Methods for preparing 3-hydroxy-propionate and 1,3-propylene glycol

Abstract

The invention disclosed a method for producing 3-hydroxy-propionate and 1,3-propylene glycol by using epoxide as raw material. In the method, a transitional metal cobalt catalyst and a cocatalyst for the hydroesterification reaction among epoxide, carbon monoxide, and alcohol were chosen, and a hydrogenation catalyst for hydrogenating 3-hydroxy-propionate as well as the corresponding process conditions were selected for producing 3-hydroxy-propionate and 1,3-propylene glycol.

Description

Claims

1. A method for producing 3-hydroxy-propionate, comprising the steps of: providing an epoxide as raw material;providing a transitional metal cobalt catalyst and a cocatalyst; andreacting the epoxide, a carbon monoxide, and an alcohol in the presence of the catalyst and the cocatalyst under appropriate reaction conditions to produce 3-hydroxy-propionate (Reaction 1);wherein, the transitional metal cobalt catalyst includes a pure dicobalt octacarbonyl, cobalt tetracarbonyl and sodium salt thereof, a fatty alcohol solution or acetone solution of a tetracarbonyl anion, and a solution of cobalt carbonyl synthesized in situ, andthe cocatalyst includes an organic compound promoter including pyridine, hydroxyl pyridine, quinoline, isoquinoline, and hydroxyl quinoline substituted by methyl or dimethyl, and derivatives thereof, and/or a inorganic compound promoter which is a salt of alkali metal or alkaline earth metal including sodium acetate, sodium carbonate, sodium bicarbonate, sodium dihydrogen phosphate, sodium sulfate, sodium chloride, sodium bromide, potassium chloride, potassium bromide, potassium hydrogen phosphate diformate, and lithium chloride.

2. A method for producing 1,3-propylene glycol, comprising the steps of: providing an epoxide as raw material;providing a transitional metal cobalt catalyst and a cocatalyst;reacting the epoxide, a carbon monoxide, and an alcohol in the presence of the catalyst and the cocatalyst under appropriate reaction conditions to produce 3-hydroxy-propionate (Reaction 1);providing a hydrogenation catalyst;providing hydrogen gas; andreacting the hydrogen gas with the 3-hydroxy-propionate in the presence the hydrogenation catalyst under appropriate reaction conditions to produce 1,3-propylene glycol (Reaction 2);wherein, the transitional metal cobalt catalyst includes a pure dicobalt octacarbonyl, cobalt tetracarbonyl and sodium salt thereof, a fatty alcohol solution or acetone solution of a tetracarbonyl anion, and a solution of cobalt carbonyl synthesized in situ,the cocatalyst includes an organic compound promoter including pyridine, hydroxyl pyridine, quinoline, isoquinoline, and hydroxyl quinoline substituted by methyl or dimethyl, and derivatives thereof, and/or a inorganic compound promoter which is a salt of alkali metal or alkaline earth metal including sodium acetate, sodium carbonate, sodium bicarbonate, sodium dihydrogen phosphate, sodium sulfate, sodium chloride, sodium bromide, potassium chloride, potassium bromide, potassium hydrogen phosphate diformate, and lithium chloride, andthe hydrogenation catalyst consists of a composite oxide of titanium dioxide and silica as a carrier and cuprous chloride as an aid.

3. A method for producing 3-hydroxy-propionate by using an epoxide as raw material according to claim 1, wherein in the catalyst system in which the transitional metal cobalt is predominant, the organic compound promoter and/or the inorganic compound promoter can be added alone and/or can be used together with water or hydrogen, and whereinthe molar ratio of dicobalt octacarbonyl to the epoxide is 1:100-1:190, and the reaction is carried out at a temperature of 50-100° C., under a pressure of 0-7.0 MPa for a reaction period of 3-5 hours.

4. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 2, wherein in the catalyst system in which the transitional metal cobalt is predominant, the organic compound promoter and/or the inorganic compound promoter can be added alone and/or can be used together with water or hydrogen, and whereinthe molar ratio of dicobalt octacarbonyl to the epoxide is 1:100-1:190, and the reaction is carried out at a temperature of 50-100° C., under a pressure of 0-7.0 MPa for a reaction period of 3-5 hours.

5. A method for producing 3-hydroxy-propionate by using an epoxide as raw material according to claim 3, wherein the temperature is 70-75° C.

6. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 4, wherein the temperature is 70-75° C.

7. A method for producing 3-hydroxy-propionate by using an epoxide as raw material according to claim 1, wherein the epoxide includes ethylene oxide and propylene oxide, and the alcohol includes methanol, ethanol or the mixture thereof.

8. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 2, wherein the epoxide includes ethylene oxide and propylene oxide, and the alcohol includes methanol, ethanol or the mixture thereof.

9. A method for producing 3-hydroxy-propionate by using an epoxide as raw material according to claim 1, wherein in reaction 1, an alcohol saturated by hydrogen is used as a reaction solvent, and hydrogen having a pressure of 0.1-1.5 MPa is added as a promoter to accelerate the activation of the catalysts.

10. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 2, wherein in reaction 1, an alcohol saturated by hydrogen is used as a reaction solvent, and hydrogen having a pressure of 0.1-1.5 MPa is added as a promoter to accelerate the activation of the catalysts.

11. A method for producing 3-hydroxy-propionate by using an epoxide as raw material according to claim 9, wherein in reaction 1, the pressure of the hydrogen added is 0.1-0.5 MPa.

12. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 10, wherein in reaction 1, the pressure of the hydrogen added is 0.1-0.5 MPa.

13. A method for producing 3-hydroxy-propionate by using an epoxide as raw material according to claim 1, wherein when an alcohol is used as the solvent in the reaction 1, water is added in an amount of 0.5-3% by weight as the promoter.

14. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 2, wherein when an alcohol is used as the solvent in the reaction 1, water is added in an amount of 0.5-3% by weight as the promoter.

15. A method for producing 3-hydroxy-propionate by using an epoxide as raw material according to claim 1, wherein 3-hydroxyl pyridine as an organic compound promoter and sodium acetate as an inorganic compound promoter are used together, with the molar ratio of 3-hydroxyl pyridine to sodium acetate of 1:1.

16. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 2, wherein 3-hydroxyl pyridine as an organic compound promoter and sodium acetate as an inorganic compound promoter are used together, with the molar ratio of 3-hydroxyl pyridine to sodium acetate of 1:1.

17. A method for producing 3-hydroxy-propionate by using an epoxide as raw material according to claim 1, wherein the cobalt carbonyl synthesized in situ is produced by using CoO, Co3O4, or CoCO3 as a cobalt source and using methanol as a solvent.

18. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 2, wherein the cobalt carbonyl synthesized in situ is produced by using CoO, Co3O4, or CoCO3 as a cobalt source and using methanol as a solvent.

19. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 2, wherein the composite oxide accounts for 55-80% by weight of the catalyst, the weight ratio of TiO2:SiO2 in the composite oxide being 0.5%-50%: 50%-99.5%, active ingredient cupper oxide being 15-40% by weight of the catalyst, and the cuprous chloride being 0.5-10% by weight of the catalyst.

20. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 19, wherein TiO2:SiO2=8%-20%:80%-92%.

21. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 2, wherein the hydrogenation catalyst is produced by:formulating compounds which contain each component of the catalyst into a solution according to the desired components and blending ratio, wherein the total concentration of the compounds is 5-40% by weight, and then co-precipitating with sodium hydroxide having a concentration of 5%-20%; ormixing a first co-precipitate of a compound containing active component and cocatalyst CuCl with a second co-precipitate of a titanium and silicon-containing complex, the concentration of sodium hydroxide being 5-20% by weight, wherein the precipitation is carried out at room temperature, and the resultant is subjected to aging process at 80° C. for 4 hours, filtrated, washed until the filtrate becomes neutral, dried at 120° C. for 16 hours, and baked at 600° C. for 4 hours; or the aid can be impregnated at the surface of the catalyst and then baked at 350° C. for 4 hours to obtain a composite oxide;crushing the composite oxide, and screening to obtain a carrier having a size of 20 to 60 mesh; andreducing the carrier with hydrogen at 300° C. for 4 hours.

22. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 19, wherein the hydrogenation catalyst is produced by:formulating compounds which contain each component of the catalyst into a solution according to the desired components and blending ratio, wherein the total concentration of the compounds is 5-40% by weight, and then co-precipitating with sodium hydroxide having a concentration of 5%-20%; ormixing a first co-precipitate of a compound containing active component and cocatalyst CuCl with a second co-precipitate of a titanium and silicon-containing complex, the concentration of sodium hydroxide being 5-20% by weight, wherein the precipitation is carried out at room temperature, and the resultant is subjected to aging process at 80° C. for 4 hours, filtrated, washed until the filtrate becomes neutral, dried at 120° C. for 16 hours, and baked at 600° C. for 4 hours; or the aid can be impregnated at the surface of the catalyst and then baked at 350° C. for 4 hours to obtain a composite oxide;crushing the composite oxide, and screening to obtain a carrier having a size of 20 to 60 mesh; andreducing the carrier with hydrogen at 300° C. for 4 hours.

23. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 20, wherein the hydrogenation catalyst is produced by:formulating compounds which contain each component of the catalyst into a solution according to the desired components and blending ratio, wherein the total concentration of the compounds is 5-40% by weight, and then co-precipitating with sodium hydroxide having a concentration of 5%-20%; ormixing a first co-precipitate of a compound containing active component and cocatalyst CuCl with a second co-precipitate of a titanium and silicon-containing complex, the concentration of sodium hydroxide being 5-20% by weight, wherein the precipitation is carried out at room temperature, and the resultant is subjected to aging process at 80° C. for 4 hours, filtrated, washed until the filtrate becomes neutral, dried at 120° C. for 16 hours, and baked at 600° C. for 4 hours; or the aid can be impregnated at the surface of the catalyst and then baked at 350° C. for 4 hours to obtain a composite oxide;crushing the composite oxide, and screening to obtain a carrier having a size of 20 to 60 mesh; andreducing the carrier with hydrogen at 300° C. for 4 hours.

24. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 21, wherein the total concentration of the compounds is 10-20% by weight of the solution, and the sodium hydroxide has a concentration of 7%-15% by weight.

25. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 22, wherein the total concentration of the compounds is 10-20% by weight of the solution, and the sodium hydroxide has a concentration of 7%-15% by weight.

26. A method for producing 1,3-propylene glycol by using an epoxide as raw material according to claim 23, wherein the total concentration of the compounds is 10-20% by weight of the solution, and the sodium hydroxide has a concentration of 7%-15% by weight.