Process for removing carbon dioxide containing acidic gases from gaseous mixtures using a basic salt activated with a hindered amine

• US 4,112,050 A
• Filed: 12/19/1977
• Issued: 09/05/1978
• Est. Priority Date: 06/26/1975
• Status: Expired due to Term

• Current Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Original Assignee: Exxon Research and Engineering Company (Exxon Mobil Corporation)
• Inventors: Sartori, Guido, Leder, Frederic
• Primary Examiner(s): Thomas, Earl C.
• Application Number:
  US05/862,196
• Time in Patent Office: 260 Days
• Field of Search: 423/220, 423/223, 423/226-229, 423/232, 423/233, 423/234, 423/236, 423/243, 252/189, 260/584 R
• US Class Current: 423/223
• CPC Class Codes: B01D 53/1475 Removing carbon dioxide
• CPC Class Codes: B01D 53/1493 Selection of liquid materials for use as absorbents
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

Carbon dioxide containing acidic gases are removed from a normally gaseous mixture by a process comprising contacting the normally gaseous mixture with an aqueous solution comprising (a) a basic alkali metal salt or hydroxide and (b) an activator for said basic salt or alkali metal salt or hydroxide comprising at least one sterically hindered amine.

Claims

1. In a process for removing CO₂ from gaseous feeds containing CO₂, which comprises:

(1) contacting said gaseous feeds with an aqueous scrubbing solution comprising;

(a) an alkaline material comprising a basic alkali metal salt or alkali metal hydroxide, (b) an activator for said basic alkali metal salt or alkali metal hydroxide comprising at least one amine activator for said alkaline material, and (c) water, and

(2) regenerating said aqueous scrubbing solution at conditions whereby CO₂ is desorbed from said aqueous scrubbing solution, the improvement which comprises providing at least one sterically hindered amine as at least one of the amine activators, and operating said process at conditions whereby the difference between the moles of carbon dioxide absorbed at the end of step (1) (absorption step) and the moles of carbon dioxide absorbed at the end of step (2) (desorption step) would be greater at the thermodynamic equilibrium (as determined from the vapor-liquid equilibrium isotherm of the reaction mixture) than in an aqueous scrubbing process wherein diethanolamine is the only amine activator utilized under similar conditions of gaseous feed composition, scrubbing solution composition, temperatures and pressures.

2. The process of claim 1 wherein the alkaline material is selected from the group consisting of potassium or sodium borate, carbonate, hydroxide, phosphate and bicarbonate.

3. The process of claim 2 wherein the alkaline material is potassium carbonate.

4. The process of claim 1 wherein the alkaline material is present in said aqueous scrubbing solution in an amount ranging from about 10 to about 40 weight percent, based on the total weight of the scrubbing solution.

5. The process of claim 1 wherein the sterically hindered amine activator is defined as a compound containing at least one secondary amino group attached to either a secondary or tertiary carbon atom or a compound containing a primary amino group attached to a tertiary carbon atom.

6. The process of claim 5 wherein the sterically hindered amine activator is selected from the group consisting of aminoethers, aminoalcohols, di- and triamines.

7. The process of claim 5 wherein the sterically hindered amine activator is selected from the group consisting of:

N₁ -tert. butyl-1,4-pentanediamine;

N₂ -isopropyl-4-methyl-2,4-pentanediamine;

N₁ -isopropyl-2-methyl-1,2-butanediamine;

2-ethylamino-2-methyl-4-aminopentane;

N-tert. pentyl-1,4-butanediamine;

N-tert. butyl-1,5-pentanediamine;

N₂ -isopropyl-2-methyl-1,2-propanediamine;

N-sec. butyl-1,3-propanediamine;

N₁ -dimethyl-1,2-diamino-2-methylbutane;

N-t-butyl-ethylenediamine;

N-t-butyl-1,3-propanediamine;

2-methylamino-2-methyl-4-amino pentane;

N₁ -t-butyl-2-methyl-1,2-propanediamine;

