Systems, methods and materials for hydrogen sulfide conversion

Patent metadata

Field	Value
Publication number	US-11413574-B2
Application number	US-201917251998-A
Country	US
Kind code	B2
Filing date	Aug 7, 2019
Priority date	Aug 9, 2018
Publication date	Aug 16, 2022
Grant date	Aug 16, 2022

Abstract

Systems and methods use bimetallic alloy particles for converting hydrogen sulfide (H2S) to hydrogen (H2) and sulfur (S), typically during multiple operations. In a first operation, metal alloy composite particles can be converted to a composite metal sulfide. In a second operation, composite metal sulfide from the first operation can be regenerated back to the metal alloy composite particle using an inert gas stream. Pure, or substantially pure, sulfur can also be generated during the second operation.

First claim

We claim:

1. A method comprising:
contacting a first gaseous input stream comprising hydrogen sulfide (H 2 S) with a metal alloy particle at a temperature between 300° C. and 450° C., the metal alloy particle comprising at least a first metal component comprising a first metal, and a second metal component comprising a second metal that is different from the first metal,
whereupon the hydrogen sulfide (H 2 S) in the first gaseous input stream reacts in a sulfidation reaction with the metal alloy particle to generate hydrogen gas (H 2 ) and one or more sulfide minerals,

collecting a first gaseous product stream comprising the hydrogen gas (H 2 );
after collecting the first gaseous product stream, contacting a second gaseous input stream comprising at least one inert gas with the one or more sulfide minerals, thereby generating sulfur gas and regenerating the metal alloy particle; and
collecting a second gaseous product stream comprising the sulfur gas.

2. The method according to claim 1 , wherein the first gaseous input stream further comprises one or more of CO, H 2 , CO 2 , and a hydrocarbon feedstock.

3. The method of claim 1 , wherein the first metal component comprises the first metal, a first metal sulfide comprising the first metal, a first metal oxide comprising the first metal, or combinations thereof, and wherein the second metal component comprises the second metal, a second metal sulfide comprising the second metal, a second metal oxide comprising the second metal, or combinations thereof.

4. The method of claim 1 , wherein each of the first metal and second metal is selected from the group consisting of iron (Fe), chromium (Cr), nickel (Ni), Zinc (Zn), cobalt (Co), manganese (Mn) and copper (Cu).

5. The method of claim 1 , wherein the sulfide mineral is selected from the group consisting of a metal sulfide, a thiospinel and combinations thereof.

6. The method of claim 5 , wherein the sulfide mineral is selected from the group consisting of an iron sulfide, a chromium sulfide, and combinations thereof.

7. The method of claim 6 , wherein the sulfide mineral comprises FeCr 2 S 4 .

8. The method of claim 1 , wherein the first metal is iron (Fe) and the second metal is chromium (Cr).

9. The method of claim 1 , wherein the at least one inert gas is selected from the group consisting of nitrogen, carbon dioxide, air and combinations thereof.

10. The method of claim 1 , wherein the metal alloy particle is a particle having a diameter of between about 100 microns and about 10 mm.

11. The method of claim 1 , wherein the step of contacting the first gaseous input stream with the metal alloy particle is carried out in a sulfidation reactor selected from the group consisting of a fixed bed reactor, a fluidized bed reactor, a co-current moving bed reactor and a counter-current moving bed reactor.

12. The method of claim 11 , wherein the molar ratio of gases:solids within the sulfidation reactor during the step of contacting the first gaseous input stream with the metal alloy particle is between about 0.2 to about 10.

13. The method of claim 1 , wherein the step of contacting the first gaseous input stream with the metal alloy particle is carried out at a first pressure between about 1 atm and about 150 atm.

14. The method of claim 1 , wherein the step of contacting the second gaseous input stream with the one or more sulfide minerals is carried out in a regeneration reactor selected from the group consisting of a fixed bed reactor, a fluidized bed reactor, a co-current moving bed reactor and a counter-current moving bed reactor.

15. The method of claim 14 , wherein the molar ratio of gases:solids within the regeneration reactor during the step of contacting the second gaseous input stream with the one or more sulfide minerals is between about 0.2 to about 10.

16. The method of claim 1 , wherein the step of contacting the second gaseous input stream with the one or more sulfide minerals is carried out at a second temperature between about 500° C. and about 1100° C., and a second pressure between about vacuum conditions and about 150 atm.

17. The method of claim 1 , wherein the first gaseous product stream comprises less than 100 ppmv H 2 S.

18. The method of claim 1 , further comprising after collecting the second gaseous product stream, contacting the regenerated metal alloy with a subsequent first gaseous input stream such that a hydrogen gas (H 2 ) production performance of the regenerated metal alloy particle is similar to a hydrogen gas (H 2 ) production performance of the metal alloy particle.

19. The method of claim 1 , wherein contacting the first gaseous input stream and contacting the second gaseous input stream is performed in a batch operational mode, in a semibatch operational mode, or in a continuous operational mode.

20. The method of claim 1 , wherein the first gaseous input stream does not include oxygen (O 2 ).

21. A metal alloy particle for use in a method of converting H 2 S to hydrogen (H 2 ) and sulfur, the metal alloy particle comprising a first metal component, a second metal component, and at least one secondary material,
wherein the first metal component comprises iron, the second metal component comprises chromium, and the at least one secondary material is molybdenum, nickel, cobalt, manganese, tungsten, vanadium or a combination thereof.

22. The metal alloy particle of claim 21 , wherein the metal alloy particle further comprises one or more support materials.

23. The metal alloy particle of claim 21 , wherein the first metal component comprises an iron sulfide and the second metal component comprises a chromium sulfide.

24. The metal alloy particle of claim 21 , wherein the at least one secondary material is a molybdenum sulfide, a nickel sulfide, a cobalt sulfide, a manganese sulfide, a tungsten sulfide, vanadium sulfide or a combination thereof.

25. The metal alloy particle of claim 21 , wherein the metal alloy particle comprises 10-95% by weight of the first metal component, 5-80% of the second metal component, and 1-50% by weight of the at least one secondary material.

26. The metal alloy particle of claim 21 , wherein the metal alloy comprises a support material selected from Al 2 O 3 , SiO 2 , TiO 2 , and ZrO 2 .

27. A method of producing the metal alloy particle of claim 21 , the method comprising mixing the first metal component with the second metal component to produce a mixture, contacting the mixture with a gas stream comprising H 2 S to produce a reacted mixture, passing nitrogen over the reacted mixture to form a bimetallic alloy, and mixing one or more secondary materials and optionally one or more support materials with the bimetallic alloy to produce the metal alloy.

Assignees

• Ohio State Innovation Foundation

Inventors

• Fan Liang-Shih
• Nadgouda Sourabh G
• Jangam Kalyani V

Classifications

• B01D2255/20784

  Chromium · CPC title

• B01J27/049 Primary

  with iron group metals or platinum group metals · CPC title

• B01D2256/245

  Methane · CPC title

• B01D53/52 Primary

  Hydrogen sulfide · CPC title

• B01D53/82

  with stationary reactants · CPC title