

[0019]

[0020] The alcohol solvent in the present invention is ethanol, propanol, butanol, ethylene glycol, propylene glycol or butylene glycol, and the dosage is 5 - 20 times the mass of allyl alcohol.

[0021] The radical initiator in the present invention is a peroxide initiator, preferably tert - butyl hydroperoxide or di - tert - butyl peroxide ether, and the dosage is 0.5 - 2% of the mass of allyl alcohol.

[0022] In the synthesis method of 3-mercapto-1-propanol according to the present invention, the reaction temperature is 70-110 °C; the reaction pressure is 1-3 MPa; the reaction time is 2-5 h.

[0023] In some preferred embodiments of the present invention, the synthesis method of 3-mercapto-1-propanol is as follows: Allyl alcohol is dissolved in ethanol to prepare a 10-15% solution, which is added to a stirring kettle equipped with a self-priming impeller, and 1-1.5% Wt of tert-butyl hydroperoxide is added. Hydrogen sulfide gas is introduced at 80-100 °C, and the pressure in the reaction kettle is maintained at 2-3 Mpa, and the reaction is carried out for 3-4 h.

[0024] The obtained solution can be directly subjected to the next reaction without separating 3-mercapto-1-propanol.

[0025] The synthesis reaction equation of 3-hydroxypropanesulfonic acid according to the present invention is as follows:

[0026]

[0027] The catalyst dosage described in the present invention is 2-5% of the mass of 3-mercapto-1-propanol.

[0028] In the synthesis reaction of 3-hydroxypropanesulfonic acid according to the present invention, the reaction temperature is 80-120 °C, preferably 90-110 °C, the pressure is 101 Kpa-400 kpa, preferably 150 Kpa-300 kpa, and the reaction time is 6-12 h, preferably 8-10 h.

[0029] The advantages of the present invention are as follows: 1) Hydrogen sulfide and allyl alcohol are used for free radical addition to obtain 3-mercapto-1-propanol, and then air oxidation is used to prepare 3-hydroxypropanesulfonic acid, a key intermediate of 1,3-PS, with high atom utilization rate. The problem of difficult treatment of waste sulfate in the existing production process is avoided. 2) A composite metal-activated carbon catalyst is used in the thiol oxidation reaction, which has the advantages of high selectivity and easy separation. 3) The total yield of the route > 90%, higher than 70% of the existing process. Detailed implementation manners

[0030] The main raw material allyl alcohol is purchased from Showa Denko of Japan, hydrogen sulfide gas is purchased from Dalian Dete Gas Co., Ltd., PdCl2, LaCl3·7H2O, RuCl3·3H2O, hydrochloric acid and NaOH are purchased from Sigma-Aldrich.

[0031] The technical solutions of the present invention will be clearly and completely described below in conjunction with the detailed implementation manners. However, those skilled in the art will understand that the following described embodiments are some embodiments of the present invention, not all embodiments, and are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention.

[0032] <Test Method>

[0033] 1. For the composition analysis of the solid-phase catalyst, inductively coupled plasma emission spectrometry (ICP) is used for analysis. For the selectivity of the addition reaction, gas chromatography is used for determination. For the selectivity of the oxidation reaction, gas chromatography and liquid chromatography are used for determination.

[0034] Example 1

[0035] (1) Preparation of 3-mercapto-1-propanol: Dissolve 10 g of allyl alcohol in 100 g of ethanol, add it to a stirring kettle equipped with a self-aspirating impeller, add 0.1 g of tert-butyl hydroperoxide, and introduce hydrogen sulfide gas at 80 °C. Maintain the pressure in the reaction kettle at 2 Mpa and react for 3 h. The obtained solution is directly used for the next reaction.

[0036] (2) Preparation of the composite metal-activated carbon catalyst: Dissolve 2.5 g of PdCl2, 0.05 g of LaCl3·7H2O, and 0.012 g of RuCl3·3H2O in 50 mL of 10% hydrochloric acid solution, and slowly drip it into a water (200 mL) suspension containing 50 g of activated carbon at room temperature. At the same time, stir it on a constant-temperature magnetic stirrer for 2 hours, and then slowly add 20% NaOH aqueous solution to adjust the pH = 14. Add 10 mL of 5% formaldehyde solution dropwise at room temperature for reduction, and then heat the solution to 80 °C and maintain it for 1 h. Subsequently, cool it to room temperature, filter, wash the filter cake with deionized water until the pH = 7, and store it for standby under a nitrogen atmosphere.

[0037] (3) Preparation of 3-hydroxypropanesulfonic acid: Add the solution prepared in reaction (2) to a reaction kettle equipped with a self-aspirating impeller, and then add 0.47 g of the composite metal-activated carbon catalyst. Control the temperature in the kettle at 90 °C, introduce air until the pressure reaches 150 Kpa, and react for 8 h. After the reaction, filter out the catalyst to obtain a concentrated ethanol solution of 3-hydroxypropanesulfonic acid. The yield of 3-hydroxypropanesulfonic acid is 92%.

