Production method for 1,4-butanediol
View Patent ↗An object of the present invention is to provide high-quality 1,4BG capable of working out to a raw material of PBT with good color tone, by efficiently removing and refining impurities mixed when producing a biomass-derived 1,4BG on an industrial scale and the present invention relates to a production method of refined 1,4BG, where a crude 1,4BG-containing solution is obtained from refined raw material 1,4BG obtained by removing bacterial cells, salt contents and water from the fermentation culture medium, through a step of removing high-boiling-point components and/or low-boiling-point components by distillation and/or a step of converting an unsaturated compound to a hydride and the target product is obtained as a side stream in a further distillation step.
1. A method for producing refined 1,4-butanediol having a concentration of a cyclic carbonyl compound having a carbon atom number of 5 or 6 of 12 ppm by mass or less, comprising biologically producing 1,4-butanediol in a culture medium for fermentation of an organism capable of producing 1,4-butanediol, at least partially removing each of a bacterial cell, a salt content and water from said fermentation culture medium to obtain a refined raw material 1,4-butanediol-containing solution, obtaining therefrom a crude 1,4-butanediol-containing solution through the following steps (b′) and (c) and optionally the following steps (a) and (b), refining said crude 1,4-butanediol-containing solution through the following step (d) and obtaining said refined 1,4-butanediol having a concentration of a cyclic carbonyl compound having a carbon atom number of 5 or 6 of 12 ppm by mass or less:
Step (a):
a step of distilling said refined raw material 1,4-butanediol-containing solution in a distillation column to remove components which are contained in said refined raw material 1,4-butanediol-containing solution and higher in the boiling point than 1,4-butanediol;
Step (b):
a step of distilling said refined raw material 1,4-butanediol-containing solution in a distillation column to remove components which are contained in said refined raw material 1,4-butanediol-containing solution and lower in the boiling point than 1,4-butanediol;
Step (b′):
a step of bringing said refined raw material 1,4-butanediol-containing solution, optionally after treatment in one or both of steps (a) and (b), into contact with a base;
Step (c):
a hydrogenating step of at least partially converting unsaturated compounds contained in said refined raw material 1,4-butanediol-containing solution obtained from step (b′) into a hydride via hydrogenation; and
Step (d):
a step of distilling said crude 1,4-butanediol-containing solution in a distillation column, withdrawing the refined 1,4-butanediol from a side stream and obtaining said refined 1,4-butanediol having a concentration of a cyclic carbonyl compound having a carbon atom number of 5 or 6 of 12 ppm by mass or less.
2. The method as claimed in claim 1 , wherein the concentration of a cyclic carbonyl compound having a carbon atom number of 5 or 6 in the refined 1,4-butanediol obtained in said step (d) is 2-10 ppm by mass.
3. The method as claimed in claim 1 , comprising step (a) and further comprising the following step (e):
Step (e):
a step of distilling components higher in the boiling point than 1,4-butanediol, which are separated in said step (a), in a distillation column and thereby separating and recovering 1,4-butanediol.
4. The method as claimed in claim 1 , wherein the water concentration in the refined raw material 1,4-butanediol-containing solution immediately before passing through any one step of said steps (a) to (c) or through the step (b′) is from 0.01 to 20 mass % and the pH thereof is 5 or more.
5. The method as claimed in claim 1 , wherein in the hydrogenation step of said step (c), hydrogenation is performed using a solid catalyst having a nickel-containing metal supported on at least either kieselguhr or silica.
6. The method as claimed in claim 1 , wherein the base in said step (b′) is a solid base.
7. The method as claimed in claim 1 , comprising said step (b), wherein the components lower in the boiling point than 1,4-butanediol in said step (b) contain 1-acetoxy-4-hydroxybutane and the 1-acetoxy-4-hydroxybutane concentration in the crude 1,4-butanediol-containing solution after the removal of said components lower in the boiling point than 1,4-butanediol is from 0.1 to 50 ppm by mass.
8. The method as claimed in claim 1 , comprising said step (b), wherein a bottom temperature of the distillation column in said step (b) is from 120 to 200° C.
9. The method as claimed in claim 1 , comprising said step (a), wherein a bottom temperature of the distillation column in said step (a) is from 150 to 200° C.
10. The method as claimed in claim 1 , comprising said step (a), wherein the components higher in the boiling point than 1,4-butanediol in said step (a) contain 2-pyrrolidone and the 2-pyrrolidone concentration in the crude 1,4-butanediol-containing solution after the removal of said components higher in the boiling point than 1,4-butanediol is 20 ppm by mass or less.
11. The method as claimed in claim 1 , comprising said step (a), wherein a heating source of the distillation column in said step (a) contacts substantially only with a bottom liquid but involves no contact with a gas-phase part.
12. The method as claimed in claim 1 , wherein a gamma-butyrolactone concentration in the overhead distillate of the distillation column in said step (d) is higher than the gamma-butyrolactone concentration in the refined 1,4-butanediol withdrawn from a side stream.
13. The method as claimed in claim 1 , comprising a step of controlling the carbonyl value in the refined raw material 1,4-butanediol-containing solution immediately before passing through any one step of said steps (a) to (c) or through the step (b′), to be 2.5 mgKOH/g or less.
14. The method as claimed in claim 1 , wherein in at least one step of said steps (b) to (d), the carbonyl value in said refined raw material 1,4-butanediol-containing solution is reduced.
15. The method as claimed in claim 1 , comprising step (a) and step (b).
16. The method as claimed in claim 1 , comprising step (a).
17. The method as claimed in claim 1 , comprising step (b).
18. The method as claimed in claim 1 , wherein the concentration of a cyclic carbonyl compound having a carbon atom number of 5 or 6 in the refined 1,4-butanediol obtained in said step (d) is 10 ppm by mass or less.
19. The method as claimed in claim 1 , wherein the concentration of a cyclic carbonyl compound having a carbon atom number of 5 or 6 in the refined 1,4-butanediol obtained in said step (d) is 2-6 ppm by mass.