Process and apparatus for removal of H.sub.2 S with separate absorber and oxidizer and a reaction chamber therebetween

• US 5,126,118 A
• Filed: 04/08/1991
• Issued: 06/30/1992
• Est. Priority Date: 04/08/1991
• Status: Expired due to Term

• Current Assignee: Merichem Company
• Original Assignee: ARI Technologies, Inc.
• Inventors: Hardison, Leslie C.
• Primary Examiner(s): Straub, Gary P.
• Assistant Examiner(s): Vanoy, Timothy C.
• Application Number:
  US07/682,592
• Time in Patent Office: 449 Days
• Field of Search: 423/576.2, 423/576.4, 423/576.5, 423/576.6, 423/576.8, 423/573.1, 423/DIG. 14, 423/220, 423/230, 423/231, 423/191, 422/193, 422/194, 422/169
• US Class Current: 423/220
• CPC Class Codes: B01D 53/52 Hydrogen sulfide
• CPC Class Codes: B01D 53/74 General processes for purification of waste gases; Apparatus or devices specially adapted therefor B01D53/92 takes precedence
• CPC Class Codes: C01B 17/05 by wet processes

Abstract

A method and apparatus including a reaction chamber interposed in a polyvalent metal redox solution flow path between an absorber chamber and an oxygenation chamber, including one or more oxygenation stages, for contact in the reaction chamber of H₂ S-laden catalytic polyvalent metal redox solution form the absorber chamber with highly oxidized polyvalent metal redox solution from the last oxygenation stage to accomplish oxidation of the dissolved H₂ S species by interaction with the oxidized redox catalyst essentially in the absence of gaseous dissolved oxygen. The highly oxidized polyvalent metal redox solution, including Fe⁺³ or V⁺⁵, contacts the H₂ S-laden solution from the absorber chamber for reoxidation of the dissolved HS^-, S⁼ and any of the polyvalent metal sulfur compounds (presumably a chelated iron sulfide or a vanadium sulfide), to avoid formation of sulfate or thiosulfate salts which reduce the yeild of sulfur and build up in the solution. To avoid the formation of crystals of iron sulfide or crystals of vanadium sulfide, thereby avoiding loss of polyvalent metal, the residence time of the redox solution after contact with the H₂ S-containing gas and prior to contacting with the oxidized metal redox solution is limited to a relatively short time. Flow of solution from the last oxygenation stage, preferably through a valve or other circulation control device, to the reaction chamber provides controlled and continuous elemental sulfur formation in the reaction chamber.

Claims

1. In a continuous process for intimate contact of a liquid reagent sequentially with first and second different gases in separate vessels, the improvement comprising:

introducing the first gas into a first mass transfer vessel for intimate contact and mass transfer with the liquid reagent;

introducing liquid reagent from said first mass transfer vessel, after mass transfer with said first gas, into a reaction chamber;

introducing the second gas into a separate, second mass transfer vessel for intimate contact and mass transfer with liquid reagent from the reaction chamber;

introducing liquid reagent from said second mass transfer vessel, after mass transfer with said second gas, into said reaction chamber for contact and mixing with liquid reagent from said first mass transfer vessel to form a reaction product in said reaction chamber;

recirculating a portion of the liquid reagent from the reaction chamber to the first mass transfer vessel, without intermediate mass transfer with said second gas, for further mass transfer with the first gas; and

continuously flowing, in a controlled flow, liquid reagent from said second mass transfer zone into the reaction chamber, where no substantial additional gas is introduced, to provide a residence time and intermixing of the liquid reagents from the first and second mass transfer vessels.

2. The process as defined in claim 1 wherein the portion of the liquid recirculated from the reaction chamber to the first mass transfer vessel is less than 75% by weight of the total liquid.

3. The process as defined in claim 1 wherein the flow of liquid through the second mass transfer vessel is achieved by solution density differences in successive mass transfer stages of the second mass transfer vessel.

4. The process as defined in claim 1 wherein the liquid reagent is a polyvalent metal redox solution, and wherein the first gas is an H₂ S-containing process gas, and wherein the second gas is an oxygen-containing gas.

