Electrochemical method for producing hydrogen and sulfur

• US 5,019,227 A
• Filed: 11/09/1987
• Issued: 05/28/1991
• Est. Priority Date: 11/09/1989
• Status: Expired due to Fees

• Current Assignee: Texas A&M University System
• Original Assignee: Texas A&M University System
• Inventors: Mao, Zhenhua, White, Ralph E., Srinivasan, Supramaniam
• Primary Examiner(s): Tung, T.
• Assistant Examiner(s): RYSER, DAVID
• Application Number:
  US07/433,698
• Time in Patent Office: 1,296 Days
• Field of Search: 204/92, 204/128, 204/129, 204/130, 423/573.1
• US Class Current: 205/617
• CPC Class Codes: C25B 1/00 Electrolytic production of inorganic compounds or non-metals
• CPC Class Codes: C25B 1/02 Hydrogen or oxygen

Abstract

A process for the electrochemical production of hydrogen gas and sulfur from hydrogen sulfide gas is disclosed. The process includes forming a substantially equimolar mixture of hydrosulfide and sodium hydrogen. That mixture is transferred to the anodic compartment of an electrochemical cell that includes a membrane that separates the anodic and cathodic compartments. A substantially pure sodium hydroxide solution is transferred to the cathodic compartment. Passage of an electric current through the electrolyte causes hydrogen gas to be produced at the cathode and sulfur in the anodic compartment.

Claims

1. A method for removing sulfide ions from a sulfide ion containing solution comprising:

providing a sulfide ion containing solution;

forming a mixture containing the sulfide ion containing solution by adding a sulfide concentration balancing amount of a basic solution; and

electrochemically precipitating sulfur from the mixture in an electrochemical cell.

2. The method of claim 1 in which the sulfide ion containing solution is a hydrosulfide containing solution.

3. The method of claim 2 further including the step of absorbing hydrogen sulfide gas in an alkaline solution producing the hydrosulfide containing solution.

4. The method of claim 3 in which the basic solution is a sodium hydroxide containing solution.

5. The method of claim 4 further including the step of feeding the mixture into the electrochemical cell after forming the mixture.

6. The method of claim 5 in which the electrochemical cell includes an anodic compartment that includes an anode, a cathodic compartment that includes a cathode, and a membrane that is substantially impenetrable to negatively charged sulfide and polysulfide ions that divides the anodic compartment from and the cathodic compartment.

7. The method of claim 6 further including the steps of feeding the mixture into the anodic compartment and feeding a zero valence sulfur lacking sodium hydroxide solution into the cathodic compartment, and in which the membrane inhibits movement of negatively charged sulfide and polysulfide ions from the anodic compartment to the cathodic compartment.

8. The method of claim 7 further including the step of producing hydrogen gas at the cathode.

9. The method of claim 8 in which the mixture includes hydrosulfide and sodium hydroxide in a molar ratio of between about 2:

1 and about 2;

3.

10. The method of claim 9 in which the mixture includes substantially equimolar amounts of hydrosulfide and sodium hydroxide.

11. A method for removing sulfide ions from a sulfide ion containing solution comprising:

providing a sulfide ion containing solution;

forming a mixture containing the sulfide ion containing solution by adding a basic solution comprising hydroxide ions in which the molar ratio of the sulfide ions to the hydroxide ions is between about 2;

1 and about 2;

3; and

electrochemically precipitating sulfur from the mixture in an electrochemical cell.

12. The method of claim 11 in which the mixture includes substantially equimolar amounts of sulfide ions and hydroxide ions.

13. A method for producing hydrogen gas and sulfur from hydrogen sulfide gas comprising:

providing a hydrosulfide containing solution;

forming a mixture containing the hydrosulfide containing by adding solution a sulfide concentration balancing amount of a basic solution;

transferring the mixture to an anodic compartment of an electrochemical cell having an anodic compartment having an anode and a cathodic compartment having a cathode;

transferring a zero valence sulfur lacking basic solution to the cathodic compartment of the electrochemical cell; and

passing an electric current through the mixture and the zero valence sulfur lacking basic solution at a sufficient current density for a sufficient time period producing hydrogen gas at the cathode in the cathodic compartment, and sulfur precipitate in the anodic compartment.

14. The method of claim 13 further including the steps of:

providing the hydrosulfide containing solution by

absorbing hydrogen sulfide gas in an alkaline solution before forming the mixture; and

separating the sulfur precipitate from the anodic compartment and the hydrogen gas from the cathodic compartment.

15. The method of claim 13 in which the basic solution is selected from the group consisting of solutions that comprise alkali metal hydroxides, salts of an alkali metal and a halogen, and mixtures thereof.