[0038] Example 2

[0039] (1) Preparation of 3-mercapto-1-propanol: Dissolve 10 g of allyl alcohol in 85 g of propanol, add it to a stirring kettle equipped with a self-aspirating impeller, add 0.12 g of di-tert-butyl peroxide, and introduce hydrogen sulfide gas at 90 °C. Maintain the pressure in the reaction kettle at 2.5 Mpa and react for 3.5 h. The obtained solution is directly used for the next reaction.

[0040] (2) Preparation of composite metal-activated carbon catalyst: Dissolve 1.25 g of PdCl2, 0.04 g of LaCl3·7H2O and 0.01 g of RuCl3·3H2O in 50 mL of 20% hydrochloric acid solution, and slowly drop it into a water (200 mL) suspension containing 50 g of activated carbon at room temperature. At the same time, stir on a constant temperature magnetic stirrer for 2 hours, and then slowly add 20% NaOH aqueous solution to adjust the pH = 14. Add 10 mL of 10% formaldehyde solution dropwise at room temperature for reduction, and then heat the solution to 80 °C and maintain it for 1 h. Subsequently, cool it to room temperature, filter, wash the filter cake with deionized water until the pH = 7, and store it for standby under a nitrogen atmosphere.

[0041] (3) Preparation of 3-hydroxypropanesulfonic acid: Add the solution prepared in reaction (2) to a reaction kettle equipped with a self-priming impeller, and then add 0.55 g of composite metal-activated carbon catalyst. Control the kettle temperature at 100 °C, introduce air to 200 Kpa, and react for 9 h. After the reaction is completed, cool down, filter out the catalyst, and obtain a concentrated solution of 3-hydroxypropanesulfonic acid in propanol. The yield of 3-hydroxypropanesulfonic acid is 95%.

[0042] Example 3

[0043] (1) Preparation of 3-mercapto-1-propanol: Dissolve 10 g of allyl alcohol in 65 g of ethylene glycol, add it to a stirring kettle equipped with a self-priming impeller, add 0.15 g of tert-butyl hydroperoxide, and introduce hydrogen sulfide gas at 100 °C. Maintain the pressure in the reaction kettle at 3 Mpa and react for 4 h. The obtained solution is directly used for the next reaction.

[0044] (2) Preparation of composite metal-activated carbon catalyst: Dissolve 1 g of PdCl2, 0.03 g of LaCl3-7H2O and 0.01 g of RuCl3-3H2O in 50 mL of 5% hydrochloric acid solution, and slowly drop it into a water (200 mL) suspension containing 50 g of activated carbon at room temperature. At the same time, stir on a constant temperature magnetic stirrer for 2 hours, and then slowly add 20% NaOH aqueous solution to adjust the pH = 13.5. Add 10 mL of 2% formaldehyde solution dropwise at room temperature for reduction, and then heat the solution to 80 °C and maintain it for 1 h. Subsequently, cool it to room temperature, filter, wash the filter cake with deionized water until the pH = 7, and store it for standby under a nitrogen atmosphere.

[0045] (3) Preparation of 3-hydroxypropanesulfonic acid: Add the solution prepared in reaction (2) to a reaction kettle equipped with a self-priming impeller, and then add 0.63 g of composite metal-activated carbon catalyst. Control the kettle temperature at 110 °C, introduce air to 300 Kpa, and react for 10 h. After the reaction is completed, cool down, filter out the catalyst, and obtain a concentrated solution of 3-hydroxypropanesulfonic acid in propanol. The yield of 3-hydroxypropanesulfonic acid is 93%.

[0046] Example 4

[0047] (1) Preparation of 3-mercapto-1-propanol: Dissolve 10 g of allyl alcohol in 65 g of ethylene glycol, add it to a stirring kettle equipped with a self-priming impeller, add 0.15 g of tert-butyl hydroperoxide, and introduce hydrogen sulfide gas at 70 °C. Maintain the pressure in the reaction kettle at 1 Mpa and react for 2 h. The resulting solution is directly subjected to the next reaction.

[0048] (2) Preparation of composite metal-activated carbon catalyst: Dissolve 1 g of PdCl2, 0.03 g of LaCl3·7H2O and 0.01 g of RuCl3·3H2O in 50 mL of 10% hydrochloric acid solution, and slowly drop it into a water (200 mL) suspension containing 50 g of activated carbon at room temperature while stirring on a constant temperature magnetic stirrer for 2 hours. Then slowly add 20% aqueous NaOH solution to adjust the pH to 14. Add 10 mL of 5% formaldehyde solution dropwise at room temperature for reduction, then heat the solution to 80 °C and maintain it for 1 h. Subsequently, cool to room temperature, filter, wash the filter cake with deionized water until the pH is 7, and store it for standby under a nitrogen atmosphere.

[0049] (3) Preparation of 3-hydroxypropanesulfonic acid: Add the solution prepared in reaction (2) to a reaction kettle equipped with a self-priming impeller, then add 0.31 g of composite metal-activated carbon catalyst, control the kettle temperature at 80 °C, introduce air to 110 Kpa, and react for 10 h. After the reaction is completed, cool down, filter out the catalyst, and obtain a concentrated solution of 3-hydroxypropanesulfonic acid propanol. The yield of 3-hydroxypropanesulfonic acid is 82%.

