Novel sorbents and purification and bulk separation of gas streams

• US 20080264254A1
• Filed: 04/09/2008
• Published: 10/30/2008
• Est. Priority Date: 04/11/2007
• Status: Abandoned Application

• Current Assignee: Penn State Research Foundation, Pennsylvania State University
• Original Assignee: Penn State Research Foundation
• Inventors: Wang, Xiaoxing, Ma, Xiaoliang, Song, Chunshan
• Application Number:
  US12/081,036
• Publication Number:
  US 20080264254A1
• Time in Patent Office: Days
• US Class Current: 95/116
• CPC Class Codes: B01D 2253/202 Polymeric adsorbents
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2257/2045 Hydrochloric acid
• CPC Class Codes: B01D 2257/2047 Hydrofluoric acid
• CPC Class Codes: B01D 2257/2064 Chlorine
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/306 Organic sulfur compounds, e.g. mercaptans
• CPC Class Codes: B01D 2257/308 Carbonoxysulfide COS
• CPC Class Codes: B01D 2257/402 Dinitrogen oxide
• CPC Class Codes: B01D 2257/404 Nitrogen oxides other than dinitrogen oxide
• CPC Class Codes: B01D 2257/406 Ammonia
• CPC Class Codes: B01D 2257/408 Cyanides, e.g. hydrogen cyanide (HCH)
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/70 Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
• CPC Class Codes: B01D 2258/0208 from fuel cells
• CPC Class Codes: B01D 2258/05 Biogas
• CPC Class Codes: B01D 2258/06 Polluted air
• CPC Class Codes: B01D 2259/40009 using sensors or gas analysers
• CPC Class Codes: B01D 2259/40088 by heating
• CPC Class Codes: B01D 2259/402 : using two beds
• CPC Class Codes: B01D 53/02 : by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/06 : with moving adsorbents, e.g. rotating beds B01D53/025 takes precedence
• CPC Class Codes: B01J 20/103 : comprising silica
• CPC Class Codes: B01J 20/16 : Alumino-silicates B01J20/12 takes precedence
• CPC Class Codes: B01J 20/20 : comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: B01J 20/22 : comprising organic material
• CPC Class Codes: B01J 20/26 : Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/28057 : Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28069 : Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/3092 : Packing of a container, e.g. packing a cartridge or column of chromatography columns B01D15/206
• CPC Class Codes: B01J 20/3204 : Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3242 : Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
• CPC Class Codes: B01J 20/3272 : Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3425 : of sorbents or filter aids comprising organic materials
• CPC Class Codes: B01J 20/3458 : in the gas phase
• CPC Class Codes: B01J 20/3483 : by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
• CPC Class Codes: B01J 2220/42 : Materials comprising a mixture of inorganic materials materials coated or impregnated on a carrier B01J20/32
• CPC Class Codes: C12M 47/18 : Gas cleaning, e.g. scrubbers; Separation of different gases separating dispersed particles from gases or vapours B01D45/00; separation of gases or vapours B01D53/00; gas washing apparatus for laboratory uses B01L5/04
• CPC Class Codes: Y02C 20/10 : of nitrous oxide (N2O)
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02E 50/30 : Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02P 20/59 : Biological synthesis; Biological purification

Abstract

Porous-material-supported polymer sorbents and process for removal of undesirable gases such as H₂S, COS, CO₂, N₂O, NO, NO₂, SO₂, SO₃, HCl, HF, HCN, NH₃, H₂O, C₂H₅OH, CH₃OH, HCHO, CHCl₃, CH₂Cl₂, CH₃Cl, CS₂, C₄H₄S, CH₃SH, and CH₃—S—CH₃ from various gas streams such as natural gas, coal/biomass gasification gas, biogas, landfill gas, coal mine gas, ammonia syngas, H₂ and oxo-syngas, Fe ore reduction gas, reformate gas, refinery process gases, indoor air, fuel cell anode fuel gas and cathode air are disclosed. The sorbents have numerous advantages such as high breakthrough capacity, high sorption/desorption rates, little or no corrosive effect and are easily regenerated. The sorbents may be prepared by loading H₂S—, COS—, CO₂—, N₂O, NO—, NO₂—, SO₂—, SO₃—, HCl—, HF—, HCN—, NH₃—, H₂O—, C₂H₅OH—, CH₃OH—, HCHO—, CHCl₃—, CH₂Cl₂—, CH₃Cl—, CS₂—, C₄H₄S—, CH₃SH—, CH₃—S—CH₃-philic polymer(s) or mixtures thereof, as well as any one or more of H₂S—, COS—, CO₂—, N₂O, NO—, NO₂—, SO₂—, SO₃—, HCl—, HF—, HCN—, NH₃—, H₂O—, C₂H₅OH—, CH₃OH—, HCHO—, CHCl₃—, CH₂Cl₂—, CH₃Cl—, CS₂—, C₄H₄S—, CH₃SH—, CH₃—S—CH₃-philic compound(s) or mixtures thereof on to porous materials such as mesoporous, microporous or macroporous materials. The sorbents may be employed in processes such as one-stage and multi-stage processes to remove and recover H₂S, COS, CO₂, N₂O, NO, NO₂, SO₂, SO₃, HCl, HF, HCN, NH₃, H₂O, C₂H₅OH, CH₃OH, HCHO, CHCl₃, CH₂Cl₂, CH₃Cl, CS₂, C₄H₄S, CH₃SH and CH₃—S—CH₃ from gas streams by use of, such as, fixed-bed sorbers, fluidized-bed sorbers, moving-bed sorbers, and rotating-bed sorbers.