N₁ -butyl-2-methyl-1,2-propanediamine;

N-sec. butyl-2-methyl-1,3-propanediamine;

N₁ -propyl-2-methyl-1,2-propanediamine;

N₁ -sec. butyl-2-methyl-1,2-propanediamine;

N-t-butyl-1,4-butanediamine;

N₂ -ethyl-1,2-hexanediamine;

1-methyl-1-phenyl ethylenediamine;

2-benzyl-1,2-propanediamine;

1-phenyl-1(2-amino-ethylamino)-propane;

N₁ -methyl-2-phenyl-1,2-butanediamine;

N₁ -cyclohexyl-1,2-propanediamine;

1-amino-1-(2-amino-isopropyl)-cyclohexane;

1-methylamino-1-aminomethyl-cyclopentane;

1-amino-1-aminomethylcycloheptane;

N-isopropyl-1,2-diaminocyclohexane;

N₂ -cyclohexyl-1,2-butanediamine;

N₂ -cyclohexyl-1,2-propanediamine;

N-cycloheptyl-ethylenediamine;

N₁ -cyclohexyl-2-methyl-1,2-propanediamine;

1-(2-aminoisopropyl)-2-amino-3-methylcyclopentane;

N-isopropyl-1,4-diaminocyclohexane;

N₁ -cyclohexyl-N₂ -methyl-ethylenediamine;

N-cyclohexyl-ethylenediamine;

N₁ -cyclohexyl-N₂ -ethyl-ethylenediamine;

N₁ -cyclohexyl-N₂ -methyl-1,2-propanediamine;

N-cyclohexyl-1,3-propanediamine;

1,8-p-menthanediamine;

1-amino-1-aminomethylcyclohexane;

1,3-diamino-1-methylcyclohexane;

N₂ -cyclohexyl-2-methyl-1,2-propanediamine;

2,4-diamino-2-methylpentane;

3,5-diamino-3-methylheptane;

N₁ -tert. butyl-N₂ -isopropyl-1,3-propanediamine;

N₁ -tert. butyl-N₂ -sec. butyl-ethylenediamine;

N₁ -tert. butyl-N₂ -isopropyl-1,3-propanediamine;

N₁ -tert. butyl-N₂ -butyl-ethylenediamine;

N₁ -tert. butyl-N₂ -isobutyl-ethylenediamine;

N₁,n₂ -diisopropyl-1,2-propanediamine;

N₁ -tert. butyl-N₂ -isopropyl-ethylenediamine;

N₁ -sec. butyl-N₂ -isopropyl-ethylenediamine;

N₁ -tert. pentyl-N₂ -isopropyl-ethylenediamine;

N₁,n₃ -diethyl-1,3-butanediamine;

N₁ -tert. butyl-N₂ -methyl-ethylenediamine;

N₁ -(2-pentyl)-N₂ -methyl-ethylenediamine;

N₁ -tert. butyl-N₂ -methyl-1,4-butanediamine;

N₁ -tert. butyl-N₂ -ethyl-1,3-propanediamine;

N₁ -tert. butyl-N₂,N₂ -diethyl ethylenediamine

N₁ -cyclohexyl-dipropylene triamine;

N₁,n₃, 2-pentamethyl-1,2,3-triaminopropane;

N₁ -isopropyl-N₂ -(3-aminopropyl)-2-methyl-1,2-propanediamine;

9. The process of claim 5 wherein the sterically hindered amine activator is selected from the group consisting of:

N-cyclohexyl-1,3-propane-diamine;

1,8-p-menthane-diamine;

1,7-bis-sec-butyl-diethylenetriamine;

2,2,5,5-tetramethyl diethylenetriamine;

3-amino-3-methyl-1-butanol;

2-amino-2-methyl-1-propanol;

N₁ -isopropyl-2-methyl-1,2-propane diamine;

N₁ -(1,1-dimethyl-2-hydroxyethyl)-2-methyl-1,2-propanediamine; and

N₁ -isopropyl-N₂ -(3-aminopropyl)-2-methyl-1,2-propanediamine.