[0050] Comparative Example 1 (only Pb metal as the oxidant)

[0051] (1) Preparation of 3-mercapto-1-propanol: Dissolve 10 g of allyl alcohol in 65 g of ethylene glycol, add it to a stirring kettle equipped with a self-priming impeller, add 0.15 g of tert-butyl hydroperoxide, and introduce hydrogen sulfide gas at 70 °C. Maintain the pressure in the reaction kettle at 1 Mpa and react for 2 h. The resulting solution is directly subjected to the next reaction.

[0052] (2) Preparation of Pd-activated carbon catalyst: Dissolve 1 g of PdCl2 in 50 mL of 10% hydrochloric acid solution, and slowly drop it into a water (200 mL) suspension containing 50 g of activated carbon at room temperature while stirring on a constant temperature magnetic stirrer for 2 hours. Then slowly add 20% aqueous NaOH solution to adjust the pH to 14. Add 10 mL of 5% formaldehyde solution dropwise at room temperature for reduction, then heat the solution to 80 °C and maintain it for 1 h. Subsequently, cool to room temperature, filter, wash the filter cake with deionized water until the pH is 7, and store it for standby under a nitrogen atmosphere.

[0053] (3) Preparation of 3-hydroxypropanesulfonic acid: The solution prepared in reaction (2) was added to a reaction kettle equipped with a self-priming impeller, and then 0.31 g of a composite metal-activated carbon catalyst was added. The temperature of the kettle was controlled at 80 °C, air was introduced until the pressure reached 110 KPa, and the reaction was carried out for 10 h. After the reaction was completed, the temperature was lowered, the catalyst was filtered off, and a concentrated solution of 3-hydroxypropanesulfonic acid in propanol was obtained. The yield of 3-hydroxypropanesulfonic acid was 50%.

Claims

1. A method for synthesizing 3-hydroxypropanesulfonic acid, characterized in that, It includes the following steps: 3-Mercapto-1-propanol reacts in air in the presence of a catalyst to obtain 3-hydroxypropanesulfonic acid.

2. The synthesis method according to claim 1, characterized in that, The catalyst is a Pd, La, Ru supported catalyst; Preferably, the mass ratio of Pd, La, Ru is: 100:1.3 - 2.2:0.3 - 0.7; Preferably, the carrier is activated carbon; Preferably, the mass ratio of Pd to the carrier is 1 - 3:

100.

3. The synthesis method according to claim 1, characterized in that, The preparation method of the catalyst is: dissolving salts of metals Pd, La, Ru in a hydrochloric acid solution, then adding this solution to an aqueous suspension of activated carbon and stirring, and then adding an alkali solution; then adding an aldehyde solution for a reduction reaction to obtain the catalyst; Preferably, stir for 1.5 - 2.5 hours, add an alkali solution to adjust the pH = 13.5 - 14; Preferably, the reduction reaction temperature is 75 - 85 °C.

4. The synthesis method according to claim 3, wherein The mass ratio of metals Pd, La, Ru in the salts of metals Pd, La, Ru is 100:1.3 - 2.2:0.3 - 0.7, and the mass ratio of activated carbon to Pd is 20 - 120:1; Preferably, the hydrochloric acid has a mass fraction of 5 - 20%, and the dosage is 20 - 50 times the mass of the metal salt. The aldehyde solution has a mass fraction of 2 - 10%, and the dosage is 3 - 10 times the mass of the metal salt; Preferably, the aldehyde solution is a formaldehyde or acetaldehyde solution; Preferably, the alkali solution is an aqueous solution of an alkali metal hydroxide.

5. The synthesis method according to claim 1, characterized in that, The synthesis method of 3-mercapto-1-propanol is: adding allyl alcohol and a radical initiator to an alcohol solvent and mixing evenly, and then introducing hydrogen sulfide gas for reaction to obtain 3-mercapto-1-propanol; Preferably, the alcohol solvent is ethanol, propanol, butanol, ethylene glycol, propylene glycol or butanediol, and the dosage is 5 - 20 times the mass of allyl alcohol; Preferably, the radical initiator is a peroxide initiator, preferably tert-butyl hydroperoxide or di-tert-butyl peroxide ether, and the dosage is 0.5 - 2% of the mass of allyl alcohol; Preferably, in the synthesis method of 3-mercapto-1-propanol, the reaction temperature is 70 - 110 °C; the reaction pressure is 1 - 3 MPa; the reaction time is 2 - 5 h.

6. The synthesis method according to any one of claims 1-5, characterized in that, The dosage of the catalyst is 2 - 5% of the mass of 3-mercapto-1-propanol.

7. The synthesis method according to any one of claims 1-6, characterized in that, In the synthesis reaction of 3-hydroxypropanesulfonic acid, the reaction temperature is 80 - 120 °C, preferably 90 - 110 °C, the pressure is 101 Kpa - 400 kpa, preferably 150 Kpa - 300 kpa, and the reaction time is 6 - 12 h, preferably 8 - 10 h.

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