IP Library Granted Patent US 9,845,539
Granted Patent B2
US 9,845,539 · App. 14/649,134 · Granted Dec 19, 2017

Treatment of hydrogen sulfide

Inventors: C. Deane Little (Niwot, CO); Joseph Victor Kosmoski (Longmont, CO); Yongan Yang (Lakewood, CO); Ryan Patrick O'Hayre (Golden, CO); Tim S. Olson (Arvada, CO)
C25B1/16B01D53/1425B01D53/1468B01D53/1493B01D53/52B01D53/73B01D53/78C25B1/00C25B15/08B01D2251/304B01D2252/10B01D2257/304
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Quick Facts
Patent No.
US 9,845,539
App. No.
14/649,134
Granted
Dec 19, 2017
Kind
B2
Abstract

A chemical process captures and convert hydrogen sulfide (H 2 S) gas into elemental sulfur, polysulfide, sulfur dioxide and/or sulfuric acid while regenerating sodium hydroxide capture agent for further use in an initial H 2 S capture step. Processing may include initial sodium hydroxide scrubbing of gas streams containing H 2 S, electrochemical regeneration of the sodium hydroxide from sodium hydrosulfide or sodium sulfide, recovery of sulfur and/or sulfur dioxide from the electrochemical processing, and production of sulfuric acid from such sulfur and/or sulfur dioxide.

Claims (81)

1. A method for processing hydrogen sulfide and preparing sulfur-containing products, the method comprising:

scrubbing hydrogen sulfide from a gas stream comprising hydrogen sulfide, the scrubbing comprising contacting the gas stream in a first reactor with basic alkali metal scrubbing reagent to form alkali metal-containing sulfide;

electrochemical processing an electrolyte solution feed comprising at least a portion of the alkali metal-containing sulfide to produce sulfur-containing product;

the electrochemical processing comprising:

feeding at least a portion of the electrolyte solution feed to a second reactor, wherein the second reactor is an electrochemical reactor including at least one electrochemical cell comprising an anode, a cathode, an anode region adjacent the anode and a cathode region adjacent the cathode;

producing the sulfur-containing product in the anode region;

producing alkali metal hydroxide in the cathode region; and

applying electrical power between the anode and cathode at a level sufficient to produce the sulfur-containing product in the anode region and the alkali metal hydroxide in the cathode region and not sufficient for water electrolysis that generates oxygen gas in the anode region; and

wherein the electrochemical processing is in the absence of adding oxygen gas to each said electrochemical cell;

wherein the electrolyte solution feed comprises dissolved alkali metal-containing carbonate; and

the method further comprises:

recovering processed electrolyte solution from the electrochemical processing, the processed electrolyte solution comprising at least a portion of the alkali metal-containing carbonate and being depleted in the alkali metal containing sulfide relative to the electrolyte solution feed; and

second electrochemical processing a second electrolyte solution feed comprising at least a portion of the processed electrolyte solution, to prepare alkali metal hydroxide and carbon dioxide gas, the second electrochemical processing being conducted in a second electrochemical reactor at a direct current voltage high enough to electrolyze water in an anode region of the second electrochemical reactor.

2. A method according to claim 1 , wherein the electrolyte

solution feed comprises a molar concentration ratio of concentration of dissolved alkali metal sulfide to concentration of dissolved alkali metal hydrosulfide of at least 1:9.

3. A method according to claim 1 , wherein the gas stream comprises a mixture including hydrogen sulfide and carbon dioxide and the scrubbing comprises selectively scrubbing hydrogen sulfide from the gas stream relative to carbon dioxide.

4. A method according to claim 3 , wherein the scrubbing comprises scrubbing at least a portion of the carbon dioxide from the gas stream in the form of alkali metal containing carbonate.

5. A method according to claim 1 , wherein the alkali metal-containing sulfide comprises a mixture of alkali metal sulfide and alkali metal hydrosulfide.

6. A method according to claim 1 , wherein during the electrochemical processing, electrical potential difference between the anode and the cathode of the electrochemical cell is smaller than 2.06 volts.

7. A method according to claim 1 , wherein the electrochemical reactor comprises multiple said electrochemical cells producing sulfur containing product and alkali metal hydroxide during the electrochemical processing and the electrochemical processing is essentially in the absence of water electrolysis generating oxygen gas in the anode region of any of said electrochemical cells.

8. A method according to claim 7 , wherein at least some of said electrochemical cells are electrically connected in series.

9. A method according to claim 1 , wherein the sulfur containing product comprises at least one member selected from the group consisting of elemental sulfur and polysulfide.

