Method of recovering 1,3-butadiene and methylethylketone from dehydration products of 2,3-butanediol

Patent metadata

Field	Value
Publication number	US-10040733-B2
Application number	US-201514969047-A
Country	US
Kind code	B2
Filing date	Dec 15, 2015
Priority date	Dec 17, 2014
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

Disclosed is a method of efficiently separating 1,3-butadiene and methylethylketone, which are compounds of interest, from byproducts or impurities in the dehydration products of 2,3-butanediol so as to recover the compounds of interest at high purity.

First claim

What is claimed is:

1. A method of recovering 1,3-butadiene and methylethylketone from dehydration products of 2,3-butanediol, comprising:
a) dehydrating 2,3-butanediol in presence of an alkaline earth metal phosphate catalyst to provide a vapor stream comprising 1,3-butadiene, butene, methylethylketone, aldehyde, alcohol and water;
b) cooling the vapor stream, thus separating a 1,3-butadiene-rich first vapor stream and a methylethylketone-rich first liquid stream;
c) transferring the first vapor stream to a 1,3-butadiene purification unit, thus recovering 1,3-butadiene;
d) subjecting the first liquid stream to phase separation, thus obtaining a second liquid stream as an organic phase and a third liquid stream as an aqueous solution phase, separately from c);
e) separating the third liquid stream into (i) a water-rich bottom stream and (ii) a fourth liquid stream comprising a methylethylketone-water azeotropic mixture as an overhead stream;
f) combining the second liquid stream and the fourth liquid stream, and removing water from the combined liquid stream, thus obtaining a fifth liquid stream, wherein f) is performed using an entrainer in an azeotropic distillation column, so that water is removed as an overhead stream and the fifth liquid stream is obtained as a bottom stream; and
g) recovering methylethylketone from the fifth liquid stream.

2. The method of claim 1 , wherein the dehydration products of 2,3-butanediol in a) contain at least 3.5 wt % of 1,3-butadiene and at least 3.5 wt % of methylethylketone.

3. The method of claim 1 , further comprising scrubbing the 1,3-butadiene-rich first vapor stream, obtained in b), using a water-containing scrubbing fluid, before being fed to c).

4. The method of claim 3 , wherein the water-containing scrubbing fluid is at least a portion of the water-rich bottom stream separated in e).

5. The method of claim 1 , wherein c) comprises:
c1) fractionating the first vapor stream, thus obtaining an overhead stream including 1,3-butadiene and butene;
c2) transferring the overhead stream obtained in c1) to an extractive distillation column, thus separating a raffinate including butene as an overhead stream and an extract including 1,3-butadiene as a bottom stream; and
c3) separating a mixture comprising 1,3-butadiene and water from the extract including 1,3-butadiene using at least one stripper.

6. The method of claim 5 , wherein an extraction solvent used in the extractive distillation column in c2) includes an N-methyl-2-pyrrolidone (NMP) aqueous solution, and a concentration (water concentration) of the NMP aqueous solution exceeds 8 wt %.

7. The method of claim 6 , wherein the concentration (water concentration) of the NMP aqueous solution exceeds 15 wt %.

8. The method of claim 5 , wherein a weight ratio of the extraction solvent in c2) to the overhead stream obtained in c) ranges from 1:5 to 1:15.

9. The method of claim 5 , wherein an amount of 1,3-butadiene in the extract is 4 to 20 wt %.

10. The method of claim 5 , further comprising transferring the mixture comprising 1,3-butadiene and water, separated in c3), to a 1,3-butadiene purification column, so that water is removed as an overhead stream and 1,3-butadiene is recovered as a bottom stream, in which a water content in the recovered 1,3-butadiene is 100 wt ppm or less.

11. The method of claim 1 , wherein the entrainer is cyclohexane.

12. The method of claim 1 , wherein g) comprises:
g1) fractionating the fifth liquid stream, thus separating a methylethylketone-containing bottom stream and an overhead stream containing a compound having a boiling point lower than that of methylethylketone; and
g2) fractionating the methylethylketone-containing bottom stream obtained in g1), thus separating an overhead stream including methylethylketone and a bottom stream including a compound having a boiling point higher than that of methylethylketone.

