Part-stream distillation

Patent metadata

Field	Value
Publication number	US-9732054-B2
Application number	US-201615246028-A
Country	US
Kind code	B2
Filing date	Aug 24, 2016
Priority date	Apr 29, 2013
Publication date	Aug 15, 2017
Grant date	Aug 15, 2017

Abstract

A continuous process for the preparation of propylene oxide, comprising (a) reacting propene, optionally admixed with propane, with hydrogen peroxide in a reaction apparatus in the presence of acetonitrile as solvent, obtaining a stream S 0 containing propylene oxide, acetonitrile, water, at least one further component B, optionally propene and optionally propane, wherein the normal boiling point of the at least one component B is higher than the normal boiling point of acetonitrile and wherein the decadic logarithm of the octanol-water partition coefficient (log K ow ) of the at least one component B is greater than zero; (b) separating propylene oxide from S 0 , obtaining a stream S 1 containing acetonitrile, water and the at least one further component B; (c) dividing S 1 into two streams S 2 and S 3 ; (d) subjecting S 3 to a vapor-liquid fractionation in a fractionation unit, obtaining a vapor fraction stream S 4 being depleted of the at least one component B; (e) recycling at least a portion of S 4 , optionally after work-up, to (a).

First claim

The invention claimed is:

1. A continuous process for preparation of propylene oxide, the process comprising
(a) reacting propene with hydrogen peroxide in a reaction apparatus in the presence of acetonitrile as solvent, obtaining a stream S 0 leaving the reaction apparatus, S 0 comprising propylene oxide, acetonitrile, water, at least one further component B, wherein a normal boiling point of the at least one component B is higher than a normal boiling point of acetonitrile and wherein a decadic logarithm of an octanol-water partition coefficient represented by log K OW of the at least one component B is greater than zero;
(b) separating propylene oxide from S 0 , obtaining a stream S 1 comprising acetonitrile, water and the at least one further component B;
(c) dividing S 1 into two streams S 2 and S 3 , wherein a total weight of S 3 relative to a total weight of S 1 is in a range of from 0.01 to 25%;
(d) subjecting S 3 to a vapor-liquid fractionation in a fractionation unit, obtaining a vapor fraction stream S 4 being depleted of the at least one component B, and obtaining a liquid bottoms stream S 4 b being depleted of acetonitrile; and
(e) recycling at least a portion of S 4 to (a).

2. The process of claim 1 , wherein in (c), the total weight of S 3 relative to the total weight of S 1 is in a range of from 0.05 to 20%.

3. The process of claim 1 , wherein from 90 to 99.9 weight-% of S 1 consist of acetonitrile and water and wherein from 0.01 to 5 weight-% of S 1 consist of the at least one component B.

4. The process of claim 1 , wherein in (d), vapor-liquid fractionation is carried out in the fractionation unit so that from 10 to 30 weight-% of the liquid bottoms stream S 4 b consist of acetonitrile and from 0.1 to 10 weight-% of the liquid bottoms stream S 4 b consist of the at least one further component B.

5. The process of claim 1 , wherein in (d), vapor-liquid fractionation is carried out in the fractionation unit at an absolute pressure in a range of from 0.1 to 10 bar.

6. The process of claim 1 , wherein in (d), a number of theoretical trays of the fractionation unit is in a range of from 1 to 100.

7. The process of claim 1 , wherein a fraction of S 4 is used after condensation as reflux.

8. The process of claim 1 , wherein the fractionation unit is operated without reflux and S 3 is fed to a top of the fractionation unit.

9. The process of claim 1 , wherein from 95 to 99.99 weight-% of S 4 consist of acetonitrile and water, and wherein from 0.0001 to 0.2 weight-% of S 4 consist of the at least one component B.

10. The process of claim 1 , wherein (e) comprises recycling at least a portion of S 4 to (a), and recycling at least a portion of S 2 to (a).

11. The process of claim 1 , wherein (e) comprises working-up S 4 , said working-up comprising combining at least a portion of S 4 with S 2 obtaining a liquid stream, subjecting said liquid stream to acetonitrile-water separation obtaining a stream enriched in acetonitrile, and recycling said stream enriched in acetonitrile to (a).

