IP Library Granted Patent US 12,227,468
Granted Patent B2
US 12,227,468 · App. 17/740,839 · Granted Feb 18, 2025

Process for the co-production of methyl mercaptan and of dimethyl disulfide from carbon oxides

Inventors: Georges Fremy (Lacq, FR); Jean-Michel Raymond (Cauneille, FR); Eric Lamant (Lacq, FR); Helori Salembier (Lacq, FR)
Assignee: Arkema France
C07C319/02C07C319/06C07C319/16C07C319/24C07C319/28
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Quick Facts
Patent No.
US 12,227,468
App. No.
17/740,839
Granted
Feb 18, 2025
Kind
B2
Abstract

The invention relates to a process for the co-production of methyl mercaptan and of dimethyl disulfide, comprising the following successive steps: a) reaction of at least one carbon oxide in the presence of hydrogen sulfide (H 2 S) and hydrogen to form a stream (M) comprising methyl mercaptan, water, and possibly unreacted hydrogen sulfide, b) purification of the stream (M) to obtain a stream (N) enriched in methyl mercaptan and a stream containing the uncondensable compounds (M uncond ), c) optional recycling of the stream of uncondensable compounds (M uncond ) obtained from step b) into step a), d) recovery of a first portion of the stream (N) including methyl mercaptan purified in step b), e) oxidation with sulfur of the second portion of the stream (N) of methyl mercaptan, to form a stream (O) comprising dimethyl disulfide, hydrogen sulfide, and possibly unreacted methyl mercaptan, f) purification of the stream (O) to separate, on the one hand, the enriched dimethyl disulfide and, on the other hand, the hydrogen sulfide and possibly the methyl mercaptan that has not reacted in step e), g) recycling of the hydrogen sulfide and possibly of the methyl mercaptan isolated in step f) into the stream (M) obtained from step a), h) recovery of the dimethyl disulfide isolated in step f).

Claims (19)

1. A process for the co-production of methyl mercaptan and of dimethyl disulfide, comprising the following successive steps:

a) reacting at least one carbon oxide in the presence of hydrogen sulfide (H 2 S) and hydrogen to form a stream (M) comprising methyl mercaptan, water, and optionally unreacted hydrogen sulfide,

b) purifying the stream (M) to obtain a stream (N) enriched in methyl mercaptan and a stream containing uncondensable compounds (M uncond ),

c) optional recycling the stream of uncondensable compounds (M uncond ) obtained from step b) into step a),

d) recovering a first portion of the stream (N) including methyl mercaptan purified in step b),

e) oxidizing with sulfur a second portion of the stream (N) of methyl mercaptan, to form a stream (O) comprising dimethyl disulfide, hydrogen sulfide, and optionally unreacted methyl mercaptan,

f) purifying the stream (O) to separate the dimethyl disulfide from the hydrogen sulfide and optionally the methyl mercaptan that has not reacted in step e),

g) recycling the hydrogen sulfide and possibly the methyl mercaptan isolated in step f) into the stream (M) obtained from step a),

h) recovering the dimethyl disulfide isolated in step f).

2. The process according to claim 1 , wherein the recycling step g) provides the stream to be recycled before the purification step b), which removes the hydrogen sulfide from the stream (M) to be purified, optionally followed by decantation and/or distillation.

3. The process according to claim 1 , wherein the streams containing the hydrogen sulfide, and optionally the methyl mercaptan that has not reacted in step e), is recycled into the stream (M) obtained from step a).

4. The process according to claim 1 , wherein in step a), the carbon oxide is carbon monoxide, carbon dioxide or a mixture thereof.

5. The process according to claim 1 , wherein in step a), the hydrogen sulfide is generated in situ by adding sulfur and hydrogen.

6. The process according to claim 1 , wherein the hydrogen sulfide in step a) is generated from sulfur and a mole ratio of carbon oxide/S/H 2 S/H 2 is between 1/0/0.05/0.05 and 1/20/40/100, or the hydrogen sulfide in step a) is not generated from sulfur and a mole ratio of carbon oxide/H 2 /H 2 S is between 1/0.05/0.05 and 1/40/100.

7. The process according to claim 1 , wherein the reaction temperature of step a) is between 200° C. and 500° C., the pressure is between 1 and 100 bar absolute, and the reaction of step a) is performed in the presence of a catalyst chosen from molybdenum and potassium catalysts of a Mo—S—K and/or Mo—O—K type on a support.

8. The process according to claim 1 , wherein the methyl mercaptan/sulfur mole ratio of the oxidation step e) is between 0.1 and 100.

9. The process according to claim 1 , wherein the reaction temperature of the oxidation step e) is between 20° C. and 200° C., the pressure is between 2 and 30 bar absolute, and the reaction of the oxidation step e) is performed in the presence of a basic catalyst chosen from homogeneous, two-phase or heterogeneous catalysts.

10. The process according to claim 1 , wherein the purification step b) includes one or more condensations, followed by one or more decantations, and optionally one or more distillations.

11. The process according to claim 1 , wherein the purification step f) includes one or more distillation steps, and optionally one or more basic catalysis steps.

Assignments (2)
CHANGE OF ADDRESS Recorded Jul 4, 2025
From: ARKEMA FRANCE
To: ARKEMA FRANCE
Reel/Frame 071814/0739 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 23, 2022
From: FREMY, GEORGES; RAYMOND, JEAN-MICHEL; LAMANT, ERIC; SALEMBIER, HELORI
To: ARKEMA FRANCE
Reel/Frame 060294/0624 →