Claims

1. A two-stage process for separation of removal a plurality of impurities from a feed gas stream comprising,

contacting a feed gas stream having a plurality of impurities therein with a first sorbent during a first stage to remove a first one of the plurality of impurities from the feed gas stream to generate a first effluent stream having a lower amount of the first impurity than in the feed gas stream,

contacting the first effluent with a second sorbent in a second stage where the second sorbent may be the same or different from the first sorbent to remove a second one of the plurality of impurities from the first effluent to produce a second effluent having a lower amount of the second one of the plurality of impurities than in the first effluent stream,

wherein in the first stage the first sorbent is maintained at about 10°

C. to about 130°

C. and the gas feed stream is contacted with the first sorbent at a first flow rate GHSV of about 200 h<sup>−

1</sup> to about 200,000 h<sup>−

1</sup> and

wherein in the second stage the second sorbent is maintained at about −

10°

C. to about 80°

C. and the first effluent is contacted with the second sorbent at a second flow rate GHSV of about 200 h<sup>−

1</sup> about 2×

10⁵ h<sup>−

l</sup>, and

wherein the first and second impurities are selected from the group consisting of H₂S, COS, CO₂, NO₂, NO, N₂O, SO₂, SO₃, HCl, HF, HCN, NH₃, H₂O, C₂H₅OH, CH₃OH, HCHO, CHCl₃, CH₂Cl₂, CH₃Cl—

, CS₂, C₄H₄S, CH₃SH, CH₃—

S—

CH₃ and mixtures thereof and

wherein the feed gas stream is selected from the group consisting of natural gas, coal/biomass gasification gas, biogas, landfill gas, coal mine gas, ammonia syngas, H₂ and oxo-syngas, Fe ore reduction gas, reformate gas, refinery process gases, indoor air, fuel cell anode fuel gas and cathode air, and

wherein each of the sorbents in the first and second stages comprises at least one of a polymer, compound or mixtures of polymer and compound on a porous support material where the polymer is selected from the group consisting of H₂S—

, COS—

CO₂—

, NO₂—

, NO—

, N₂O—

, SO₂—

, SO₃—

, HCl—

, HF—

, HCN—

, NH₃—

, H₂O—

, C₂H₅OH—

, CH₃OH—

, HCHO—

, CHCl₃—

, CH₂Cl₂—

, CH₃Cl—

, CS₂—

, C₄H₄S—

, CH₃SH— and

CH₃—

S—

CH-phillic polymers or mixtures thereof and the compound is selected from the group consisting of H₂S—

, COS—

CO₂—

, NO₂—

, NO—

, N₂O—

, SO₂—

, SO₃—

, HCl—

, HF—

, HCN—

, NH₃—

, H₂O—

, C₂H₅OH—

, CH₃OH—

, HCHO—

, CHCl₃—

, CH₂Cl₂—

, CH₃Cl—

, CS₂—

, C₄H₄S—

, CH₃SH—

, CH₃—

S—

CH-phillic compounds or mixtures thereof,

wherein the polymeric and organic compound are each selected from the group consisting of polyethylenimine, polyethyleneglycolamine, polyethanolamine, polyisopropanolamine, polyalkylene glycol dimethyl ether, polyethylene glycol, n-methylpyrrolidinone, n-formylmorpholine, N-acetylmorpholine, propylene carbonate, sulfolane and mixtures thereof and

wherein the porous support material is selected from the group consisting of alumino-silicates, activated carbon, carbon sieves, silica gel, fumed silica, silica and mixtures thereof.

2. The process of claim 1 wherein the gas feed stream is coal/biomass gasification gas, the polymer is polyethylenimine, the support is an alumino-silicate, stage 1 is at a temperature of 75°

C. the first one of the impurities is CO₂, stage 2 is at a temperature of 22°

C. and the second one of the impurities is H₂S.

3. The process of claim 2 wherein the GHSV of the feed gas is 486 h⁻

1 and the GHSV of the first effluent is 486 h<sup>−

1</sup>.

