PROCESS AND REACTOR SYSTEM FOR PRODUCING AMMONIA USING IONIC LIQUIDS

US 20120027661A1
Filed: 01/27/2011
Published: 02/02/2012
Est. Priority Date: 01/28/2010
Status: Active Grant

First Claim

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1. A process for producing ammonia comprising the steps of:

(a) combining nitrogen and hydrogen in the presence of a catalyst under conditions of temperature and pressure whereby ammonia is produced; and

(b) contacting the ammonia produced with at least one ionic liquid whereby at least a portion of the ammonia is absorbed by an ionic liquid.

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Abstract

A process and a reactor system for producing ammonia is described. The ammonia produced, such as by the Haber process, is absorbed into an ionic liquid. The removal of ammonia shifts the reaction equilibrium toward the production of ammonia, resulting in higher yields of ammonia.

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17 Claims

1. A process for producing ammonia comprising the steps of:
- (a) combining nitrogen and hydrogen in the presence of a catalyst under conditions of temperature and pressure whereby ammonia is produced; and
  
  (b) contacting the ammonia produced with at least one ionic liquid whereby at least a portion of the ammonia is absorbed by an ionic liquid.
- View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11)
- - 2. The process according to claim 1 wherein an ionic liquid comprises a cation selected from the group consisting of cations represented by the structures of the following formulae:
  - 3. The process according to claim 1 further comprising a step of recovering the ammonia absorbed by an ionic liquid.
  - 4. The process according to claim 1 wherein an ionic liquid comprises an anion selected from one or more members of the group consisting of [CH₃CO₂]⁻
    - , [HSO₄]⁻, [CH₃OSO₃]⁻,[C₂H₅OSO₃]⁻, [AlCl₄]⁻, [CO₃]²⁻, [HCO₃]⁻, [NO₂]⁻, [NO₃]⁻, [SO₄]²⁻, [PO₃]³⁻, [HPO₃]²⁻, [H₂PO₃]¹⁻, [PO₄]³⁻, [HPO₄]²⁻, [H₂PO₄]⁻, [HSO₃]⁻, [CuCl₂]⁻, Cl⁻, Br⁻, I⁻, SCN⁻, carborates optionally substituted with alkyl or substituted alkyl;
      
      carboranes optionally substituted with alkylamine, substituted alkylamine, alkyl or substituted alkyl; and
      
      a fluorinated anion.
  - 5. The process according to claim 1 wherein an ionic liquid comprises a cation selected from one or more members of the group consisting of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, phosphonium, ammonium, benzyltrimethylammonium, choline, dimethylimidazolium, guanidinium, phosphonium choline, tetramethylammonium, and tetramethylphosphonium cations.
  - 6. The process according to claim 1 wherein an ionic liquid comprises an anion selected from one or more members of the group consisting of aminoacetate, ascorbate, benzoate, catecholate, citrate, dimethylphosphate, formate, fumarate, gallate, glycolate, glyoxylate, iminodiacetate, isobutyrate, kojate, lactate, levulinate, oxalate, pivalate, propionate, pyruvate, salicylate, succinamate, succinate, tiglate, tetrafluoroborate, tetrafluoroethanesulfonate, tropolonate, [CH₃CO₂]⁻
    - , [HSO₄]⁻, [CH₃OSO₃]⁻, [C₂H₅OSO₃]⁻, [AlCl₄]⁻, [CO₃]²⁻, [HCO₃]⁻, [NO₂]⁻, [NO₃]⁻, [SO₄]²⁻, [PO₃]³⁻, [HPO₄]²⁻, [H₂PO₄]⁻, [HSO₃]⁻, [CuCl₂]⁻, Cl⁻, Br⁻, I⁻, SCN⁻, [BF₄]⁻, [PF₆]⁻, [SbF₆]⁻, [CF₃SO₃]⁻, [HCF₂CF₂SO₃]⁻, [CF₃HFCCF₂SO₃]⁻, [HCClFCF₂SO₃]⁻,[(CF₃SO₂)₂N]⁻, [(CF₃CF₂SO₂)₂N]⁻, [(CF₃SO₂)₃C]⁻, [CF₃CO₂]⁻, [CF₃OCFHCF₂SO₃]⁻, [CF₃CF₂OCFHCF₂SO₃]⁻, [CF₃CFHOCF₂CF₂SO₃]⁻, [CF₂HCF₂OCF₂CF₂SO₃]⁻, [CF₂ICF₂OCF₂CF₂SO₃], [CF₃CF₂OCF₂CF₂SO₃]⁻, [(CF₂HCF₂SO₂)₂N]₋, [(CF₃CFHCF₂SO₂)₂N]⁻, F⁻, and anions represented by the structure of the following formula;
  - 7. The process according to claim 1 wherein an ionic liquid is selected from the group consisting of1-butyl-3-methylimidazolium hexafluorophosphate,1-butyl-3-methylimidazolium tetrafluoroborate,1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-hexyl-3-methylimidazolium chloride,1-ethyl-3-methylimidazolium acetate,1-ethyl-3-methylimidazolium ethylsulfate,1-ethyl-3-methylimidazolium thiocyanate, andN,N-dimethylethanolammonium ethanoate.
  - 8. The process according to claim 1 wherein the temperature in step (a) is in the range of about 300°
    - C. to about 550°
      
      C.
  - 9. The process according to claim 1 wherein the pressure in step (a) is in the range of about 8 MPa to about 40 MPa.
  - 10. The process according to claim 1 wherein ammonia and an ionic liquid are contacted in step (b) at a temperature in the range of about 20°
    - C. to about 200°
      
      C.
  - 11. The process according to claim 1 wherein ammonia and an ionic liquid are contacted in step (b) at a pressure in the range of about 100 kPa to about 40 MPa.

