Methanol and sulfuric acid co-production system

Patent metadata

Field	Value
Publication number	US-12496533-B2
Application number	US-202217945796-A
Country	US
Kind code	B2
Filing date	Sep 15, 2022
Priority date	Dec 7, 2021
Publication date	Dec 16, 2025
Grant date	Dec 16, 2025

Abstract

Disclosed is a methanol and sulfuric acid co-production system capable of producing methanol and sulfuric acid in equal equivalents. Specifically, the system includes an oxidation reaction unit configured to produce methyl bisulfate (CH 3 OSO 3 H) by reacting methane gas with an acid solution in the presence of a catalyst, a reactive distillation unit disposed downstream of the oxidation reaction unit and configured to esterify methyl bisulfate (CH 3 OSO 3 H) supplied from the oxidation reaction unit with trifluoroacetic acid (CF 3 COOH) to obtain a product and to separate the product into methyl trifluoroacetate (CF 3 COOCH 3 ) and sulfuric acid (H 2 SO 4 ) through thermal distillation, and a hydrolysis reaction unit disposed downstream of the reactive distillation unit and configured to produce methanol by hydrolyzing methyl trifluoroacetate (CF 3 COOCH 3 ) supplied from the reactive distillation unit, in which the reactive distillation unit recirculates the sulfuric acid resulting from separation to the oxidation reaction unit.

First claim

What is claimed is:

1 . A methanol and sulfuric acid co-production system, comprising:
an oxidation reaction unit configured to produce methyl bisulfate (CH 3 OSO 3 H) by reacting methane gas with an acid solution in the presence of a catalyst; a reactive distillation unit disposed downstream of the oxidation reaction unit and configured to esterify methyl bisulfate (CH 3 OSO 3 H) supplied from the oxidation reaction unit with trifluoroacetic acid (CF 3 COOH) to obtain a product and to separate the product into methyl trifluoroacetate (CF 3 COOCH 3 ) and sulfuric acid (H 2 SO 4 ) through thermal distillation; and a hydrolysis reaction unit disposed downstream of the reactive distillation unit and configured to produce methanol by hydrolyzing methyl trifluoroacetate (CF 3 COOCH 3 ) supplied from the reactive distillation unit, wherein the reactive distillation unit recirculates the sulfuric acid resulting from separation to the oxidation reaction unit; and further comprising an unreacted material recovery unit disposed between the oxidation reaction unit and the reactive distillation unit and configured to perform gas-liquid separation of a product supplied from the oxidation reaction unit into methyl bisulfate (CH 3 OSO 3 H) and an unreacted material and to recirculate the unreacted material to the oxidation reaction unit.

2 . The methanol and sulfuric acid co-production system of claim 1 , wherein the catalyst comprises at least one of Pt (0), PtCl 2 , PtBr 2 , Ptl 2 , K 2 PtCl 4 , Pt(acac) 2 , Pt(OAc) 2 , (bpym) PtCl 2 , (DMSO) 2 PtCl 2 , Nal, KI, Lil, CH 3 l, CH 3 CH 2 I, CH 3 CH 2 CH 2 I, or any combination thereof.

3 . The methanol and sulfuric acid co-production system of claim 1 , wherein a concentration of the catalyst in the oxidation reaction unit ranges from about 1 mM to 3 mM based on a reactant.

4 . The methanol and sulfuric acid co-production system of claim 1 , wherein the acid solution comprises at least one of sulfuric acid, fuming sulfuric acid, or any combination thereof.

5 . The methanol and sulfuric acid co-production system of claim 1 , wherein the unreacted material recovery unit comprises a plurality of flash drums connecting in series.

6 . The methanol and sulfuric acid co-production system of claim 1 , wherein the reactive distillation unit allows methyl bisulfate (CH 3 OSO 3 H) and trifluoroacetic acid (CF 3 COOH) to react at a molar ratio of about 1:1 to 1:10.

