Gas Purification by Adsorption of Hydrogen Sulfide

• US 20100011955A1
• Filed: 07/17/2008
• Published: 01/21/2010
• Est. Priority Date: 07/17/2008
• Status: Active Grant

• Current Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Quinn, Robert, Sorensen, Erin Marie, Hufton, Jeffrey Raymond, Golden, Timothy Christopher, Maliszewskyj, Robin Joyce, Weist, Edward Landis JR.
• Granted Patent: US 7,909,913 B2
• Time in Patent Office: Days
• US Class Current: 95/136
• CPC Class Codes: B01D 2253/106 Silica or silicates
• CPC Class Codes: B01D 2253/112 Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
• CPC Class Codes: B01D 2253/202 Polymeric adsorbents
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2259/40056 Gases other than recycled product or process gas
• CPC Class Codes: B01D 2259/41 using plural beds of the same adsorbent in series
• CPC Class Codes: B01D 2259/4145 arranged in series
• CPC Class Codes: B01D 53/047 Pressure swing adsorption
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: C01B 2203/0205 containing a reforming step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/042 Purification by adsorption on solids
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0485 the impurity being a sulfur compound
• CPC Class Codes: C01B 2203/84 Energy production
• CPC Class Codes: C01B 3/32 by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
• CPC Class Codes: C01B 3/48 : followed by reaction of water vapour with carbon monoxide
• CPC Class Codes: C01B 3/56 : by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

Hydrogen sulfide is removed from a hydrogen rich gas stream using adsorbents having a low loss of carbon dioxide adsorption capacity upon sulfur loading including high purity silica gels, titania or highly cross-linked, non-chemically reactive resins. The adsorbents may be used to adsorb both carbon dioxide and hydrogen sulfide, or may be used as a guard bed upstream of a separate carbon dioxide adsorbent.

Claims

1. A process for the removal of hydrogen sulfide from a feed gas containing at least hydrogen sulfide as an impurity, said process comprising contacting the feed gas with an adsorbent for hydrogen sulfide, and adsorbing hydrogen sulfide from said feed gas to produce a hydrogen sulfide depleted feed gas, said adsorbent for hydrogen sulfide having a sulfur deposition rate of less than 0.04 wt % S per day H₂S exposure when continuously exposed to a 1% H₂S dry gas at 20°

C.

4. A process as claimed in claim 1, wherein the adsorbent for hydrogen sulfide comprises or consists of a silica gel having an SiO₂ content of at least 99%.

5. A process as claimed in claim 1, wherein the adsorbent for hydrogen sulfide comprises or consists of titania.

6. A process as claimed in claim 1, wherein the feed gas contains at least 0.2 vol % hydrogen sulfide.

7. A process as claimed in claim 1, wherein the feed gas contains at least 50 vol % hydrogen.

8. A process as claimed in claim 1, wherein the feed gas contains at least 80 vol % of hydrogen and carbon dioxide.

9. A process as claimed in claim 1, wherein the feed gas contains hydrogen as a desired component and at least hydrogen sulfide and carbon dioxide as impurities and purified hydrogen is obtained as an end product by contacting the feed gas with a single homogeneous adsorbent consisting of an adsorbent material with a sulfur deposition rate of less than 0.04 wt % S per day H₂S exposure.

10. A process as claimed in claim 1, wherein said feed gas is synthesis gas produced by steam reforming of a carbon source which is solid or liquid at STP, followed by a water gas shift reaction.

11. A process as claimed in claim 1, wherein said feed gas contains at least both hydrogen sulfide and carbon dioxide as impurities, and said hydrogen sulfide depleted feed gas is passed from said adsorbent for hydrogen sulfide to contact an adsorbent for carbon dioxide, and carbon dioxide is adsorbed from said hydrogen sulfide depleted feed gas by said adsorbent for carbon dioxide to form a hydrogen sulfide and carbon dioxide depleted feed gas.

12. A process as claimed in claim 11, wherein said adsorbent for hydrogen sulfide is contained in a first column and said adsorbent for carbon dioxide is contained in a second column connected for gas flow to said first column.

13. A process as claimed in claim 1, wherein said adsorbent for hydrogen sulfide is regenerated at intervals by desorption of hydrogen sulfide therefrom.