12. A reactor system comprising:
- (a) a first stage wherein nitrogen and hydrogen are combined in the presence of a catalyst under conditions of temperature and pressure whereby ammonia is produced; and
  
  (b) a second stage wherein the ammonia produced is contacted with at least one ionic liquid whereby at least a portion of the ammonia is absorbed by the ionic liquid.
- View Dependent Claims (13, 14, 15, 16, 17)
- - 13. The reactor system according to claim 12 wherein an ionic liquid comprises a cation selected from the group consisting of cations represented by the structures of the following formulae:
  - 14. The reactor system according to claim 12 wherein an ionic liquid comprises an anion selected from one or more members of the group consisting of [CH₃CO₂]⁻
    - , [HSO₄]⁻, [CH₃OSO₃]⁻, [C₂H₅OSO₃]⁻, [AlCl₄]⁻, [CO₃]²⁻, [HCO₃]⁻, [NO₂]⁻, [NO₃]⁻, [SO₄]²⁻, [PO₃]³⁻, [HPO₃]²⁻, [H₂PO₃]¹⁻, [PO₄]³⁻, [HPO₄]²⁻, [H₂PO₄]⁻, [HSO₃]⁻, [CuCl₂]⁻, Cl⁻, Br⁻, I⁻, SCN⁻, carborates optionally substituted with alkyl or substituted alkyl;
      
      carboranes optionally substituted with alkylamine, substituted alkylamine, alkyl or substituted alkyl; and
      
      a fluorinated anion.
  - 15. The reactor system according to claim 12 wherein an ionic liquid comprises a cation selected from one or more members of the group consisting of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, phosphonium, ammonium, benzyltrimethylammonium, choline, dimethylimidazolium, guanidinium, phosphonium choline, tetramethylammonium, and tetramethylphosphonium cations.
  - 16. The reactor system according to claim 12 wherein an ionic liquid comprises an anion selected from one or more members of the group consisting of aminoacetate, ascorbate, benzoate, catecholate, citrate, dimethylphosphate, formate, fumarate, gallate, glycolate, glyoxylate, iminodiacetate, isobutyrate, kojate, lactate, levulinate, oxalate, pivalate, propionate, pyruvate, salicylate, succinamate, succinate, tiglate, tetrafluoroborate, tetrafluoroethanesulfonate, tropolonate, [CH₃CO₂]⁻
    - , [HSO₄]⁻, [CH₃OSO₃]⁻, [C₂H₅OSO₃]⁻, [AlCl₄]⁻, [CO₃]²⁻, [HCO₃]⁻, [NO₂]⁻, [NO₃]⁻, [SO₄]²⁻, [PO₃]³⁻, [HPO₄]²⁻, [H₂PO₄]⁻, [HSO₃]⁻, [CuCl₂]⁻, Cl⁻, Br⁻, I⁻, SCN⁻, [BF₄]⁻, [PF₆]⁻, [SbF₆]⁻, [CF₃SO₃]⁻, [HCF₂CF₂SO₃]⁻, [CF₃HFCCF₂SO₃]⁻, [HCClFCF₂SO₃]⁻, [(CF₃SO₂)₂N]⁻, [(CF₃CF₂SO₂)₂N]⁻, [(CF₃SO₂)₃C]⁻, [CF₃CO₂]⁻, [CF₃OCFHCF₂SO₃]⁻, [CF₃CF₂OCFHCF₂SO₃]⁻, [CF₃CFHOCF₂CF₂SO₃]⁻, [CF₂HCF₂OCF₂CF₂SO₃]⁻, [CF₂ICF₂OCF₂CF₂SO₃], [CF₃CF₂OCF₂CF₂SO₃]⁻, [(CF₂HCF₂SO₂)₂N]₋, [(CF₃CFHCF₂SO₂)₂N]⁻, F⁻, and anions represented by the structure of the following formula;
  - 17. The reactor system according to claim 12 wherein an ionic liquid is selected from the group consisting of1-butyl-3-methylimidazolium hexafluorophosphate,1-butyl-3-methylimidazolium tetrafluoroborate,1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-hexyl-3-methylimidazolium chloride,1-ethyl-3-methylimidazolium acetate,1-ethyl-3-methylimidazolium ethylsulfate,1-ethyl-3-methylimidazolium thiocyanate, andN,N-dimethylethanolammonium ethanoate.

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Current Assignee
E. I. du Pont de Nemours and Company (Corteva, Inc.)
Original Assignee
E. I. du Pont de Nemours and Company (Corteva, Inc.)
Inventors
Shiflett, Mark Brandon, Yokozeki, Akimichi

Granted Patent

US 8,808,659 B2
Time in Patent Office

Days
Field of Search
US Class Current

423/359
CPC Class Codes

C01C 1/0464 by absorption in liquids, e...

Y02P 20/52 using catalysts, e.g. selec...

PROCESS AND REACTOR SYSTEM FOR PRODUCING AMMONIA USING IONIC LIQUIDS

First Claim

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Abstract

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17 Claims

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PROCESS AND REACTOR SYSTEM FOR PRODUCING AMMONIA USING IONIC LIQUIDS

First Claim

1 Assignment

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Abstract

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17 Claims

Specification

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