7 . The methanol and sulfuric acid co-production system of claim 1 , wherein a temperature of the reactive distillation unit ranges from about 60° C. to 100° C.

8 . The methanol and sulfuric acid co-production system of claim 1 , wherein a temperature of the hydrolysis reaction unit ranges from about 50° C. to 100° C.

9 . The methanol and sulfuric acid co-production system of claim 1 , further comprising a mixing unit disposed between the reactive distillation unit and the hydrolysis reaction unit and configured to supply a mixture of methyl trifluoroacetate (CF 3 COOCH 3 ) supplied from the reactive distillation unit and water to the hydrolysis reaction unit.

10 . The methanol and sulfuric acid co-production system of claim 1 , further comprising a methanol separation unit disposed downstream of the hydrolysis reaction unit and configured to separate a product supplied from the hydrolysis reaction unit into methanol and trifluoroacetic acid (CF 3 COOH) through thermal distillation and to recirculate the trifluoroacetic acid (CF 3 COOH) to the reactive distillation unit.

11 . A methanol and sulfuric acid co-production system, comprising:
an oxidation reaction unit configured to produce methyl bisulfate (CH 3 OSO 3 H) by reacting methane gas with an acid solution in the presence of a catalyst; a reactive distillation unit disposed downstream of the oxidation reaction unit and configured to esterify methyl bisulfate (CH 3 OSO 3 H) supplied from the oxidation reaction unit with trifluoroacetic acid (CF 3 COOH) to obtain a product and to separate the product into methyl trifluoroacetate (CF 3 COOCH 3 ) and sulfuric acid (H 2 SO 4 ) through thermal distillation; and a hydrolysis reaction unit disposed downstream of the reactive distillation unit and configured to produce methanol by hydrolyzing methyl trifluoroacetate (CF 3 COOCH 3 ) supplied from the reactive distillation unit, wherein the reactive distillation unit recirculates the sulfuric acid resulting from separation to the oxidation reaction unit, further comprising a heat recovery unit configured to recover heat of the sulfuric acid separated in the reactive distillation unit, wherein the heat recovery unit supplies the recovered heat to at least one of a product of the oxidation reaction unit and a product of the hydrolysis reaction unit.

12 . A methanol and sulfuric acid co-production system, comprising:
an oxidation reaction unit configured to produce methyl bisulfate (CH 3 OSO 3 H) by reacting methane gas with an acid solution in the presence of a catalyst; a reactive distillation unit disposed downstream of the oxidation reaction unit and configured to esterify methyl bisulfate (CH 3 OSO 3 H) supplied from the oxidation reaction unit with trifluoroacetic acid (CF 3 COOH) to obtain a product and to separate the product into methyl trifluoroacetate (CF 3 COOCH 3 ) and sulfuric acid (H 2 SO 4 ) through thermal distillation; and a hydrolysis reaction unit disposed downstream of the reactive distillation unit and configured to produce methanol by hydrolyzing methyl trifluoroacetate (CF 3 COOCH 3 ) supplied from the reactive distillation unit, wherein the reactive distillation unit recirculates the sulfuric acid resulting from separation to the oxidation reaction unit, further comprising a mixing unit disposed between the reactive distillation unit and the hydrolysis reaction unit and configured to supply a mixture of methyl trifluoroacetate (CF 3 COOCH 3 ) supplied from the reactive distillation unit and water to the hydrolysis reaction unit wherein the hydrolysis reaction unit is configured to distill a hydrolyzed product to separate an unreacted material therefrom and to recirculate the unreacted material to the mixing unit.

Assignees

• Korea Inst Sci & Tech

Inventors

• Lee Ung
• Lee Hyun Joo
• Kim Hong Gon
• Kim Kyeong Su
• Im Jae Hyung
• Lee He Won

Classifications

• C07C29/095 Primary

  of esters of organic acids · 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

• C07C303/24

  of esters of sulfuric acids · CPC title

• C01B17/90 Primary

  Separation; Purification · CPC title

• C07C31/04

  Methanol · CPC title