Methods for producing a methanol precursor, methanol, and a methyl ester from methane in high purities

Patent metadata

Field	Value
Publication number	US-11021429-B1
Application number	US-202016943179-A
Country	US
Kind code	B1
Filing date	Jul 30, 2020
Priority date	Feb 7, 2020
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

A method for producing a methanol precursor, methyl trifluoroacetate, having high-purity includes the steps of (a) preparing methyl bisulfate by mixing a catalyst with an acid solution comprising a sulfur-containing acid to provide a first mixture and supplying methane gas to the first mixture to prepare the methyl bisulfate; and (b) preparing methyl trifluoroacetate (CF 3 CO 2 CH 3 ) by adding trifluoroacetic acid (CF 3 CO 2 H) to the first mixture including the methyl bisulfate to provide a second mixture and distilling the second mixture under heating to prepare, separate and purify the methyl trifluoroacetate (CF 3 CO 2 CH 3 ). Methanol may be produced by adding water to the methyl trifluoroacetate (CF 3 CO 2 CH 3 ). A methyl ester represented by Formula 2 below may be produced by adding a carboxylic acid represented by Formula 1 below to the methyl trifluoroacetate (CF 3 CO 2 CH 3 ):

R 1 CO 2 H  (1),
where R 1 is selected from C 1 -C 10 alkyl groups,

R 1 CO 2 CH 3   (2),
where R 1 is as defined in Formula 1.

First claim

What is claimed is:

1. A method for producing methyl trifluoroacetate having high-purity, comprising the steps of:
(a) preparing methyl bisulfate by mixing a catalyst with an acid solution comprising a sulfur-containing acid to provide a first mixture and supplying methane gas to the first mixture to prepare the methyl bisulfate; and
(b) preparing methyl trifluoroacetate (CF 3 CO 2 CH 3 ) by adding trifluoroacetic acid (CF 3 CO 2 H) to the first mixture including the methyl bisulfate to provide a second mixture and distilling the second mixture under heating to prepare, separate and purify the methyl trifluoroacetate (CF 3 CO 2 CH 3 ).

2. The method according to claim 1 , wherein the catalyst is selected from the group consisting of Pt 0 , PtCl 2 , PtBr 2 , PtI 2 , Pt, Pt(acac) 2 , Pt(OAc) 2 , (bpym)PtCl 2 , (DMSO) 2 PtCl 2 , NaI, KI, LiI, CH 3 I, CH 3 CH 2 I, and CH 3 CH 2 CH 2 I.

3. The method according to claim 1 , wherein the sulfur-containing acid is sulfuric acid or oleum.

4. The method according to claim 1 , wherein, in step (b), the methyl bisulfate and the trifluoroacetic acid (CF 3 CO 2 H) are mixed in a molar ratio ranging from 1:1 to 1:10.

5. The method according to claim 1 , wherein step (b) is carried out at a temperature ranging from 70 to 100° C.

6. A method for producing methanol, comprising the steps of:
(a) preparing methyl bisulfate by mixing a catalyst with an acid solution comprising a sulfur-containing acid to provide a first mixture and supplying methane gas to the first mixture to prepare the methyl bisulfate;
(b) preparing methyl trifluoroacetate (CF 3 CO 2 CH 3 ) by adding trifluoroacetic acid (CF 3 CO 2 H) to the first mixture containing the methyl bisulfate to provide a second mixture and distilling the second mixture under heating to prepare, separate and purify the methyl trifluoroacetate (CF 3 CO 2 CH 3 ); and
(c) preparing methanol by adding water to the methyl trifluoroacetate (CF 3 CO 2 CH 3 ) to produce the methanol.

7. The method according to claim 6 , wherein the catalyst is selected from the group consisting of Pt 0 , PtCl 2 , PtBr 2 , PtI 2 , Pt, Pt(acac) 2 , Pt(OAc) 2 , (bpym)PtCl 2 , (DMSO) 2 PtCl 2 , NaI, KI, LiI, CH 3 I, CH 3 CH 2 I, and CH 3 CH 2 CH 2 I.

8. The method according to claim 6 , wherein the sulfur-containing acid is sulfuric acid or oleum.

9. The method according to claim 6 , wherein in step (b), the methyl bisulfate and the trifluoroacetic acid (CF 3 CO 2 H) are mixed in a molar ratio of 1:1 to 1:10.

10. The method according to claim 1 , wherein step (b) is carried out at a temperature ranging from 70 to 100° C.

11. A method for producing a methyl ester, comprising the steps of:
(a) preparing methyl bisulfate by mixing a catalyst with an acid solution comprising a sulfur-containing acid to provide a first mixture and supplying methane gas to the first mixture to prepare the methyl bisulfate;
(b) preparing methyl trifluoroacetate (CF 3 CO 2 CH 3 ) by adding trifluoroacetic acid (CF 3 CO 2 H) to the first mixture including the methyl bisulfate to provide a second mixture and distilling the second mixture under heating to prepare, separate and purify the methyl trifluoroacetate (CF 3 CO 2 CH 3 ); and
(c) preparing a methyl ester represented by Formula 2 below by adding a carboxylic acid represented by Formula 1 below to the methyl trifluoroacetate (CF 3 CO 2 CH 3 ):
R 1 CO 2 H (1),

where R 1 is selected from C 1 -C 10 alkyl groups,
R 1 CO 2 CH 3   (2),

where R 1 is as defined in Formula 1.

12. The method according to claim 11 , wherein the catalyst is selected from the group consisting of Pt 0 , PtCl 2 , PtBr 2 , PtI 2 , Pt, Pt(acac) 2 , Pt(OAc) 2 , (bpym)PtCl 2 , (DMSO) 2 PtCl 2 , NaI, KI, LiI, CH 3 I, CH 3 CH 2 I, and CH 3 CH 2 CH 2 I.

13. The method according to claim 11 , wherein the sulfur-containing acid is sulfuric acid or oleum.

14. The method according to claim 11 , wherein, in step (b), the methyl bisulfate and the trifluoroacetic acid (CF 3 CO 2 H) are mixed in a molar ratio ranging from 1:1 to 1:10.

15. The method according to claim 11 , wherein step (B) is carried out at a temperature ranging from 70 to 100° C.

Assignees

• Korea Inst Sci & Tech

Inventors

• Lee Hyun Joo
• Lee Ung
• Lee He Won
• Dang Tran Huyen
• Cheong Seok Hyeon

Classifications

• Y02P20/52

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

• C07C67/11 Primary

  being mineral ester groups · CPC title

• C07C67/10

  by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond (preparation from carboxylic acid halides C07C67/14) · CPC title

• C07C29/12

  of esters of mineral acids · CPC title

• C07C303/24

  of esters of sulfuric acids · CPC title