10. The process of claim 5 wherein said sterically hindered amine is N-cyclohexyl-1,3-propanediamine.

11. The process of claim 1 wherein said scrubbing solution additionally includes an additive selected from the antifoaming agents, antioxidants, corrosion inhibitors and mixtures thereof.

12. The process of claim 1 wherein the scrubbing solution which has been desorbed in reused to absorb a feed containing CO₂.

14. The process of claim 12 wherein said contacting takes place at a temperature ranging from about 35 to about 150°

C. and at a pressure ranging from about 100 to 500 psig for a period of from 0.1 to about 60 minutes.

15. The process of claim 12 wherein said scrubbing solution is regenerated at a temperature ranging from about 100°

to 160°

C. and at a pressure ranging from about 2 to about 75 psia. is reduced to a capacity of less than 25%.

17. The process of claim 15 wherein said aqueous scrubbing solution additionally includes an additive selected from the group consisting of antifoaming agents, antioxidants, corrosion inhibitors and mixtures thereof.

18. The process of claim 12 wherein said aqueous scrubbing solution includes a sterically nonhindered amine.

20. The process of claim 18 wherein said alkaline material is selected from the group consisting of potassium or sodium borate, carbonate, hydroxide, phosphate and bicarbonate.

22. The process of claim 18 wherein the sterically hindered amine activator is defined as a compound containing at least one secondary amino group attached to either a secondary or tertiary carbon atom or a compound containing a primary amino group attached to a tertiary carbon atom.

24. The process of claim 22 wherein the sterically hindered amine activator is selected from the group consisting of:

N-cyclohexyl-1,3-propanediamine;

1,8-p-menthanediamine;

1,7-bis-sec-butyl-diethylenetriamine;

2,2,5,5-tetramethyl diethylenetriamine;

3-amino-3-methyl-1-butanol;

2-amino-2-methyl-1-propanol;

N₁ -isopropyl-2-methyl-1,2-propanediamine;

N₁ -(1,1-dimethyl-2-hydroxyethyl)-2-methyl-1,2-propanediamine; and

N₁ -isopropyl-N₂ -(3-aminopropyl)-2-methyl-1,2-propanediamine.

25. The process of claim 22 wherein the sterically hindered amine activator is N-cyclohexyl-1,3-propanediamine.

26. The process of claim 18 wherein the process is operated at conditions whereby the difference between the moles of carbon dioxide absorbed at the end of step (1)(absorption step) and the moles of carbon dioxide absorbed at the end of step (2)(desorption step) would be at least 15% greater at the thermodynamic equilibrium (as determined from the vapor liquid equilibrium isotherm of the scrubbing solution) than in an aqueous scrubbing process wherein diethanolamine or 1,6-hexanediamine is the only amine activator utilized under similar conditions of gaseous feed composition, scrubbing solution composition, temperatures and pressures.

27. The process of claim 18 wherein said scrubbing solution additionally includes an additive selected from the group consisting of antifoaming agents, antioxidants, corrosion inhibitors and mixtures thereof.

28. The process of claim 18 wherein the scrubbing solution from step (2) which has been desorbed in reused to absorb a feed containing carbon dioxide.

29. The process of claim 18 wherein said contacting in step (1)(absorption step) takes place at a temperature ranging from about 25°

to about 200°

C. and at a pressure ranging from about 5 to about 2000 psig for a period ranging from 0.1 to 60 minutes.

30. The process of claim 18 wherein the scrubbing solution is regenerated at a temperature ranging from 25°

to 200°

C. and at a pressure ranging from about 16 to about 100 psia.

31. The process of claim 1 wherein said gaseous feed contains CO₂ in combination with H₂ S.

32. The process of claim 6 wherein said sterically hindered amine is selected from the group consisting of monoprimary aliphatic diamines;

arylaliphatic diamines in which the amino groups are separated by up to 5 or more than 6 carbon atoms;