10. A method according to claim 1 , comprising:

making fresh alkali metal hydroxide, separate from the electrochemical processing, the making fresh alkali metal hydroxide comprising:

electrolyzing a second electrolyte solution comprising dissolved alkali metal salt selected from the group consisting of alkali metal sulfate, alkali metal bisulfate and combinations thereof; and the electrolyzing comprises electrolyzing water of the second electrolyte solution to generate the fresh alkali metal hydroxide and dilute sulfuric acid;

wherein, the scrubbing reagent comprises at least a portion of the fresh alkali metal hydroxide.

11. A method according to claim 1 , wherein the alkali metal is sodium.

12. A method according to claim 1 , wherein the alkali metal-containing sulfide is selected from the group consisting of alkali metal sulfide, alkali metal hydrosulfide and combinations thereof.

13. A method according to claim 1 , wherein during the electrochemical processing, electrical potential difference between the anode and the cathode of the electrochemical cell is no larger than 2.0 volts.

14. A method according to claim 1 , comprising producing hydrogen gas in the cathode region.

15. A method according to claim 14 , wherein the electrochemical reactor comprises multiple said electrochemical cells producing sulfur-containing product, alkali metal hydroxide and hydrogen gas during the electrochemical processing and the electrochemical processing is essentially in the absence of water electrolysis generating oxygen gas in the anode region of any of said electrochemical cells.

16. A method for processing hydrogen sulfide and preparing sulfur-containing products, the method comprising;

scrubbing hydrogen sulfide from a gas stream comprising hydrogen sulfide, the scrubbing comprising contacting the gas stream with basic alkali metal scrubbing reagent to form alkali metal-containing sulfide;

electrochemical processing an electrolyte solution feed comprising at least a portion of the alkali metal-containing sulfide to produce sulfur-containing product;

the electrochemical processing comprising:

feeding at least a portion of the electrolyte solution feed to an electrochemical reactor including at least one electrochemical cell comprising an anode, a cathode, an anode region adjacent the anode and a cathode region adjacent the cathode;

producing the sulfur-containing product in the anode region;

producing alkali metal hydroxide in the cathode region;

applying electrical power between the anode and cathode at a level sufficient to produce the sulfur-containing product in the anode region and the alkali metal hydroxide in the cathode region and not sufficient for water electrolysis that generates oxygen gas in the anode region; and

feeding oxygen gas to the anode region.

17. A method according to claim 16 , wherein the alkali metal-containing sulfide comprises a mixture of alkali metal sulfide and alkali metal hydrosulfide.

18. A method according to claim 16 , wherein during the electrochemical processing, electrical potential difference between the anode and the cathode of the electrochemical cell is smaller than 2.06 volts.

19. A method according to claim 16 , wherein the electrochemical reactor comprises multiple said electrochemical cells producing sulfur containing product and alkali metal hydroxide during the electrochemical processing and the electrochemical processing is essentially in the absence of water electrolysis generating oxygen gas in the anode region of any of said electrochemical cells.

20. A method according to claim 16 , wherein the sulfur containing product comprises at least one member selected from the group consisting of elemental sulfur and polysulfide.

21. A method according to claim 16 , comprising:

making fresh alkali metal hydroxide, separate from the electrochemical processing, the making fresh alkali metal hydroxide comprising:

electrolyzing a second electrolyte solution comprising dissolved alkali metal salt selected from the group consisting of alkali metal sulfate, alkali metal bisulfate and combinations thereof; and the electrolyzing comprises electrolyzing water of the second electrolyte solution to generate the fresh alkali metal hydroxide and dilute sulfuric acid;

wherein, the scrubbing reagent comprises at least a portion of the fresh alkali metal hydroxide.

22. A method according to claim 16 , wherein the alkali metal is sodium.

23. A method according to claim 16 , wherein the alkali metal-containing sulfide is selected from the group consisting of alkali metal sulfide, alkali metal hydrosulfide and combinations thereof.

24. A method according to claim 16 , wherein during the electrochemical processing, electrical potential difference between the anode and the cathode of the electrochemical cell is no larger than 2.0 volts.

25. A method according to claim 16 , comprising producing hydrogen gas in the cathode region.

26. A method according to claim 25 , wherein the electrochemical reactor comprises multiple said electrochemical cells producing sulfur-containing product, alkali metal hydroxide and hydrogen gas during the electrochemical processing and the electrochemical processing is essentially in the absence of water electrolysis generating oxygen gas in the anode region of any of said electrochemical cells.

