Methods of making mercaptan compounds using nickel-molybdenum catalysts

Patent metadata

Field	Value
Publication number	US-11851397-B2
Application number	US-202117493921-A
Country	US
Kind code	B2
Filing date	Oct 5, 2021
Priority date	Oct 7, 2020
Publication date	Dec 26, 2023
Grant date	Dec 26, 2023

Abstract

Methods for synthesizing a mercaptan compound include the steps of contacting a nickel-molybdenum catalyst with H2S at a sulfiding temperature of less than or equal to 235° C. to form a supported sulfur-containing catalyst, and then contacting an alcohol compound or an olefin compound, H2S, and the supported sulfur-containing catalyst to form a reaction mixture containing the mercaptan compound.

First claim

We claim:

1. A process for producing a mercaptan compound, the process comprising:
(i) contacting a nickel-molybdenum catalyst with inlet H 2 S at an inlet sulfiding temperature from about 10° C. to about 90° C. and sulfiding the nickel-molybdenum catalyst with H 2 S at a sulfiding temperature of less than or equal to about 235° C. to form a supported sulfur-containing catalyst; and
(ii) contacting an alcohol compound or an olefin compound, H 2 S, and the supported sulfur-containing catalyst to form a reaction mixture comprising the mercaptan compound.

2. The process of claim 1 , wherein:
the alcohol compound, H 2 S, and the supported sulfur-containing catalyst are contacted in step (ii);
the mercaptan compound has formula (A): R 1 —SH;
the alcohol compound has formula (B): R 1 —OH; and
R 1 is a C 1 to C 18 substituted or unsubstituted, cycloalkyl group or linear or branched alkyl group.

3. The process of claim 1 , wherein:
the olefin compound, H 2 S, and the supported sulfur-containing catalyst are contacted in step (ii);
the mercaptan compound has formula (C): R 2 —SH;
the olefin compound has the formula H 2 C═CH 2 or formula (D): R 1 —CH═CH 2 ;
R 1 is a C 1 to C 18 substituted or unsubstituted, cycloalkyl group or linear or branched alkyl group; and
R 2 is a C 3 to C 20 substituted or unsubstituted, cycloalkyl group or linear or branched alkyl group.

4. The process of claim 1 , wherein:
the alcohol compound comprises methanol, ethanol, a propanol, a butanol, a pentanol, a hexanol, a heptanol, an octanol, a nonanol, a decanol, an undecanol, a dodecanol, a tridecanol, a tetradecanol, a pentadecanol, a hexadecanol, a heptadecanol, an octadecanol, cyclopentanol, cyclohexanol, or any combination thereof; and
the olefin compound comprises ethylene, propylene, a butene, a pentene, a hexene, a heptene, an octene, a decene, a dodecene, a tetradecene, a hexadecene, an octadecene, cyclopentene, cyclohexene, or any combination thereof.

5. The process of claim 1 , wherein the mercaptan compound is methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, or sec-butyl mercaptan.

6. The process of claim 1 , wherein step (i) is conducted at:
a sulfiding temperature from about 60° C. to about 200° C.; and
a sulfiding pressure from about 50 to about 250 psig.

7. The process of claim 1 , wherein the inlet sulfiding temperature is from about 20° C. to about 80° C.

8. The process of claim 1 , wherein step (ii) is conducted at:
a temperature in a range from about 100° C. to about 300° C.;
a pressure in a range from about 50 to about 1000 psig; and
a WHSV in a range from about 0.01 to about 3.

9. The process of claim 1 , wherein step (ii) comprises contacting the alcohol compound or the olefin compound and H 2 S with a fixed bed of the supported sulfur-containing catalyst.

10. The process of claim 1 , wherein a molar ratio of H 2 S:alcohol compound or H 2 S:olefin compound is in a range from about 3:1 to about 30:1.

11. The process of claim 1 , further comprising, prior to step (i), a step of contacting the nickel-molybdenum catalyst with an inert gas at a purging temperature of less than or equal to about 235° C.

12. The process of claim 11 , wherein:
the inert gas comprises nitrogen; and
the purging temperature is from about 60° C. to about 200° C.

13. The process of claim 1 , wherein:
a yield to the mercaptan compound is at least about 50 mol %; and/or
a conversion of the alcohol compound or the olefin compound is at least about 50 mol %.

14. The process of claim 1 , wherein the reaction mixture contains less than or equal to about 10 mol % of non-mercaptan reaction products.

15. The process of claim 1 , wherein a selectivity of the mercaptan compound is at least about 80 mol %, based on the total mercaptan compounds in the reaction mixture.

16. The process of claim 1 , further comprising a step of isolating the mercaptan compound from the reaction mixture to form a product stream containing the mercaptan compound.

17. The process of claim 1 , wherein unreacted alcohol compound or unreacted olefin compound is recycled after step (ii).

18. The process of claim 1 , wherein the nickel-molybdenum catalyst and the supported sulfur-containing catalyst independently comprise:
a solid support;
from about 1 to about 5 wt. % nickel; and
from about 4 to about 18 wt. % molybdenum.

19. The process of claim 18 , wherein the nickel-molybdenum catalyst and the supported sulfur-containing catalyst independently contain less than or equal to about 3 wt. % carbon.

20. The process of claim 18 , wherein the nickel-molybdenum catalyst and the supported sulfur-containing catalyst independently are characterized by a BET surface area from about 100 to about 300 m 2 /g.

21. The process of claim 18 , wherein the supported sulfur-containing catalyst contains from about 3 to about 18 wt. % sulfur.

22. The process of claim 18 , wherein the solid support comprises silica, alumina, magnesia, boria, titania, zirconia, a zeolite, a mixed oxide thereof, or a mixture thereof.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Kreider Jason L
• Hasenberg Daniel M
• Gerlach Brian
• Solaas Dale M
• Lassen Kenneth M

Classifications

• C07C319/08 Primary

  by replacement of hydroxy groups or etherified or esterified hydroxy groups · CPC title

• C07C319/04 Primary

  by addition of hydrogen sulfide or its salts to unsaturated compounds · CPC title

• B01J23/883

  and nickel · CPC title

• C07C321/04

  of an acyclic saturated carbon skeleton · CPC title