Removal of corrosive contaminants from alkanolamine absorbent process

• US 6,334,886 B1
• Filed: 05/12/2000
• Issued: 01/01/2002
• Est. Priority Date: 05/12/2000
• Status: Expired due to Fees

• Current Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Bixler, Arthur Daniel, Barnes, David Richard Jr.
• Primary Examiner(s): SMITH, DUANE
• Application Number:
  US09/569,732
• Time in Patent Office: 599 Days
• Field of Search: 210/662, 210/670, 210/673, 210/677, 210/681, 210/683, 423/228, 423/229, 951/81, 951/83, 951/86, 951/87, 951/90, 952/35, 952/36, 962/34
• US Class Current: 95/181
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/1425 Regeneration of liquid absorbents
• CPC Class Codes: B01J 41/05 in the strongly basic form
• CPC Class Codes: B01J 41/07 in the weakly basic form
• CPC Class Codes: C02F 1/42 by ion-exchange ion-exchange in general B01J
• CPC Class Codes: C07C 213/10 Separation; Purification; Stabilisation; Use of additives
• CPC Class Codes: C07C 215/08 with only one hydroxy group and one amino group bound to the carbon skeleton
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02P 20/151 Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

A process is provided for removing CO₂ and/or H₂S from a gas mixture containing as impurities CO₂ and/or H₂S and at least one other impurity selected from the group consisting of a cyanide and ammonia. The process includes contacting at least a portion of the reflux stream from the overhead vapor from a stripping column of an acid gas removal solvent (i.e., alkanolamine) treatment plant with an anion exchange resin to remove corrosive impurities. The ion-exchanged reflux stream is then recycled to the top of the stripping column or into the bulk circulating acid gas removal solvent (i.e., alkanolamine) passing from the bottom of the stripping column.

Claims

1. In a process for removing CO₂ and/or H₂S from a gas mixture containing as impurities CO₂ and/or H₂S and at least one other impurity selected from the group consisting of a cyanide and ammonia, wherein:

said gas mixture is conveyed to an absorber vessel and contacted with an aqueous absorbent solution containing an acid gas removal solvent to remove CO₂ and/or H₂S from said gas mixture and form a rich aqueous absorbent solution enriched in CO₂ and/or H₂S removed from said gas mixture;

said rich aqueous absorbent solution is conveyed from said absorber vessel to a stripping vessel, and thermally stripped of CO₂ and/or H₂S to form a lean aqueous absorbent solution depleted of CO₂ and/or H₂S, and an overhead vapor stream rich in CO₂ and/or H₂S and said at least one other impurity;

said lean aqueous absorbent solution is recycled from said stripping vessel to said absorber vessel to absorb additional amounts of said gas mixture;

said overhead vapor stream is cooled in a heat exchanger to provide a two phase outlet stream and said two phase outlet stream is separated in a separator vessel to provide an acid gas rich stream and an acid gas removal solvent rich aqueous solution; and

recycling said acid gas removal solvent rich aqueous solution for further use in said process,

the improvement comprising contacting at least a portion of said acid gas removal solvent rich aqueous solution with an anion exchange resin to remove from said acid gas removal solvent rich aqueous solution at least a part of said at least one other impurity prior to said recycling of said acid gas removal solvent rich aqueous solution for further use in said process.

2. The process of claim 1, wherein said gas mixture contains impurities comprising CO₂ and/or H₂S, and cyanide and/or ammonia.

3. The process of claim 2, wherein said gas mixture further comprises at least one member selected from the group consisting of carboxylic acids and mixtures thereof.

4. The process of claim 1, wherein said acid gas removal solvent is an alkanolamine selected from the group consisting of monoethanolamine, diethanolamine, methyl diethanolamine, diisopropanol amine, triethanol amine methanol, potassium carbonate, diglycolamine, propylene carbonate, glycerol triacetate, butoxy diethylene glycol acetate, methoxy triethylene glycol acetate, dimethyl ether of propylene glycol, N-methyl-2 pyrrolidone, tri-n-butylphosphate, tetrahydrothiophene 1-1 dioxide, di-isopropanolamine.

5. The process of claim 1, wherein said acid gas removal solvent is monoethanolamine.

6. The process of claim 1, wherein said anion exchange resin is a Type II strong base anionic resin.

7. The process of claim 1, wherein said anion exchange resin is a member selected from the group consisting of weak base anionic resins.