5. The method of claim 4 further including the step of removing elemental sulfur from the reaction chamber together with some polyvalent metal redox solution, and separating the sulfur from the polyvalent metal redox solution.

6. The method of claim 4 wherein the process gas further includes a cyanide gas.

7. The method of claim 4 wherein the concentration and flow rate of polyvalent metal redox solution in the first mass transfer zone provides 90% or less of the stoichiometric quantity of polyvalent metal redox solution required for reaction with all of the H₂ S in the process gas.

8. The method of claim 4 wherein the solution is a catalytic ferric iron chelate solution that is reduced by hydrogen sulfide gas to a ferrous iron solution in said first mass transfer vessel.

9. The process of claim 4 wherein the polyvalent metal redox solution contains a vanadium salt, or a combination of chelated iron and vanadium.

10. The process of claim 1 wherein the liquid reagent solution contains an anthraquinone or an anthraquinone sulfonate.

11. The process of claim 1 wherein the liquid reagent solution contains a naphthaquinone or a naphthaquinone sulfonate.

12. The method of claim 1 including the step of introducing the liquid reagent from the second mass transfer vessel through an intermediate flow channel, wherein essentially no additional gas is dispersed, into the reaction chamber, said intermediate flow channel for retaining a continuous supply of the liquid reagent between the second mass transfer zone and the reaction chamber, and continuously flowing a portion of the liquid reagent from the reaction chamber to the second mass transfer zone at a controlled rate.

13. The method of claim 1 wherein the second mass transfer vessel includes a plurality of mass transfer stages in open liquid communication, one with another, and wherein the reaction chamber is in open liquid communication with the second mass transfer vessel including introducing the second gas into a first stage of the second mass transfer zone in contact with said liquid reagent;

and thereafter contacting the liquid reagent received from the first stage of the second mass transfer vessel with the second gas in a second stage of the second mass transfer vessel.

14. A method of contacting a liquid reagent with different gases sequentially in separate mass transfer vessels, said mass transfer vessels operatively connected in liquid communication with each other comprising:

intimately contacting the liquid reagent with a process gas in a first mass transfer vessel, to effect mass transfer between said liquid reagent and said process gas, thereby forming a treated gas and a less active liquid reagent;

introducing the less active liquid reagent into a reaction chamber, said reaction chamber in fluid communication with said second mass transfer vessel;

flowing a portion of the less active liquid reagent from the reaction chamber to the second mass transfer vessel and flowing the remainder of the less active liquid reagent to the first mass transfer vessel;

introducing a second gas, different from said process gas, into said second mass transfer vessel in contact with less active liquid reagent, thereby effecting mass transfer between said less active liquid reagent and said second gas to form a more active liquid reagent; and

controlling the rate of flow of said more active liquid reagent from said second mass transfer vessel to the reaction chamber to control the amount of mass transfer in said second mass transfer vessel.

15. The method of claim 14 wherein the process gas includes a hydrogen sulfide gas contaminant and said liquid reagent is a reducible catalytic oxidation-reduction solution, thereby effecting reduction of the catalytic solution in said first mass transfer vessel to form a reduced catalytic solution and to effect oxidation of the hydrogen sulfide gas, and wherein the second gas is capable of oxidizing the reduced catalytic solution so that the oxidized catalytic solution is capable of further oxidation of the process gas in the first mass transfer vessel, to form elemental sulfur.

16. The method of claim 15 wherein the catalytic solution is a ferric iron chelate solution that is reduced by hydrogen-sulfide gas in said first mass transfer vessel to a ferrous iron solution.