16. The method of claim 15 in which the mixture is a substantially equimolar mixture of hydrosulfide and a composition selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, and mixtures thereof.

17. The method of claim 16 further including the steps of maintaining the pH of the mixture between about 9.0 and about 14.0 and heating the mixture and the zero valance sulfur lacking basic solution to a temperature between about 60°

C. and about 110°

C.

21. The method of claim 16 further including the steps of absorbing the hydrogen sulfide gas in a solution comprising a composition selected from the group consisting of sodium hydroxide, sodium chloride, and a mixture of sodium hydroxide and sodium chloride, adding to the hydrosulfide containing solution a solution comprising a composition selected from the group consisting of sodium hydroxide, sodium chloride, and a mixture of sodium hydroxide and sodium chloride, and transferring a solution to a cathodic compartment of the electrochemical cell comprising a composition selected from the group consisting of sodium hydroxide, sodium chloride, and a mixture of sodium hydroxide and sodium chloride.

22. The method of claim 21 in which the mixture includes a substantially equimolar mixture of hydrosulfide and a composition selected from the group consisting of sodium hydroxide, sodium chloride, and a mixture of sodium hydroxide and sodium chloride.

23. The method of claim 22 further including the step of heating the mixture to a temperature between about 60°

C. and about 110°

C.

18. A method for producing hydrogen gas and sulfur from hydrogen sulfide gas comprising:

providing a hydrosulfide containing solution;

forming a mixture containing the hydrosulfide containing solution by adding a basic solution comprising hydroxide ions in which the molar ratio of the hydrosulfide to the hydroxide ions is between about 2;

1 and about 2;

3;

transferring the mixture to an anodic compartment of an electrochemical cell having an anodic compartment having an anode and a cathodic compartment having a cathode;

transferring a zero valence sulfur lacking basic solution to the cathodic compartment of the electrochemical cell; and

passing an electric current through the mixture and the zero valence sulfur lacking basic solution at a sufficient current density for a sufficient time period to produce hydrogen gas at the cathode in the cathodic compartment, and sulfur precipitate in the anodic compartment.

19. The method of claim 18 in which the mixture includes substantially equimolar amounts of hydrosulfide and hydroxide ions.

20. A method for producing hydrogen gas and sulfur from hydrogen sulfide gas comprising:

absorbing hydrogen sulfide gas in a solution comprising a composition selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, and mixtures thereof, forming a hydrosulfide containing solution;

adding a sulfide concentration balancing amount of a solution comprising a composition selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, and mixtures thereof, to the hydrosulfide containing solution forming a mixture;

transferring the mixture to an anodic compartment of an electrochemical cell having an anode compartment having an anode, a cathodic compartment having a cathode, and a membrane that is substantially impenetrable to negatively charged sulfide and polysulfide ions that divides the anodic compartment from the cathodic compartment of the electrochemical cell;

transferring a solution comprising selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium chloride, potassium chloride, and mixtures thereof, to the cathodic compartment of the electrochemical cell;

passing an electric current through the mixture producing hydrogen gas at the cathode in the cathodic compartment and sulfur precipitate in the anodic compartment; and

separating the sulfur precipitate from the anodic compartment and the hydrogen gas from the cathodic compartment.

24. A method for producing hydrogen gas and sulfur from hydrogen sulfide gas comprising:

absorbing hydrogen sulfide gas in a solution comprising sodium hydroxide to produce a hydrosulfide containing solution;

adding a sufficient amount of sodium hydroxide to the hydrosulfide containing solution to form a mixture that includes hydrosulfide and sodium hydroxide in a molar ratio between about 2;

1 and about 2;

3.

transferring the mixture to an anodic compartment of an electrochemical cell having an anodic compartment having an anode, a cathodic compartment having a cathodic, and a membrane that is substantially impenetrable to negatively charged sulfide and polysulfide ions that divides the anodic compartment from the cathodic compartment of the electrochemical cell;

transferring a zero valence sulfur lacking sodium hydroxide containing solution to the cathodic compartment of the electrochemical cell;

heating the mixture to a temperature between about 60°

C. and about 110°

C.;

passing an electric current through the mixture producing hydrogen gas at the cathode in the cathodic compartment and sulfur precipitate in the anodic compartment; and

separating the sulfur precipitate from the anodic compartment and the hydrogen gas from the cathodic compartment.

25. The method of claim 24 further including the step of adding a sufficient amount of sodium hydroxide to the hydrosulfide containing solution forming a mixture that includes substantially equimolar amounts of hydrosulfide and sodium hydroxide.