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

• US 4,217,237 A
• Filed: 05/30/1978
• Issued: 08/12/1980
• 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): Padgett, Benjamin R.
• Assistant Examiner(s): Barr, J. L.
• Application Number:
  US05/910,861
• Time in Patent Office: 805 Days
• Field of Search: 252/189, 252/192, 252/190, 423/220, 423/223, 423/226-229, 423/232, 423/233, 423/236, 423/243, 260/564 R
• US Class Current: 252/192
• CPC Class Codes: B01D 53/1493 Selection of liquid materials for use as absorbents
• 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. A composition comprising an aqueous solution which comprises (1) 10 to about 40 weight percent of an alkaline material selected from the group consisting of a basic alkali metal salt or alkali metal hydroxide, and (2) at least 2 weight percent of at least one sterically hindered amine, wherein said sterically hindered amine is defined as containing at least one secondary amino group attached to either a secondary or tertiary carbon atom or a primary amine group attached to a tertiary carbon atom and selected from the group consisting of:

aminoethers, aminoalcohols, di- and triamines.

2. The composition of claim 1 wherein said alkaline material is potassium carbonate.

3. The composition of claim 2 wherein the potassium carbonate is present in an amount ranging from about 20 to about 30 weight percent.

4. The composition of claim 1 wherein the sterically hindered amine 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 composition of claim 1 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 amino 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-hydroxyalkyl ethers;

2-substituted piperidines;

piperazine derivatives; and

azacyclo alkanes.

10. The composition of claim 1 wherein said sterically hindered amine is a cycloaliphatic diamine.

11. The composition of claim 9 wherein said cycloaliphatic diamine is selected from the group consisting of:

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-methyl-cyclopentane;

N-isopropyl-1,4-diamino-cyclohexane;

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; and

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

12. The composition of claim 9 wherein said cycloaliphatic diamine is N-cyclohexyl-1,3-propanediamine.

13. The composition of claims 1, 4, 8, 9, 10 or 11 which additionally includes an additive selected from the group consisting of antifoaming agents, antioxidants, corrosion inhibitors and mixtures thereof.

5. 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-hydroxy methyl-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.

6. A composition comprising an aqueous solution which comprises:

(1) 20 to about 30 weight percent potassium carbonate and (2) at least 2 weight percent of at least one sterically hindered amine 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-tetramethyldiethylenetriamine;

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.

8. The composition of claim 6 which additionally includes an additive selected from the group consisting of antifoaming agents, antioxidants, corrosion inhibitors and mixtures thereof.

7. A composition comprising an aqueous solution which comprises:

(a) 20 to about 30 weight percent potassium carbonate and (b) at least 2 weight percent of N-cyclohexyl-1,3-propanediamine.