14. A process as claimed in claim 13, wherein said adsorbent for hydrogen sulfide is regenerated at first intervals by desorption of hydrogen sulfide therefrom and wherein said adsorbent for carbon dioxide is regenerated at second intervals by desorption of carbon dioxide therefrom.

2. A process for the removal of hydrogen sulfide from a feed gas containing at least hydrogen sulfide as an impurity, said process comprising contacting the feed gas with an adsorbent for hydrogen sulfide, and adsorbing hydrogen sulfide from said feed gas to produce a hydrogen sulfide depleted feed gas, said adsorbent for hydrogen sulfide having an loss of adsorption capacity for carbon dioxide upon accumulation of sulfur on the adsorbent produced by continuous seven day exposure to a 1% H₂S dry gas at 20°

C. of less than 2.0% capacity loss/wt % S loading.

3. A process for the removal of hydrogen sulfide from a feed gas containing at least hydrogen sulfide as an impurity, said process comprising contacting the feed gas with an adsorbent for hydrogen sulfide, and adsorbing hydrogen sulfide from said feed gas to produce a hydrogen sulfide depleted feed gas, wherein the adsorbent for hydrogen sulfide comprises or consists of a cross-linked resin having no ionic groups and no hydrogen sulfide reactive functional groups.

15. Apparatus for use in purifying hydrogen by removal of impurities from a hydrogen feed gas, said apparatus comprising a flow path for said feed gas containing an adsorbent for hydrogen sulfide, said flow path having a feed direction, and said adsorbent for hydrogen sulfide a sulfur deposition rate of less than 0.04 wt % S per day H₂S exposure when continuously exposed to a 1% H₂S dry gas at 20°

C., and an adsorbent for carbon dioxide in said flow path downstream in said feed direction from said adsorbent for hydrogen sulfide.

16. Apparatus as claimed in claim 15, further comprising a gasifier for steam reforming of a carbon source and a water gas shift reactor for producing said hydrogen feed gas connected in said flow path and located upstream with respect to said feed direction from said adsorbent for hydrogen sulfide.

17. Apparatus as claimed in claim 16, further comprising an air separation unit (ASU) for producing separate flows of nitrogen and of oxygen respectively, said flow of oxygen being directed to said gasifier.

18. Apparatus as claimed in claim 17, further comprising a power generating combustor connected to receive hydrogen purified by said adsorbent for hydrogen sulfide and said adsorbent for carbon dioxide and further connected to receive said flow of nitrogen to act as a diluent for combustion of said purified hydrogen in said combustor.

19. Apparatus as claimed in claim 17, wherein said flow of nitrogen is connected to flow counter current to said feed direction as a regeneration gas flow through said adsorbent for hydrogen sulfide and further comprising a flow controller for selecting between feed gas flow through said adsorbent for hydrogen sulfide and regeneration gas flow therethrough.

20. A process for the purification of a hydrogen rich feed gas containing at least carbon dioxide and hydrogen sulfide as impurities, comprising contacting the feed gas with a first adsorbent contained in a first adsorbent vessel and thereby removing hydrogen sulfide from said feed gas to form a hydrogen sulfide depleted feed gas and contacting said hydrogen sulfide depleted feed gas with at least a second adsorbent contained in a second adsorbent vessel to remove at least carbon dioxide from said hydrogen sulfide depleted feed gas, and at intervals regenerating said first adsorbent and at different intervals regenerating said second adsorbent, wherein said first adsorbent is silica gel, titania, or a cross-linked resin having no ionic groups and no hydrogen sulfide reactive functional groups.

21. Apparatus for use in purifying hydrogen by removal of impurities from a hydrogen feed gas, said apparatus comprising a flow path for said feed gas containing a first adsorbent in a first adsorbent vessel for adsorbing hydrogen sulfide, said flow path having a feed direction, a second adsorbent in a second adsorbent vessel for adsorbing at least carbon dioxide in said flow path downstream in said feed direction from said first adsorbent vessel, a source of at least one regeneration gas, a regeneration controller for at first intervals directing a regeneration gas from said source of regeneration gas to regenerate said first adsorbent, and for at second intervals directing a regeneration gas from said source of regeneration gas to regenerate said second adsorbent, wherein said first adsorbent is is silica gel, titania, or a cross-linked resin having no ionic groups and no hydrogen sulfide reactive functional groups.