cycloaliphatic diamines;

biprimary aliphatic diamines in which the nitrogen atoms are separated by up to 5 or more than 6 carbon atoms;

disecondary aliphatic diamines;

secondary-tertiary diamines;

cycloaliphatic triamines;

aliphatic triamines containing at most one primary amino group;

biprimary or triprimary aliphatic triamines in which any two vicinal groups are separated by up to 5 or more than 6 carbon atoms;

cycloaliphatic diaminoalcohols;

diaminoalcohols-containing at most one primary amino group;

sterically hindered primary monoaminoalcohols;

sterically hindered amino-hydroxyalkylethers;

2-substituted piperidines;

piperazine derivatives;

azacyclo alkanes; and

aminoacids.

33. The process of claim 6 wherein said sterically hindered amine is a cycloaliphatic diamine.

35. The process of claim 33 wherein said scrubbing solution additionally includes an additive selected from the group consisting of antifoaming agents, antioxidants, corrosion inhibitors and mixtures thereof.

36. The process of claim 33 wherein the scrubbing solution from step (2) which has been desorbed is reused to absorb a feed containing carbon dioxide.

37. The process of claim 33 wherein said contacting in step (1) (absorption step) takes place at a temperature ranging from about 25°

to about 200°

C. and at a pressure ranging from about 5 to about 2000 psig for a period ranging from 0.1 to 60 minutes.

38. The process of claim 33 wherein the scrubbing solution is regenerated at a temperature ranging from 25 to 200°

C. and at a pressure ranging from about 16 to about 100 psia.

39. The process of claim 33 wherein the gaseous feed contains CO₂ and H₂ S.

8. 2-dimethyl-diethylenetriamine;

N₁ -tert. butyl-1,2,3-triaminopropane;

2,2,5,5-tetramethyldiethylenetriamine;

1-amino-1-aminomethyl-2-hydroxymethylcyclohexane;

N-hydroxyethyl-1,2-diaminocyclohexane;

N-cyclohexyl-1,3-diamino-2-propanol;

N-(2-hydroxycyclohexyl)-1,3-propanediamine;

N-isopropanol-1,2-diaminocyclohexane;

N-(2-hydroxybutyl)-1,4-diaminocyclohexane;

N₁ (1-hydroxy-2-butyl)-2-methyl-1,2-propanediamine;

N(1-hydroxy-2-methyl-2-butyl)-1,3-propanediamine;

N₁ (1,1-dimethyl-2-hydroxyethyl)-2-methyl-1,2-propanediamine;

N₃ -isobutyl-2-methyl-2,3-diamino-1-propanol;

N(3-hydroxy-2-butyl)-2,3-diaminobutane;

N₁ -hydroxyethyl-2-methyl-1,2-propanediamine;

2,N₃,N₃ -trimethyl-2,3-diamino-1-propanol;

N₁,2-dimethyl-N₁ -hydroxyethyl-1,2-propanediamine;

N(1,1-dimethyl-2-hydroxyethyl)-1,3-propanediamine;

N-tert. butyl-1,3-diamino-2-propanol;

3-amino-3-methyl-2-pentanol;

1-hydroxymethyl-cyclopentylamine;

2,3-dimethyl-3-amino-1-butanol;

2-amino-2-ethyl-1-butanol;

1-methyl-2-hydroxycyclopentylamine;

2-amino-2-methyl-3-pentanol;

2,4-dimethyl-2-amino cyclohexanol;

1-hydroxyethyl cyclohexylamine;

1-hydroxymethyl-3-methyl cyclohexylamine;

2-hydroxymethyl-1-methyl-cyclohexylamine;

2-amino-2-methyl-1-propanol;

2-amino-2-methyl-1-butanol;

3-amino-3-methyl-1-butanol;

3-amino-3-methyl-2-butanol;

2-amino-2,3-dimethyl-3-butanol;

2-amino-2,3-dimethyl-1-butanol;

1-hydroxymethylcyclohexylamine;