27. A method for processing hydrogen sulfide and preparing sulfur-containing products, the method comprising:

scrubbing hydrogen sulfide from a gas stream comprising hydrogen sulfide, the scrubbing comprising contacting the gas stream in a first reactor with basic alkali metal scrubbing reagent to form alkali metal-containing sulfide;

electrochemical processing an electrolyte solution feed comprising at least a portion of the alkali metal-containing sulfide to produce sulfur-containing product;

the electrochemical processing comprising:

feeding at least a portion of the electrolyte solution feed to a second reactor, wherein the second reactor is an electrochemical reactor including at least one electrochemical cell comprising an anode, a cathode, an anode region adjacent the anode and a cathode region adjacent the cathode;

producing the sulfur-containing product in the anode region;

producing alkali metal hydroxide in the cathode region; and

applying electrical power between the anode and cathode at a level sufficient to produce the sulfur-containing product in the anode region and the alkali metal hydroxide in the cathode region and not sufficient for water electrolysis that generates oxygen gas in the anode region; and

wherein the electrochemical processing is in the absence of adding oxygen gas to each said electrochemical cell;

wherein the gas stream comprises a mixture including hydrogen sulfide and carbon dioxide and the scrubbing comprises selectively scrubbing hydrogen sulfide from the gas stream relative to carbon dioxide;

wherein the scrubbing comprises scrubbing at least a portion of the carbon dioxide from the gas stream in the form of alkali metal containing carbonate;

the scrubbing comprises recovering a pregnant scrubbing solution comprising the alkali metal-containing sulfide and the alkali metal-containing carbonate; and

the method comprises prior to the electrochemical processing, selectively removing by precipitation at least a portion of the alkali metal-containing carbonate from the pregnant scrubbing solution relative to the alkali metal-containing sulfide.

28. A method according to claim 27 , wherein the metal

alkali-containing carbonate is selected from the group consisting of alkali metal carbonate, alkali metal bicarbonate and combinations thereof.

29. A method according to claim 27 , wherein the alkali metal-containing sulfide comprises a mixture of alkali metal sulfide and alkali metal hydrosulfide.

30. A method according to claim 27 , wherein during the electrochemical processing, electrical potential difference between the anode and the cathode of the electrochemical cell is smaller than 2.06 volts.

31. A method according to claim 27 , wherein the electrochemical reactor comprises multiple said electrochemical cells producing sulfur containing product and alkali metal hydroxide during the electrochemical processing and the electrochemical processing is essentially in the absence of water electrolysis generating oxygen gas in the anode region of any of said electrochemical cells.

32. A method according to claim 27 , wherein the sulfur containing product comprises at least one member selected from the group consisting of elemental sulfur and polysulfide.

33. A method according to claim 27 , comprising:

making fresh alkali metal hydroxide, separate from the electrochemical processing, the making fresh alkali metal hydroxide comprising:

electrolyzing a second electrolyte solution comprising dissolved alkali metal salt selected from the group consisting of alkali metal sulfate, alkali metal bisulfate and combinations thereof; and the electrolyzing comprises electrolyzing water of the second electrolyte solution to generate the fresh alkali metal hydroxide and dilute sulfuric acid;

wherein, the scrubbing reagent comprises at least a portion of the fresh alkali metal hydroxide.

34. A method according to claim 27 , wherein the alkali metal is sodium.

35. A method according to claim 27 , wherein the alkali metal-containing sulfide is selected from the group consisting of alkali metal sulfide, alkali metal hydrosulfide and combinations thereof.

36. A method according to claim 27 , wherein during the electrochemical processing, electrical potential difference between the anode and the cathode of the electrochemical cell is no larger than 2.0 volts.

37. A method according to claim 27 , comprising producing hydrogen gas in the cathode region.

38. A method according to claim 37 , wherein the electrochemical reactor comprises multiple said electrochemical cells producing sulfur-containing product, alkali metal hydroxide and hydrogen gas during the electrochemical processing and the electrochemical processing is essentially in the absence of water electrolysis generating oxygen gas in the anode region of any of said electrochemical cells.

Assignments (4)
CHANGE OF NAME Recorded Sep 28, 2018
From: NEW SKY ENERGY INTELLECTUAL PROPERTY HOLDING COMPANY, LLC
To: SULFURCYCLE INTELLECTUAL PROPERTY HOLDING COMPANY LLC
Reel/Frame 047004/0971 →
NUNC PRO TUNC ASSIGNMENT Recorded Nov 30, 2016
From: NEW SKY ENERGY, LLC
To: NEW SKY ENERGY INTELLECTUAL PROPERTY HOLDING COMPANY, LLC
Reel/Frame 040462/0882 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 30, 2016
From: NEW SKY ENERGY, LLC
To: NEW SKY ENERGY INTELLECTUAL PROPERTY HOLDING COMPANY, LLC
Reel/Frame 039056/0444 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 21, 2015
From: LITTLE, C. DEANE; KOSMOSKI, JOSEPH VICTOR; YANG, YONGAN; O'HAYRE, RYAN PATRICK; OLSON, TIM S.
To: NEW SKY ENERGY, LLC
Reel/Frame 036847/0306 →
Continuity (2)
Provisional Application 61745355 · Dec 21, 2012
Related Publication 20150322580A1 · Nov 12, 2015