13. The method of claim 1 , wherein an amount of 1,3-butadiene in the first vapor stream is 65 to 95 wt %, and an amount of methylethylketone in the first liquid stream is 20 to 80 wt %.

14. The method of claim 5 , wherein an amount of 1,3-butadiene in the overhead stream in c1) is 80 to 99.5 wt %.

15. The method of claim 5 , wherein c3) is performed using a first stripper, and a second stripper operating at a pressure lower than the first stripper, and
the second stripper is configured such that 1,3-butadiene contained in a bottom stream of the first stripper is additionally separated as an overhead stream and the overhead stream is recycled to the first stripper.

16. The method of claim 1 , wherein c) comprises:
c′1) fractionating the first vapor stream, thus obtaining an overhead stream including 1,3-butadiene and butene;
c′2) transferring the overhead stream obtained in c′1) to a distillation column, thus separating, as an overhead stream, a mixture comprising 1-butene and 1,3-butadiene, and as a bottom stream, a mixture comprising 1,3-butadiene and 2-butene;
c′3) recovering the mixture comprising 1-butene and 1,3-butadiene from the overhead stream separated in c′2); and
c′4) transferring the bottom stream separated in c′2) to a 1,3-butadiene recovery column, thus separating 1,3-butadiene as an overhead stream and 2-butene as a bottom stream, and recovering the 1,3-butadiene.

17. The method of claim 16 , wherein the overhead stream obtained in c′2) includes 80 to 95 wt % of 1,3-butadiene and 5 to 20 wt % of 1-butene, and the bottom stream obtained in c′2) includes 96 to 98.5 wt % of 1,3-butadiene and 0.5 to 3.5 wt % of 2-butene.

18. The method of claim 1 , wherein the entrainer is used in an amount of 0.01 wt % or less relative to the combined liquid stream.

19. A method of preparing 1,3-butadiene and methylethylketone from 2,3-butanediol, comprising:
a′) fermenting a substrate comprising biomass, CO or CO 2 by a strain, thus producing 2,3-butanediol;
b′) subjecting the 2,3-butanediol to dehydration in presence of an alkaline earth metal phosphate catalyst, thus providing a vapor stream comprising 1,3-butadiene, butene, methylethylketone, aldehyde, alcohol and water;
c′) cooling the vapor stream, thus separating a 1,3-butadiene-rich first vapor stream and a methylethylketone-rich first liquid stream;
d′) transferring the first vapor stream to a 1,3-butadiene purification unit, thus recovering 1,3-butadiene;
e′) subjecting the first liquid stream to phase separation, thus obtaining a second liquid stream as an organic phase and a third liquid stream as an aqueous solution phase, separately from d′);
f′) separating the third liquid stream into (i) a water-rich bottom stream and (ii) a fourth liquid stream comprising a methylethylketone-water azeotropic mixture as an overhead stream;
g′) combining the second liquid stream and the fourth liquid stream, and removing water from the combined liquid stream, thus obtaining a fifth liquid stream, wherein g′) is performed using an entrainer in an azeotropic distillation column, so that water is removed as an overhead stream and the fifth liquid stream is obtained as a bottom stream; and
h′) recovering methylethylketone from the fifth liquid stream.

Assignees

• Sk Innovation Co Ltd
• Sk Global Chemical Co Ltd

Inventors

• Song Dae Sung
• Park Sung Bum
• Shin Woong Chul

Classifications

• B01D3/002

  by continuous methods · CPC title

• Y02E50/343

  Cross-Sectional Technologies · mapped topic

• B01D2256/24

  Hydrocarbons · CPC title

• C07C45/81

  by change in the physical state, e.g. crystallisation · CPC title

• C07C7/08 Primary

  by extractive distillation · CPC title