Method for preparing methyl formate and coproducing dimethyl ether

Patent metadata

Field	Value
Publication number	US-9938227-B2
Application number	US-201415526868-A
Country	US
Kind code	B2
Filing date	Nov 17, 2014
Priority date	Nov 17, 2014
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

Method for preparing methyl formate and coproducing dimethyl ether by reacting a formaldehyde and methanol raw material (molar ratio range of 1:4 to 1:0.05) in a First Reaction Region at ranges from 50° C. to 100° C. with Catalyst A resulting in post-reaction material separated into Constituent I. Reacting Constituent I in a Second Reaction Region at ranges from 50° C. to 200° C. and from 0.1 MPa to 10 MPa with Catalyst B resulting in post-reaction material, which is separated into methyl formate, dimethyl ether and Constituent II. At least 1% of dimethyl ether is product, and recycling the rest to the First Reaction Region. Constituent II is recycled to the Second Reaction Region. Each component is gaseous phase and/or liquid phase, independently. The method shows long catalyst life, mild reaction condition, high utilization ratio of raw materials, continuous production and large scale industrial application potential.

First claim

The invention claimed is:

1. A method for preparing methyl formate and coproducing dimethyl ether, which at least contains the steps as follows:
a) introducing a raw material containing formaldehyde and methanol into a First Reaction Region and contacting with a Catalyst A to react, and separating the post-reaction material to obtain Constituent I;
b) introducing the Constituent I obtained in step a) into a Second Reaction Region and contacting with a Catalyst B to react, and separating the post-reaction material to obtain Constituent II, dimethyl ether and the product methyl formate;
c) taking at least 1% of dimethyl ether obtained in step b) as product, and recycling the rest of dimethyl ether obtained in step b) to the First Reaction Region and recycling the Constituent II to the Second Reaction Region;
wherein in step a), the reaction temperature of the First Reaction Region ranges from 50° C. to 100° C.;
in said raw material, the molar ratio range of formaldehyde to methanol is from 1:4 to 1:0.05, and the molar of formaldehyde and methanol are calculated according to the molar of carbon atoms contained in formaldehyde and methanol, respectively; the weight hourly space velocity of formaldehyde in the raw material ranges from 0.01 h −1 to 15.0 h −1 ;
wherein in step b), the reaction temperature of the Second Reaction Region ranges from 50° C. to 200° C. and the reaction pressure ranges from 0.1 MPa to 10 MPa;
wherein each component in the First Reaction Region and the Second Reaction Region is gaseous phase and/or liquid phase, independently.

2. A method for preparing methyl formate and coproducing dimethyl ether according to claim 1 , wherein in step a), the Catalyst A is loaded in a distillation reaction device; and in the distillation reaction device, the reflux ratio ranges from 0.5 to 10, and the temperature ranges from 60° C. to 90° C.; the weight hourly space velocity of formaldehyde in the raw material ranges from 0.5 h −1 to 3.0 h −1 .

3. A method for preparing methyl formate and coproducing dimethyl ether according to claim 1 , wherein in step c), at least 10% of dimethyl ether obtained in step b) is taken as product, and recycling the rest of dimethyl ether obtained in step b) to the First Reaction Region.

4. A method for preparing methyl formate and coproducing dimethyl ether according to claim 1 , wherein in step c), at least 90% of dimethyl ether obtained in step b) is taken as product, and recycling the rest of dimethyl ether obtained in step b) to the First Reaction Region.

5. A method for preparing methyl formate and coproducing dimethyl ether according to claim 1 , wherein in step a), the Catalyst A is a strong acidic cation exchanger resin.

6. A method for preparing methyl formate and coproducing dimethyl ether according to claim 1 , wherein in step a), the Catalyst A is a sulfonated styrene-divinylbenzene copolymer resin with strong acid and macro-pores.

7. A method for preparing methyl formate and coproducing dimethyl ether according to claim 1 , wherein in step b), the reaction temperature of the Second Reaction Region ranges from 60° C. to 150° C. and the reaction pressure ranges from 0.1 MPa to 2 MPa.

8. A method for preparing methyl formate and coproducing dimethyl ether according to claim 1 , wherein in step b), the Catalyst B is at least one selected from acid molecular sieves or strong acidic cation exchanger resins.

9. A method for preparing methyl formate and coproducing dimethyl ether according to claim 1 , wherein in step b), the Catalyst B is at least one selected from H-type MCM-22 zeolite, H-type ZSM-5 zeolite, H-type Y zeolite, H-type BETA zeolite, H-type ferrierite, H-type mordenite or perfluorosulfonate resin.

10. A method for preparing methyl formate and coproducing dimethyl ether according to claim 1 , wherein the Second Reaction Region is composed of a fixed-bed reactor; or the Second Reaction Region is composed of a number 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

• B01J29/18

  of the mordenite type · CPC title

• B01J8/02

  with stationary particles, e.g. in fixed beds · CPC title

• B01J2231/50

  Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C67/48

  Separation; Purification; Stabilisation; Use of additives · CPC title