2(2-amino-2-methylpropoxy)-ethanol;

2-piperidine methanol;

2-piperidine ethanol;

2-(1-hydroxyethyl)-piperidine;

5-hydroxy-2-methyl piperidine;

2-methyl-3-hydroxy piperidine;

2,6-dimethyl-3-hydroxy piperidine;

2,5-dimethyl-4-hydroxy piperidine;

2-tert. butylamino-methyl-1,4-dimethyl-piperazine;

1-tert. butylamino-3,6-dimethyl-3,6-diaza-cycloheptane; and

N-cyclohexyl-beta-alanine.

13. A process for removing CO₂ from gaseous feeds containing CO₂ which comprises contacting said feed with an aqueous solution comprising (a) potassium carbonate in an amount ranging from about 10 to about 40 weight percent, (b) at least about 2 weight percent of an amine activator comprising a sterically hindered amine selected from the group consisting of:

N-cyclohexyl-1,3-propanediamine;

1,8-menthanediamine;

1,7-bis-sec-butyl-diethylenetriamine;

2,2,5,5-tetramethyl diethylenetriamine;

3-amino-3-methyl-1-butanol;

2-amino-2-methyl-1-propanol, N₁ -isopropyl-2-methyl-1,2-propanediamine;

N₁ (1,1-dimethyl-2-hydroxyethyl)-2-methyl-1,2-propanediamine; and

N₁ -isopropyl-N₂ -(3-aminopropyl)-2-methyl-1,2-propanediamine.

16. A process for removing CO₂ from gaseous feeds containing CO₂ which comprises contacting said feed with an aqueous solution comprising:

(a) potassium carbonate in an amount ranging from about 10 to about 40 weight percent, (b) at least 2 weight percent of an amine activator comprising N-cyclohexyl-1,3-propanediamine and (c) water.

19. In a process for removing carbon dioxide from gaseous feeds containing carbon dioxide which comprises, in sequential steps:

(1) contacting said feed with an aqueous scrubbing solution comprising;

(a) an alkaline material comprising a basic alkali metal salt or alkali metal hydroxide in an amount ranging from about 10 to about 40 weight percent, (b) at least 2 weight percent of an amine activator, and (c) water, at conditions whereby said carbon dioxide is absorbed in said scrubbing solution, and

(2) regenerating said scrubbing solution at conditions whereby carbon dioxide is desorbed from said scrubbing solution, the improvement which comprises providing a sterically hindered amine as an amine activator, and operating said process at conditions whereby the difference between the moles of carbon dioxide absorbed at the end of step (1)(absorption step) and the moles of carbon dioxide absorbed at the end of step (2)(desorption step) would be greater at the thermodynamic equilibrium (as determined from the vapor-liquid equilibrium isotherm of the reaction mixture) than in an aqueous scrubbing process wherein diethanolamine or 1,6-hexanediamine is the only amine activator utilized under similar conditions of gaseous feed composition, scrubbing solution composition, temperatures and pressures.

21. The process of claim 19 wherein said alkaline material is potassium carbonate.

23. The process of claim 21 wherein the sterically hindered amine activator is selected from the group consisting of aminoethers, aminoalcohols, di- and triamines.

34. In a process for removing CO₂ from gaseous feeds containing CO₂ which comprises, in sequential steps:

(1) contacting said feed with an aqueous scrubbing solution comprising (a) from about 20 to about 35 weight percent of potassium carbonate, (b) from about 2 to about 20 weight percent of an amine activator, and (c) water, at conditions whereby said CO₂ is absorbed in said scrubbing solution;

(2) regenerating said scrubbing solution at conditions whereby carbon dioxide is desorbed from said scrubbing solution, the improvement which comprises providing an asymmetrical sterically hindered cycloaliphatic diamine as an amine activator wherein the sterically hindered cycloaliphatic diamine is defined as a compound having a boiling point of at least 80°

C. and containing at least one secondary amino group attached to a secondary carbon atom.