17. A continuous process for intimate contact of a liquid reagent sequentially with first and second different gases in first and second separate mass transfer vessels, said second mass transfer vessel including a second mass transfer zone including one or more mass transfer stages serially arranged with an upper portion of one mass transfer stage in liquid communication with a lower portion of a succeeding mass transfer stage and a reaction chamber in liquid communication with said second mass transfer zone;

said reaction chamber being in liquid flow communication with liquid reagent in the second transfer zone, such that liquid reagent introduced into the reaction chamber flows into the second mass transfer zone, for intimate contact with the second gas and flowing out of the second mass transfer zone through a liquid reagent outlet near an upper portion of said second mass transfer zone;

introducing the first gas into a first mass transfer vessel, in liquid communication with the second mass transfer vessel, for intimate contact and mass transfer with said liquid reagent;

introducing the second gas into said second mass transfer zone for intimate contact and mass transfer with said liquid reagent after said liquid reagent has been intimately contacted and mass transferred with the first gas in the first mass transfer vessel;

controlling the flow rate of said liquid reagent from said second mass transfer zone to said reaction chamber to effect continuous circulation of liquid reagent from the second mass transfer zone to the reaction chamber; and

continuously flowing a portion of the liquid reagent from said second mass transfer zone into the reaction chamber and continuously flowing a portion of the liquid reagent from the reaction chamber into the second mass transfer zone, while flowing liquid reagent from the first mass transfer vessel to the reaction chamber and a portion of the liquid reagent from the second mass transfer vessel into the first mass transfer vessel for continuous recirculation of liquid and sequential intimate contact of said liquid reagent with said two gases.

18. The method of claim 17 wherein the process gas includes a hydrogen sulfide gas contaminant and said liquid reagent is a catalytic oxidation-reduction solution, thereby effecting oxidation of the hydrogen sulfide gas and reduction of the catalytic solution in the first transfer vessel;

and wherein the second gas is capable of oxidizing the reduced catalytic solution to form an oxidized catalytic solution so that the oxidized catalytic solution is capable of further oxidation of the process gas in the first mass transfer vessel.

19. Apparatus for effecting mass transfer of a liquid reagent sequentially with two different gases in a separate mass transfer vessel for each gas, comprising:

a first mass transfer vessel for intimate contact and mass transfer between the liquid reagent and a first gas;

means for directing the liquid reagent and the first gas into the first mass transfer vessel to form a treated gas and a reacted liquid reagent;

a second mass transfer vessel including a plurality of mass transfer stages serially arranged with an upper end of one mass transfer stage in liquid communication with a lower end of a succeeding mass transfer stage through an intermediate flow channel wherein essentially no additional gas is dispersed in the liquid within the intermediate flow channel, and an integral reaction chamber, wherein essentially no additional gas is dispersed, in liquid communication with a first mass transfer stage;

means for directing the reacted liquid reagent from the first mass transfer vessel into the reaction chamber;

means for directing a portion of the liquid reagent from an upper portion of the reaction chamber into a lower portion of the first mass transfer stage of the second mass transfer vessel;

means for directing a second gas into each mass transfer stage of the second mass transfer vessel for intimate contact and mass transfer with the liquid reagent, said stages of said second mass transfer vessel disposed in a single mass transfer vessel including baffles separating the mass transfer stages, defining said intermediate flow channels, to prevent gas from the mass transfer stages of the second mass transfer vessel from contacting liquid reagent in the reaction chamber; and

means operatively connected between the second mass transfer vessel and the reaction chamber thereof for controlling the flow rate of liquid reagent in the second mass transfer vessel between a last mass transfer stage and the reaction chamber, while maintaining continuous flow of liquid reagent between the first mass transfer vessel, reaction chamber, and the mass transfer stages of the second mass transfer vessel.

20. The apparatus of claim 19 wherein the baffles separating the reaction chamber and the first mass transfer stage of the second mass transfer vessel are two spaced, overlapping vertically baffles overlapping within the liquid reagent to allow liquid reagent flow between an upper portion of the reaction chamber and a lower portion of the first mass transfer stage of the second mass transfer vessel.

21. The apparatus of claim 20 further including a first conduit operatively connected between the reaction chamber and the first mass transfer vessel and a second conduit operatively connected between a mass transfer stage of said second mass transfer vessel and said first mass transfer vessel to provide liquid communication of said first mass transfer vessel with both the reaction chamber and the second mass transfer vessel, said conduits each including a valve adapted to adjust the flow of said liquid reagent from said second mass transfer vessel to said first mass transfer vessel and between a mass transfer stage of said second mass transfer vessel and said reaction chamber.