Method for producing nitrous acid ester, and method for producing dialkyl oxalate and dialkyl carbonate

Patent metadata

Field	Value
Publication number	US-9499473-B2
Application number	US-201314389583-A
Country	US
Kind code	B2
Filing date	Feb 27, 2013
Priority date	Apr 2, 2012
Publication date	Nov 22, 2016
Grant date	Nov 22, 2016

Abstract

A method for producing nitrous acid ester in which nitric oxide, oxygen, and an alcohol are reacted, thereby generating nitrous acid ester includes a step of generating nitrous acid ester by supplying a bottom liquid from a bottom part of the reaction column, and nitric oxide and/or carbon monoxide, a step of supplying nitrous acid ester to the reaction column; a step of supplying a reaction liquid containing water, nitric acid, and the alcohol to a nitric acid condensing column from the reactor; and a step of separating a low-boiling point component by distillation from the reaction liquid under control of a concentration of the alcohol in a condensed liquid being generated at a bottom part of the nitric acid condensing column to be less than 4.0% by weight so as to introduce the condensed liquid into the reactor from the nitric acid condensing column.

First claim

The invention claimed is:

1. A method for producing nitrous acid ester in which an alcohol is supplied to an upper part of a reaction column for producing nitrous acid ester, is made to flow downward from the upper part to a lower part of the reaction column, nitric oxide and oxygen, or a gas mixture thereof is supplied to the lower part of the reaction column, and nitric oxide, oxygen, and the alcohol are reacted, thereby generating nitrous acid ester, the method comprising:
a step of extracting a bottom liquid containing water, nitric acid, and an alcohol from the bottom part of the reaction column so as to supply the bottom liquid to a reactor, and supplying nitric oxide and/or carbon monoxide to the reactor;
a step of generating nitrous acid ester by brining nitric oxide and/or carbon monoxide into contact with the bottom liquid in the reactor;
a step of supplying nitrous acid ester obtained in the reactor to the reaction column;
a step of supplying a reaction liquid containing water, nitric acid, and the alcohol to a nitric acid condensing column from a lower part of the reactor; and
a step of separating a low-boiling point component by distillation from the reaction liquid in the nitric acid condensing column under control of a concentration of an alcohol in a condensed liquid being generated at a bottom part of the nitric acid condensing column to be less than 4.0% by weight, and extracting the condensed liquid from the lower part of the nitric acid condensing column so as to introduce the condensed liquid into the reactor.

2. The method for producing nitrous acid ester according to claim 1 ,
wherein the nitrous acid ester obtained in the reactor is supplied to the reaction column from a supply opening provided at a middle part, a lower part, or a part between the middle part and the lower part of the reaction column.

3. The method for producing nitrous acid ester according to claim 1 ,
wherein the bottom liquid extracted from the lower part of the reaction column is introduced into and cooled in a cooler, and the bottom liquid which is cooled is circulated to the middle part of the reaction column.

4. The method for producing nitrous acid ester according to claim 1 ,
wherein a pressure in the nitric acid condensing column is lower than an atmospheric pressure.

5. The method for producing nitrous acid ester according to claim 1 ,
wherein the reaction liquid is supplied to the nitric acid condensing column from a supply opening provided at above a middle part of the nitric acid condensing column.

6. The method for producing nitrous acid ester according to claim 1 ,
wherein an alcohol obtained by purifying the low-boiling point component separated by distillation in the nitric acid condensing column is supplied to the reaction column from a supply opening provided at above a middle part of the reaction column.

7. The method for producing nitrous acid ester according to claim 1 ,
wherein a temperature of the nitric acid condensing column in a bottom part is 90° C. or lower.

8. The method for producing nitrous acid ester according to claim 1 ,
wherein a gas containing carbon monoxide is supplied to the reactor, and the carbon monoxide and the reaction liquid are brought into contact with each other in the reactor in the presence of a platinum group catalyst.

9. A method for producing a dialkyl oxalate, comprising a step of producing a nitrous acid ester according to method of claim 1 ; and:
a step of producing a dialkyl oxalate by reacting the nitrous acid ester and carbon monoxide in the presence of a catalyst.

10. A method for producing a dialkyl carbonate, comprising a step of producing a nitrous acid ester according to method of claim 1 ; and:
a step of producing a dialkyl carbonate by reacting the nitrous acid ester and carbon monoxide in the presence of a catalyst.

Assignees

• Ube Industries

Inventors

• Tanaka Syuji
• Il Hirofumi
• Hino Akira
• FUKUI Yuya
• Ueda Satoshi

Classifications

• C07C67/36

  by reaction with carbon monoxide or formates (C07C67/02, C07C67/03, C07C67/10 take precedence) · CPC title

• C07C68/00

  Preparation of esters of carbonic or haloformic acids · CPC title

• C07C201/04 Primary

  Preparation of esters of nitrous acid · CPC title

• C07C69/96

  Esters of carbonic or haloformic acids · CPC title

• C07C203/00

  Esters of nitric or nitrous acid · CPC title