Method for preparing methyl formate

Patent metadata

Field	Value
Publication number	US-9944588-B2
Application number	US-201415526780-A
Country	US
Kind code	B2
Filing date	Nov 17, 2014
Priority date	Nov 17, 2014
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

A method for preparing methyl formate in which a raw material containing formaldehyde, methanol and/or dimethyl ether is introduced into a first reaction zone to come into contact with a catalyst A, and a component I is obtained by separation, the component I is introduced into a second reaction zone to come into contact with a catalyst B so as to obtain, by separation, methyl formate as a product, dimethyl ether that is returned to the first reaction zone and a component II that is returned to the second reaction zone, the catalysts have a long service life, the reaction conditions are mild, and the utilization rate of the raw material is high, thus enabling a continuous production for large-scale industrial application.

First claim

What is claimed is:

1. A method for preparing methyl formate, comprising at least the steps of:
a) introducing a raw material containing formaldehyde, methanol and/or dimethyl ether into a first reaction zone to come into contact with a catalyst A, so as to obtain a component I;
b) introducing the component I obtained by separation in step a) into a second reaction zone to come into contact with a catalyst B, so as to obtain methyl formate as a product, dimethyl ether, and a component II by separation; and
c) returning dimethyl ether obtained in step b) to the first reaction zone, and returning the component II to the second reaction zone;
wherein, in step a), the temperature is 50-100° C. in the first reaction zone; the ratio of formaldehyde, methanol and/or dimethyl ether in the raw material is formaldehyde:methanol and/or dimethyl ether=1:2-4 based on the mole number of carbon atoms contained in respective component; and the mass hourly space velocity of formaldehyde in the raw material is 0.01-15.0 h−1;
in step b), the temperature is 50-200° C. and the pressure is 0.1-10 Mpa in the second reaction zone; and
the components in the first reaction zone and the second reaction zone are each independently a gas phase and/or a liquid phase.

2. The method according to claim 1 , wherein in step a), the catalyst A is charged in a rectification unit for reaction; the rectification unit for reaction has a reflux ratio of 0.5-10 and a temperature of 60-90° C.; and the mass hourly space velocity of formaldehyde in the raw material is 0.5-3.0 h−1.

3. The method according to claim 1 , wherein in step a), the molar ratio of methanol and/or methanol in dimethyl ether in the raw material is 0-50% based on the mole number of carbon atoms contained in respective component.

4. The method according to claim 1 , wherein in step a), dimethyl ether in methanol and/or dimethyl ether in the raw material is partially or entirely obtained from the second reaction zone by separation.

5. The method according to claim 1 , wherein in step a), the catalyst A is a strong acidic cation exchange resin.

6. The method according to claim 1 , wherein in step a), the catalyst A is a strong acidic macroporous resin of sulfonated styrene-divinyl benzene copolymer.

7. The method according to claim 1 , wherein in step b), the temperature is 60-150° C. and the pressure is 0.1-2 MPa in the second reaction zone.

8. The method according to claim 1 , wherein in step b), the catalyst B is one or more of an acidic molecular sieve and a strong acidic cation exchange resin.

9. The method according to claim 1 , wherein in step b), the catalyst B is selected from one or more of a hydrogen type MCM-22 molecular sieve, a hydrogen type ZSM-5 molecular sieve, a hydrogen type Y zeolite, a hydrogen type Beta molecular sieve, a hydrogen type ferrierite, a hydrogen type zeolite mordenite, and a perfluorosulfonic acid resin.

10. The method according to claim 1 , wherein the second reaction zone is consisted of a fixed bed reactor; or the second reaction zone is consisted of a plurality of fixed bed reactors in parallel and/or in series.

Assignees

• Dalian Inst Chem & Physics Cas

Inventors

• Ni Youming
• Zhu Wenliang
• Liu Yong
• Liu Hongchao
• Liu Zhongmin
• Li Lina
• Liu Shiping
• Zhou Hui

Classifications

• C07C43/043

  Dimethyl ether · CPC title

• C08F212/36

  Divinylbenzene · CPC title

• B01J29/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively · CPC title

• C07C69/06 Primary

  of monohydroxylic compounds · CPC title

• C07C43/10

  of polyhydroxy compounds · CPC title