Removal of acidic gases from hydrocarbon streams

• US 4,041,129 A
• Filed: 07/23/1974
• Issued: 08/09/1977
• Est. Priority Date: 03/20/1970
• Status: Expired due to Term

• Current Assignee: Stone & Webster Engineering Corporation
• Original Assignee: Stone & Webster Engineering Corporation
• Inventors: Humphries, James J. Jr., Foster, Raymond C.
• Primary Examiner(s): Thomas, Earl C.
• Application Number:
  US05/490,935
• Time in Patent Office: 1,113 Days
• Field of Search: 423/210, 423/225, 423/234, 423/242, 423/220, 423/245, 423/226, 204/98, 204/104, 204/108 P
• US Class Current: 423/234
• CPC Class Codes: B01D 2251/304 of sodium
• CPC Class Codes: B01D 2251/604 Hydroxides
• CPC Class Codes: B01D 53/1418 Recovery of products
• CPC Class Codes: B01D 53/1456 Removing acid components
• CPC Class Codes: B01D 53/1462 Removing mixtures of hydrogen sulfide and carbon dioxide
• CPC Class Codes: B01D 53/1493 Selection of liquid materials for use as absorbents
• CPC Class Codes: B01D 53/326 in electrochemical cells
• CPC Class Codes: B01D 53/526 Mixtures of hydrogen sulfide and carbon dioxide
• CPC Class Codes: C07C 11/00 Aliphatic unsaturated hydrocarbons
• CPC Class Codes: C07C 7/1485 oxides; hydroxides; salts C07C7/156 takes precedence
• CPC Class Codes: C10K 1/122 containing only carbonates, bicarbonates, hydroxides or oxides of alkali-metals (including Mg)
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02P 20/151 Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

An apparatus and process for substantially reducing carbon dioxide and/or hydrogen sulfide levels in a hydrocarbon gas with simultaneous regeneration of reagent materials are disclosed. The process consists of passing the gas through an aqueous sodium hydroxide solution, reacting the effluent liquid with an acidic reagent, stripping the acidic gases therefrom and subjecting the resulting aqueous sodium sulfate solution to an electrolytic process. The apparatus used to carry out the process comprises an acidic gas absorbing unit, means for reacting the resulting effluent liquid, means for stripping the acidic gases and an electrolytic cell to convert soluble alkali metal salts into the corresponding alkali metal hydroxide and acidic reagents.

Claims

1. In a cyclic process for substantially reducing the carbon dioxide and/or hydrogen sulfide content present as acidic gases in a gas obtained from the cracking of a hydrocarbon selected from the group consisting of gas oil, naphtha and ethane, and said gas further containing undesirable organic impurities therein, with simultaneous regeneration of reagent materials which comprises:

a. passing the cracked gas containing the acidic gases through an aqueous sodium hydroxide solution and obtaining an effluent containing the undesirable organic impurities and said acidic gases in converted form;

b. reacting said effluent liquid with aqueous sulfuric acid or an aqueous mixture containing sulfuric acid and sodium sulfate in an amount sufficient to substantially liberate the converted acidic gases consisting essentially of hydrogen sulfide and/or carbon dioxide that may be present therein;

c. subjecting said treated effluent liquid to a stripping operation to remove any liberated gases therefrom and thereby leaving an aqueous sodium sulfate containing solution; and

d. subjecting said resulting aqueous sodium sulfate containing solution to an electrolytic process treatment whereby aqueous sulfuric acid or an aqueous mixture of sulfuric acid and sodium sulfate is collected at the anode and is recycled for utilization in the aforesaid reaction step and aqueous sodium hydroxide which forms at the cathode is collected and recycled for use in the sodium hydroxide treatment step, the improvement which comprises treating the effluent from the alkali metal hydroxide treatment of step (a) to remove substantially all organic impurities therefrom.

2. The process according to claim 1 wherein said aqueous sodium hydroxide solution contains sodium sulfate.

3. The process according to claim 1 wherein said sodium hydroxide which forms at the cathode contains sodium sulfate.

4. The process according to claim 1 wherein to the cathode compartment involved in the electrolytic process is added aqueous sodium sulfate in an amount sufficient to maintain the electrolytic membrane free from solids.

5. The process according to claim 1 wherein said effluent liquid contains a small amount of sodium hydroxide.

6. The process according to claim 1 wherein said effluent liquid contains sodium bisulfide and/or sodium bicarbonate.

7. The process according to claim 1 wherein the effluent liquid from sodium hydroxide contacting is extracted with a substantially water-immiscible organic solvent.

8. The process according to claim 7 wherein said organic solvent is a hydrocarbon having a boiling point no higher than that of a gas oil.

9. The process according to claim 8 wherein said hydrocarbon solvent is a naphtha.

10. The process according to claim 8 wherein said hydrocarbon solvent is a gas oil.

11. The process according to claim 1 wherein said effluent liquid from sodium hydroxide contacting is contacted with an adsorbent.

12. The process according to claim 1 wherein said sodium hydroxide treatment step consists of contacting said gas substantially countercurrently with said sodium hydroxide solution.

13. The process according to claim 1 wherein the liberated gases from the stripping operation include hydrogen sulfide which is converted to sulfur.

14. The process according to claim 1 wherein the aqueous sodium sulfate from the stripping operation is filtered before it is subjected to the electrolytic process.

15. The process according to claim 1 wherein said electrolytic process is carried out in an electrolytic cell capable of converting soluble alkali metal salts into their corresponding alkali metal hydroxides and acids.

16. The process according to claim 15 wherein said soluble alkali metal salt is sodium sulfate which is converted to sodium hydroxide and sulfuric acid.

17. The process according to claim 15 wherein said electrolytic cell is a three compartment cell comprising a cathode compartment, a center compartment and an anode compartment, the cathode compartment being separated from the center compartment by a cation selective ion exchange membrane and the center compartment being separated from the anode compartment by a fluid-permeable diaphram.