4. The process of claim 1 wherein the gas feed stream is biogas, the polymer is polyethylenimine, the support is fumed silica, stage 1 is at a temperature of 75°

C. the first one of the impurities is CO₂, stage 2 is at a temperature of 25°

C. and the second one of the impurities is H₂S.

5. The process of claim 4 wherein the GHSV of the feed gas is 1263 h⁻

1 and the GHSV of the first effluent is 3797 h<sup>−

1</sup>

6. The process of claim 1 wherein the feed gas stream is landfill gas, the polymer is polyethylenimine, the support is fumed silica, stage 1 is at a temperature of 75°

C. the first one of the impurities is CO₂, stage 2 is at a temperature of 25°

C. and the second one of the impurities is H₂S.

15. The process of claim 2 wherein the feed gas is natural gas.

16. The process of claim 2 wherein the feed gas is biogas.

17. The process of claim 2 wherein the feed gas is landfill gas.

18. The process of claim 2 wherein the feed gas is coal mine gas.

19. The process of claim 2 wherein the feed gas is reformate gas.

20. The process of claim 2 wherein the feed gas is hydrogen.

21. The process of claim 2 wherein the feed gas is indoor air.

7. A sorbent for sorbing one or more impurities from a gas stream, the sorbent comprising a first component for sorbing one or more impurities from the gas stream, and a second component comprising a porous support material for supporting the first component, wherein the first component is selected from the group consisting of polyethyleneglycolamine (PEGA), polyethanolamine (PEA), polyisopropanolamine (PIPA), polyalkylene glycol dimethyl ether (PAGDE), polyethylene glycol (PEG), n-methylpyrrolidinone (NMP), n-formylmorpholine (NFM), N-acetylmorpholine (NAM), propylene carbonate, sulfolane, or mixtures thereof, and the porous support material is selected from the group consisting of alumino-silicates, activated carbon, carbon sieve, silica gel, fumed silica, silica or mixtures thereof.

9. The sorbent of claim 7 wherein the first component is polyethylene glycol and the porous support is alumino-silicate.

8. A sorbent for sorbing one or more impurities from a gas stream, the sorbent comprising a first component for sorbing one or more impurities from the gas stream, and a second component comprising a porous support material for supporting the first component, wherein the first component is selected from the group consisting of polyethylenimine (PEI), polyethyleneglycolamine (PEGA), polyethanolamine (PEA), polyisopropanolamine (PIPA), polyalkylene glycol dimethyl ether (PAGDE), polyethylene glycol (PEG), n-methyl pyrrolidinone (NMP), n-formylmorpholine (NFM), N-acetylmorpholine (NAM), propylene carbonate, sulfolane, modified polymers listed above or mixtures thereof, and the porous support material is selected from the group consisting of activated carbon, carbon sieve, silica gel, fumed silica, silica or mixtures thereof.

10. The sorbent of claim 8 wherein the first component is polyethylenimine and the porous support is fumed silica.

11. A sorbent for sorbing one or more impurities from a gas stream, the sorbent comprising a mixture of polyethylenimine polyethylene glycol on an alumino silicate.

12. A single stage process for separation of an impurity from a feed gas stream comprising,

contacting the feed gas stream having an impurity over a bed of a sorbent at a flow rate GHSV of about 200 h⁻

1 to about 200,000 h<sup>−

1</sup> at a temperature of about −

10°

C. to about 80°

C. to remove the impurity from the gas stream to produce an effluent that has a lower amount of the impurity than the feed gas stream,

wherein the impurity is selected from the group consisting of CO₂, H₂S, COS, NO₂, NO, N₂O, SO₂, SO₃, HCl, HF, HCN, NH₃, H₂O, C₂H₅OH, CH₃OH, HCHO, CHCl₃, CH₂Cl₂, CH₃C₁—

, CS₂, C₄H₄S, CH₃SH, CH₃—

S—

CH₃ and mixtures thereof and

the gas stream is selected from the group consisting of natural gas, coal/biomass gasification gas, biogas, landfill gas, coal mine gas, ammonia syngas, H₂ and oxo-syngas, Fe ore reduction gas, reformate gas, refinery process gases, indoor air, fuel cell anode fuel gas and cathode air, and wherein the sorbent comprises a first component for sorbing one or more impurities from the gas stream, and a second component comprising a porous support material for supporting the first component, wherein the first component is selected from the group consisting of polyethyleneglycolamine (PEGA), polyethanolamine (PEA), polyisopropanolamine (PIPA), polyalkylene glycol dimethyl ether (PAGDE), polyethylene glycol (PEG), n-methyl pyrrolidinone (NMP), n-formylmorpholine (NFM), N-acetylmorpholine (NAM), propylene carbonate, sulfolane, or mixtures thereof, and the porous support material is selected from the group consisting of alumino-silicates, activated carbon, carbon sieve, silica gel, fumed silica, silica or mixtures thereof.

13. The process of claim 12 wherein the feed gas is dry coal/biomass gasification gas that has H₂S impurity, the sorbent comprises polyethylenimine on alumino-silicate support, the temperature is 22°

C. and the GHSV of the feed gas over the sorbent is 674 h<sup>−

1</sup>.

14. The process of claim 12 wherein the feed gas is dry flue gas that has CO₂ impurity, the flow rate GHSV of the feed gas over the sorbent is 337 h⁻

1 and the temperature is 75°

C.