Process for the preparation of propylene oxide

Patent metadata

Field	Value
Publication number	US-9688648-B2
Application number	US-201414906852-A
Country	US
Kind code	B2
Filing date	Jul 16, 2014
Priority date	Jul 24, 2013
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

A continuous process for the preparation of propylene oxide, comprising (i) providing a liquid feed stream comprising propene, hydrogen peroxide, acetonitrile, water, dissolved potassium dihydrogen phosphate, and optionally propane; (ii) passing the liquid feed stream provided in (i) into an epoxidation reactor comprising a catalyst comprising a titanium zeolite of structure type MWW, and subjecting the liquid feed stream to epoxidation reaction conditions; (iii) removing an effluent stream from the epoxidation reactor; wherein the concentration of the dissolved potassium dihydrogen phosphate in the liquid feed stream is at least 10% of the solubility limit of the potassium dihydrogen phosphate in the liquid feed stream.

First claim

The invention claimed is:

1. A process for preparing propylene oxide, comprising:
(i) preparing a liquid feed stream comprising propene, hydrogen peroxide, acetonitrile, water, and dissolved potassium dihydrogen phosphate;
(ii) feeding the liquid feed stream into an epoxidation reactor comprising a catalyst comprising a titanium zeolite of framework structure MWW;
(iii) subjecting the liquid feed stream to epoxidation reaction conditions in the epoxidation reactor to obtain a reaction mixture comprising propylene oxide, acetonitrile, water, and potassium dihydrogen phosphate;
(iv) removing the reaction mixture as an effluent stream from the epoxidation reactor; and
(v) separating the propylene oxide from the effluent stream;
wherein
operations (i) to (v) are conducted as a continuous method, and
in the liquid feed stream:
a concentration of the dissolved potassium dihydrogen phosphate is at least 10% of a solubility limit of potassium dihydrogen phosphate in the liquid feed stream.

2. The process of claim 1 , wherein the concentration of the dissolved potassium dihydrogen phosphate in the liquid feed stream prepared in (i) is from 50 to 100% of the solubility limit of potassium dihydrogen phosphate in the liquid feed stream provided in (i).

3. The process of claim 1 , wherein in the liquid feed stream prepared in (i)
a weight-% of acetonitrile is from 60 to 75 weight-%, based on a total weight of the liquid feed stream;
a weight-% of hydrogen peroxide is from 6 to 10 weight-%, based on the total weight of the liquid feed stream;
a molar ratio of water relative to acetonitrile is at most 1:4;
a molar ratio of propene relative to hydrogen peroxide in the liquid feed stream is from 1:1 to 1.5:1; and
a molar ratio of potassium dihydrogen phosphate relative to hydrogen peroxide in the liquid feed stream is from 25×10 −6 :1 to 1000×10 −6 :1;
wherein at least 95 weight-% of the liquid feed stream prepared in (i) consist of propene, hydrogen peroxide, acetonitrile, water] and the dissolved potassium dihydrogen phosphate.

4. The process of claim 1 , wherein the liquid feed stream prepared in (i) further comprises ammonium NH 4 + in an amount of at most 2 weight-ppm and sodium in a molar ratio of sodium relative to hydrogen peroxide of from 1×10 −6 :1 to 250×10 −6 :1.

5. The process of claim 1 ,
wherein in (i), the liquid feed stream is prepared by combining a stream comprising hydrogen peroxide, a stream comprising acetonitrile, and a stream comprising propene,
wherein an aqueous stream comprising the dissolved potassium dihydrogen phosphate is combined with the stream comprising hydrogen peroxide, or with the stream comprising acetonitrile, or with the stream comprising propene, or with a mixed stream of two or three thereof,
wherein a hydrogen peroxide concentration in the stream comprising hydrogen peroxide is from 25 to 75 weight-%, based on a total weight of the aqueous hydrogen peroxide stream, and
the aqueous hydrogen peroxide stream further comprises sodium and a molar ratio of the sodium relative to the hydrogen peroxide is from 1×10 −6 :1 to 250×10 −6 :1.

6. The process of claim 1 , wherein the liquid feed stream fed to the epoxidation reactor in (ii) has a temperature of from 0 to 60° C. and a pressure of from 14 to 100 bar.

7. The process of claim 1 , further comprising controlling the temperature of the epoxidation reaction mixture to a temperature of from 20 to 100° C. using a heat transfer medium,
wherein the epoxidation reaction temperature is defined as the temperature of the heat transfer medium prior to controlling the temperature of the reaction mixture.

8. The process of claim 1 , wherein in (ii), an epoxidation reaction pressure is from 14 to 100 bar,
wherein the epoxidation reaction pressure is defined as a pressure at an exit of the epoxidation reactor, and
wherein the epoxidation reaction mixture is liquid under the epoxidation conditions.

9. The process of claim 1 , wherein in (ii), a catalyst loading is from 0.05 to 1.25 h −1 , wherein the catalyst loading is defined as a ratio of a mass flow rate in kg/h of hydrogen peroxide comprised in the liquid feed stream prepared in (i) divided by an amount in kg of catalyst comprising the titanium zeolite of structure MWW in the epoxidation reactor in (ii).

10. The process of claim 1 , wherein in (ii), the catalyst comprising a titanium zeolite of framework structure MWW is present in the reactor as fixed-bed catalyst.

11. The process of claim 1 , wherein a weight % of titanium in the titanium zeolite of framework structure MWW is from 0.1 to 5 weight-%, in (ii), calculated as elemental titanium, based on a total weight of the titanium zeolite of framework structure MWW.

12. The process of claim 1 , wherein a weight-% zinc of the titanium zeolite of framework structure MWW, calculated as elemental zinc, is from 0.1 to 5 weight-%, based on a total weight of the titanium zeolite of framework structure MWW.

13. The process of claim 1 , wherein the effluent stream removed in (iv) comprises
propylene oxide in amount of from 5 to 20 weight-%, based on a total weight of the effluent stream;
acetonitrile in amount of from 60 to 75 weight-%, based on the total weight of the effluent stream;
water in amount of from 10 to 25 weight-%, based on the total weight of the effluent stream; and
the dissolved potassium dihydrogenphosphate with a molar ratio of potassium dihydrogenphosphate relative to hydrogen peroxide comprised in the feed stream in a range of from 25×10 −6 :1 to 1000×10 −6 :1;
wherein at least 95 weight-% of the effluent stream removed in (iii) consists of propylene oxide, acetonitrile, water and potassium dihydrogen phosphate.

14. The process of claim 13 , wherein the effluent stream removed in (iv) comprises molecular oxygen with a molar ratio of the molecular oxygen in the effluent stream removed in (iv) relative to hydrogen peroxide in the liquid feed stream provided in (i) in a range of from 0.05:100 to 2.5:100.

15. The process of claim 1 , wherein the effluent stream removed in (iv) comprises propene and wherein the process further comprises
(iv) separating propene and oxygen from the effluent stream, thus obtaining a stream S01 enriched in propylene oxide, acetonitrile and water; and
(v) separating propylene oxide from S01, further obtaining a top stream comprising propylene oxide and being depleted of acetonitrile and water.

Assignees

• Basf Se
• Dow Global Technologies Llc

Inventors

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

Classifications

• B01J29/7088

  MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25 · CPC title

• B01J37/0201

  Impregnation · CPC title

• C07D301/36 Primary

  Use of additives, e.g. for stabilisation · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C07D301/12

  with hydrogen peroxide or inorganic peroxides or peracids · CPC title