8. The process of claim 1, wherein a minor portion of said acid gas removal solvent rich aqueous solution is conveyed to an upper portion of said stripping vessel without being ionically exchanged, and a major portion of said acid gas removal solvent rich aqueous solution is contacted with said anion exchange resin and then conveyed to an upper portion of said absorber vessel.

9. The process of claim 8, wherein said gas mixture contains impurities comprising CO₂ and/or H₂S, and cyanide and/or ammonia, said acid gas removal solvent is monoethanolamine, and said anion exchange resin is a Type II base anionic resin.

10. The process of claim 1, wherein all of said acid gas removal solvent rich aqueous solution is conveyed from said separator vessel to said anion exchange resin, and an effluent of said anion exchange resin is conveyed to an upper portion of said stripping vessel.

11. The process of claim 1, wherein said anion exchange resin is periodically taken offline and regenerated by caustic.

12. An acid gas removal solvent processing apparatus adapted to perform the process of claim 1, said apparatus comprising:

an absorber vessel comprising a sour gas mixture inlet and a rich aqueous absorbent solution outlet below a purified gas outlet and an acid gas removal solvent rich aqueous solution inlet;

a stripping vessel comprising in order from top to bottom, an overhead vapor outlet, a recycled reflux inlet, a rich aqueous absorbent solution inlet and a lean aqueous absorbent solution outlet, wherein said rich aqueous absorbent solution inlet is in fluid communication with said rich aqueous absorbent solution outlet and said lean aqueous absorbent solution outlet is in fluid communication with said acid gas removal solvent rich aqueous solution inlet;

a heat exchanger comprising an overhead vapor stream inlet and a two phase stream outlet on one side and a coolant stream inlet and a coolant stream outlet on the other side wherein said overhead vapor stream inlet is in fluid communication with said overhead vapor stream outlet;

a separator vessel comprising in order from top to bottom, an acid gas rich stream outlet, a two phase stream inlet, and an alkanolamine rich aqueous solution outlet, wherein said two phase stream inlet is in fluid communication with said two phase stream outlet and said alkanolamine rich aqueous solution outlet is in fluid communication with said recycled reflux inlet; and

a resin bed comprising said anion exchange resin, a resin bed inlet, and a resin bed outlet, wherein said resin bed inlet is in fluid communication with said alkanolamine rich aqueous solution outlet, and said resin bed outlet is in fluid communication with said alkanolamine rich aqueous solution inlet.

13. An alkanolamine processing apparatus adapted to perform the process of claim 1, said apparatus comprising:

an absorber vessel comprising a sour gas mixture inlet and a rich aqueous absorbent solution outlet below a purified gas outlet and an alkanolamine rich aqueous solution inlet;

a stripping vessel comprising in order from top to bottom, an overhead vapor outlet, a recycled reflux inlet, a rich aqueous absorbent solution inlet and a lean aqueous absorbent solution outlet, wherein said rich aqueous absorbent solution inlet is in fluid communication with said rich aqueous absorbent solution outlet and said lean aqueous absorbent solution outlet is in fluid communication with said alkanolamine rich aqueous solution inlet;

a separator vessel comprising in order from top to bottom, an acid gas rich stream outlet, a rich reflux gas inlet, and an alkanolamine rich aqueous solution outlet, wherein said rich reflux gas inlet is in fluid communication with said rich reflux gas outlet and said alkanolamine rich aqueous solution outlet is in fluid communication with said recycled reflux inlet; and

a resin bed comprising said anion exchange resin, a resin bed inlet, and a resin bed outlet, wherein said resin bed inlet is in fluid communication with said alkanolamine rich aqueous solution outlet, and said resin bed outlet is in fluid communication with said alkanolamine rich aqueous solution inlet.

a heat exchanger comprising an overhead vapor stream inlet and a two phase stream outlet on one side and a coolant stream inlet and a coolant stream outlet on the other side wherein said overhead vapor stream inlet is in fluid communication with said overhead vapor stream outlet;

a separator vessel comprising in order from top to bottom, an acid gas rich stream outlet, a two phase stream inlet, and an alkanolamine rich aqueous solution outlet, wherein said two phase stream inlet is in fluid communication with said two phase stream outlet; and

a resin bed comprising said anion exchange resin, a resin bed inlet, and a resin bed outlet, wherein said resin bed inlet is in fluid communication with said alkanolamine rich aqueous solution outlet, and said resin bed outlet is in fluid communication with said recycled reflux inlet.