12. The process of claim 11 , wherein (e) comprises
(i) preparing a liquid stream S 5 by adding a liquid stream P to S 2 , or to at least a portion of S 4 , or to the liquid stream obtained from combining S 2 and at least the portion of S 4 ,
wherein P comprises at least 95 weight-% of C 3 , based on a total weight of P,
wherein C 3 is propene;
(ii) subjecting S 5 to a temperature of 92° C. at most and a pressure of at least 10bar, obtaining a first liquid phase L 1 and a second liquid phase L 2 ,
wherein at least 95 weight-% of L 1 consist of C 3 , acetonitrile, water and the at least one component B, the water content of L 1 being less than 10 weight-% based on a total weight of L 1 , and
wherein at least 95 weight-% of L 2 consist of C 3 , acetonitrile, water and the at least one component B, a C 3 content of L 2 being 5 weight-% at most, based on a total weight of L 2 , and an acetonitrile content of L 2 being less than 45 weight-%, based on the total weight of L 2 ;
(iii) separating L 1 from L 2 ; and
(iv) recycling L 1 as the stream enriched in acetonitrile to (a).

13. The process of claim 12 , further comprising working up L 1 , said working-up comprising subjecting L 1 to a distillation stage wherefrom a bottoms stream BL 1 is obtained, wherein at least 95 weight-% of BL 1 consist of C 3 , acetonitrile, water and the at least one component B, wherein a C 3 content of BL 1 is in a range of from 7 to 18 weight-%, and recycling BL 1 as the stream enriched in acetonitrile to (a).

14. The process of claim 13 , wherein from 0.01 to 5 weight-% of BL 1 consist of the at least one component B.

15. The process of claim 1 , wherein (b) comprises
(I) separating propene from S 0 , obtaining a stream S 01 enriched in propylene oxide, acetonitrile, water, and the at least one component B; and
(II) separating propylene oxide from S 01 , obtaining a stream S 02 enriched in acetonitrile, water and the at least one component B and wherein a weight ratio of acetonitrile relative to water is greater than 1:1.

16. The process of claim 15 , wherein (b) further comprises
(IIIa) subjecting S 02 obtained from (II) to hydrogenation to obtain a hydrogenated stream; and/or
(IIIb) subjecting the stream obtained from (II) or (IIIa) to distillation to obtain a bottoms stream,
wherein the hydrogenated stream obtained from (IIIa) or the bottoms stream obtained from (IIIb) is subjected to (c) as S 1 .

17. The process of claim 1 , wherein in (a), propene is reacted with hydrogen peroxide in the presence of a heterogeneous catalyst.

18. The process of claim 1 , wherein from 90 to 97 weight-% of S 0 consist of acetonitrile, water, and propylene oxide, and wherein from 0.01 to 3 weight-% of S 0 consist of the at least one component B.

19. The process of claim 1 , wherein the at least one component B is propionitrile, 1-nitropropane, 2-nitropropane, 3-methylbutanenitrile, n-pentanenitrile, 1-pentanol, 2-pentanol, 2-butanone, 2-pentanone, 2-hexanone, 4-methyl-2-heptanone, 2,6-dimethyl-4-heptanol, 4,6-dimethyl-2-heptanol, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 2,6-dimethyl-4,6-heptandiol, 2,4-dimethyloxazoline, 2,5-dimethyloxazoline, cis-2,4-dimethyl-1,3-dioxolane, trans-2,4-dimethyl-1,3-dioxolane, at least one impurity contained in the hydrogen peroxide employed in (a), or a combination of two or more of these compounds.

20. The process of claim 19 , wherein the at least one impurity contained in the hydrogen peroxide employed in (a) is an alkyl phosphate, a nonyl alcohol, an alkylcyclohexanol ester, an N,N-dialkyl carbonamide, an N-alkyl-N-aryl carbonamide, an N,N-dialkyl carbamate, a tetraalkyl urea, a cycloalkyl urea, a phenylalkyl urea, an N-alkyl-2-pyrrolidone, an N-alkyl caprolactam, or a combination of two or more of these compounds.

Assignees

• Basf Se
• Dow Global Technologies Llc

Inventors

• Teles Joaquim Henrique
• Riedel Dominic
• Seelig Bianca
• Kampe Philip
• Urbanczyk Daniel
• Weber Markus
• Schroeder Alexander
• Parvulescu Andrei-Nicolae
• Mueller Ulrich
• Weidenbach Meinolf
• Witzl Werner J
• Baer Holger

Classifications

• C07D301/32

  Separation; Purification · CPC title

• B01D3/143

  by two or more of a fractionation, separation or rectification step · CPC title

• C07D301/12 Primary

  with hydrogen peroxide or inorganic peroxides or peracids · CPC title