Adsorptive xenon recovery process from a gas or liquid stream at cryogenic temperature

Patent metadata

Field	Value
Publication number	US-11650010-B2
Application number	US-201816961402-A
Country	US
Kind code	B2
Filing date	Dec 12, 2018
Priority date	Jan 11, 2018
Publication date	May 16, 2023
Grant date	May 16, 2023

Abstract

The present invention relates to an adsorption process for xenon recovery from a cryogenic liquid or gas stream wherein a bed of adsorbent is contacted with a xenon-containing liquid or gas stream selectively adsorbing the xenon from said stream. The adsorption bed is operated to at least near full breakthrough with xenon to enable a deep rejection of other stream components, prior to regeneration using the temperature swing method. After the stripping step, the xenon adsorbent bed is drained to clear out the liquid residue left in the nonselective void space and the xenon molecules in those void spaces is recycled upstream to the ASU distillation column for increasing xenon recovery. The xenon adsorbent bed is optionally purged with oxygen, followed by purging with gaseous argon at cryogenic temperature (≤160 K) to displace the oxygen co-adsorbed on the AgX adsorbent due to higher selectivity of argon over oxygen on the AgX adsorbent. By the end of this step, the xenon adsorbent bed is filled with argon and xenon. Then the entire adsorbent bed is heated indirectly without utilizing any of the purge gas for direct heating. Operating the adsorption bed to near full breakthrough with xenon and displacing the adsorbed oxygen and other residues with argon, prior to regeneration, along with indirect heating of the bed, enables production of a high purity product ≥40 vol % xenon from the adsorption bed and further enables safely heating without any purge gas and ease for downstream product collection, even in cases where hydrocarbons are co-present in the feed stream.

First claim

We claim:

1. An adsorption process for the recovery of xenon from a liquid or gas cryogenic feed stream comprising xenon and at least one other adsorbable component which comprises:
i. feeding the feed stream at cryogenic temperatures into the inlet of an adsorption vessel containing an adsorbent bed loaded with at least one adsorbent selective for xenon, wherein said adsorbent bed has an inlet and an outlet,
ii. maintaining the feed to said adsorbent bed until the xenon product concentration at the outlet of said bed is greater than or equal to 90% of the xenon feed concentration at the inlet to said adsorbent bed,
iii. ending the feed to the adsorption bed,
iv. draining said bed if the feed stream is a liquid or depressurizing said bed if the feed stream is a gas,
v. purging the adsorbent bed with a purge gas at a temperature effective to desorb any oxygen co-adsorbed on the adsorbent in said adsorbent bed and to remove said at least one other adsorbable component from the non-selective void spaces of the bed,
vi. increasing the temperature of said adsorbent bed to a temperature effective to desorb substantially all xenon from the adsorbent in said adsorbent bed, followed by purging the heated adsorbent bed to sweep out any remaining xenon held on the adsorbent and/or left in the void space of the vessel,
vii. recovering the xenon product desorbed from said adsorbent bed,
viii. cooling said adsorbent bed to cryogenic temperatures, and repeating steps i.-viii. in a cyclic manner.

2. The process of claim 1 wherein said purge gas is selected from argon, helium, or krypton or any combination thereof.

3. The process of claim 1 wherein the temperature of the bed is increased by
i. heating the bed directly with an embedded heating device inside the adsorbent bed,
ii. heating the bed by applying heated product xenon to purge the adsorbent bed for regeneration, or
iii. heating the bed with an indirect heating method.

4. The process of claim 3 wherein the adsorbent vessel is jacketed and an indirect heating method is utilized.

5. The process of claim 1 wherein vacuum is provided in step vi to assist in recovering the xenon desorbed from the adsorbent, wherein said vacuum is generated by a sealed vacuum generating device at <760 torr.

6. The process of claim 5 wherein said vacuum is at least ≤100 torr.

7. The process of claim 1 wherein said at least one other adsorbable component in said cryogenic feed stream comprises hydrocarbon, krypton or combinations thereof.

8. The process of claim 7 wherein said hydrocarbon is methane, ethane, ethylene, propane or combinations thereof.

9. The process of claim 1 wherein said feed stream comprises from about 1-2000 ppm xenon, 10-20000 ppm Kr, 500-8000 ppm hydrocarbons, 0-200 ppm N 2 O, 0-100 ppm CO 2 , 0-1200 ppm of Ar, ppm amounts of N 2 and other atmospheric gases, balance O 2 .

10. The process of claim 1 wherein said adsorbent bed of step i. is pre-cooled to a temperature of ≤120K.

11. The process of claim 1 wherein said purge step is continued until the hydrocarbons level at the outlet of said adsorbent bed is ≤50 ppm.

12. The process of claim 11 wherein said purge step is continued until the hydrocarbons level at the outlet of said adsorbent bed is ≤10 ppm.

13. The process of claim 1 wherein in step iv., the temperature of the adsorbent bed is increased from cryogenic temperatures to at least 250 K in order to recover a xenon product at a concentration of ≥20% xenon.

14. The process of claim 1 wherein in step viii., the adsorbent bed is cooled to a temperature of ≤120 K.

15. The process of claim 1 wherein said adsorbent bed is maintained on feed until the xenon product concentration at the outlet of said bed is greater than or equal to 95% of the xenon feed concentration at the inlet to said adsorbent bed.

16. The process of claim 1 comprising at least two adsorbent beds wherein said adsorbent beds are out of phase with each other and wherein said two adsorbent beds are connected in series for a portion of the feed step.

17. The process of claim 1 wherein said xenon selective adsorbent is selected from a silver ion exchanged zeolite of type X, wherein the ion exchange level is at least 80% Ag on an equivalents basis, or a silver ion exchanged zeolite of type X, wherein the ion exchange level is at least 90% Ag on an equivalents basis.

18. The process of claim 1 wherein the recovered xenon product from step vii is at least 10% by volume concentration.

19. The process of claim 18 wherein the recovered xenon product is at least 40% by volume concentration.

20. The process of claim 18 wherein the released xenon product is ≥90% by volume concentration.

21. The process of claim 1 wherein prior to purging the bed according to step v., liquid or gaseous oxygen is introduced to the bed in order to purge any remaining hydrocarbon left in said bed.

22. The process of claim 2 wherein the adsorbent bed is purged with a gaseous purge gas at a cryogenic temperature of ≤160 K.

23. The process of claim 1 wherein the purge sweep of step vi is not commenced until the adsorbent bed temperature reaches ≥400 K.

24. The process of claim 1 wherein the purge gas of step vi is selected from helium, krypton, oxygen, nitrogen, dry air or a combination of two or more of said purge gases.

Assignees

• Praxair Technology Inc

Inventors

• Du Hai
• Dray Michael J
• Meagher James P
• Falta Steven R

Classifications

• F25J3/04751

  Producing pure krypton and/or xenon recovered from a crude krypton/xenon mixture · CPC title

• C01B23/0078 Primary

  Temperature swing adsorption · CPC title

• F25J2205/68

  Cooling the adsorption vessel · CPC title

• B01J20/3483

  by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling · CPC title

• B01D53/0423

  Beds in columns · CPC title