Process for the removal of carbon dioxide from 3,4-epoxy-1-butene process recycle streams

• US 6,270,739 B1
• Filed: 06/16/2000
• Issued: 08/07/2001
• Est. Priority Date: 06/16/2000
• Status: Expired due to Fees

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Chemical Company
• Inventors: Stavinoha, Jerome Leonard Jr., Barnicki, Scott Donald, Kline, Robert Sterling, Hartley, Gary Wayne, Monnier, John Robert
• Primary Examiner(s): Lambkin, Deborah C.
• Application Number:
  US09/596,246
• Time in Patent Office: 417 Days
• Field of Search: 423/229, 423/228
• US Class Current: 423/229
• CPC Class Codes: C07D 301/32 Separation; Purification

Abstract

Disclosed is a process for the efficient removal of carbon dioxide from a gas recycle system generated in an epoxidation process wherein 1,3-butadiene is selectively oxidized to 3,4-epoxy-1-butene. Carbon dioxide at low partial pressure is absorbed into an alkanolamine solution from a low pressure recycle gas stream containing high levels of oxygen. Also disclosed is a means for reclaiming the alkanolamine from a solution of a carbon dioxide-alkanolamine salt or adduct formed in the carbon dioxide removal process.

Claims

1. Process for the removal of carbon dioxide from a butadiene epoxidation effluent recycle gas stream comprising about 3 to 15 mole percent butadiene, about 8 to 25 mole percent oxygen, about 55 to 88 mole percent inert diluent gas and about 0.5 to 10 mole percent carbon dioxide which comprises feeding the gas stream to an absorption vessel wherein the gas stream is intimately contacted with a liquid solution of an alkanolamine at a pressure of about 0.1 to 1 MPa and a temperature of about 20 to 65°

C. to obtain;

(1) a vapor effluent comprising butadiene, oxygen, inert diluent gas and about 0.005 to 0.5 mole percent carbon dioxide from the upper section of the absorption vessel; and

(2) a liquid effluent comprising the alkanolamine solution and carbon dioxide-alkanolamine adduct from the lower section of the absorption vessel;

wherein butadiene is 1,3-butadiene.

2. Process according to claim 1 wherein the liquid solution of alkanolamine comprises a solution of at least one primary or secondary alkanolamine containing up to about 10 carbon atoms and having a boiling point of less than about 250°

C. in water, an alkanol, a glycol or a mixture of any two or more thereof.

3. Process according to claim 2 wherein said alkanolamine is selected from the group consisting of monoethanolamine;

2-amino-2-methyl-1-propanol, 3-amino-3-methyl-2-pentanol, 2,3-dimethyl-3-amino-1-butanol, 2-amino-2-ethyl-1-butanol, 2-amino-2-methyl-3-pentanol, 2-amino-2-methyl-1-butanol, 2-amino-2-methyl-1-pentanol, 3-amino-3-methyl-1-butanol, 3-amino-3-methyl-2-butanol, 2-amino-2,3-dimethyl-1-butanol, 1-amino-3-buten-2-ol, 2-amino-3-buten-1-ol, 1-aminobutan-2-ol, 2-amino-butan-1-ol, diethanolamine, 2-(ethylamino)-ethanol, 2-(methylamino)-ethanol, 2-(propylamino)ethanol, 2-(isopropylamino)ethanol, 2-(butylamino)ethanol, 1-(ethylamino)ethanol, 1-(methylamino)-ethanol, 1-(propylamino)ethanol, 1-(isopropylamino)ethanol, and 1-(butylamino)-ethanol, 1-methylamino-3-buten-2-ol, 2-methylamino-3-buten-1-ol, 1-ethylamino-3-buten-2-ol, 2-ethylamino-3-buten-1-ol, 1-propylamino-3-buten-2-ol, 2-propylamino-3-buten- 1-ol, 1-butylamino-3-buten-2-ol, 2-butylamino-3-buten- 1-ol.

4. Process for the removal of carbon dioxide from a butadiene epoxidation effluent recycle gas stream about 3 to 15 mole percent butadiene, about 8 to 25 mole percent oxygen, about 55 to 88 mole percent inert diluent gas and about 0.5 to 10 mole percent carbon dioxide which comprises the steps of:

(I) feeding the gas stream to a first absorption vessel wherein the gas stream is intimately contacted with a liquid solution of an alkanolamine at a pressure of about 0.1 to 1 MPa (14.5 to 145 psia) and a temperature of about 20 to 65°

C. to obtain;

(i) a vapor effluent comprising butadiene, oxygen, inert diluent gas, about 0.005 to 0.5 mole percent carbon dioxide from the upper section of the absorption vessel, and about 20 to 2000 ppmv alkanolamine; and

(ii) a liquid effluent comprising the alkanolamine solution and carbon dioxide-alkanolamine adduct from the lower section of the first absorption vessel; and

(II) feeding vapor effluent (i) to a second absorption vessel wherein the gas stream is intimately contacted with a solvent at a pressure of about 0.1 to 1.1 MPa and a temperature of about 20 to 65°

C. to obtain;

(iii) a vapor effluent comprising butadiene, oxygen, inert diluent gas, about 0.005 to 0.5 mole percent carbon dioxide from the upper section of the absorption vessel, and less than 10 ppmv alkanolamine; and

(iv) a liquid effluent comprising solvent and absorbed alkanolamine from the lower section of the absorption vessel;

wherein butadiene is 1,3-butadiene.

5. Process according to claim 4 wherein the liquid solution of alkanolamine comprises a solution of at least one primary or secondary alkanolamine containing up to about 10 carbon atoms and having a boiling point of less than about 250°

C. in water, an alkanol, a glycol or a mixture of any two or more thereof and the solvent of step (II) comprises water, an alkanol, a glycol or a mixture of any two or more thereof.

6. Process according to claim 4 wherein the liquid solution of alkanolamine comprises a solution of at least one primary or secondary alkanolamine in water, an alkanol, a glycol or a mixture of any two or more thereof wherein the alkanolamine is selected from the group consisting of monoethanolamine, 2-amino-2-methyl-1-propanol, 3-amino-3-methyl-2-pentanol, 2,3-dimethyl-3-amino-1-butanol, 2-amino-2-ethyl-1-butanol, 2-amino-2-methyl-3-pentanol, 2-amino-2-methyl-1-butanol, 2-amino-2-methyl-1-pentanol, 3-amino-3-methyl-1-butanol, 3-amino-3-methyl-2-butanol, 2-amino-2,3-dimethyl-1-butanol, 1-amino-3-buten-2-ol, 2-amino-3-buten-1-ol, 1-aminobutan-2-ol, 2-amino-butan-1-ol, diethanolamine, 2-(ethylamino)-ethanol, 2-(methylamino)ethanol, 2-(propylamino)ethanol, 2-(isopropyl-amino)ethanol;

2-(butylamino)-ethanol, 1-(ethylamino)ethanol, 1-(methylamino)-ethanol, 1-(propylamino)ethanol, 1-(isopropylamino)-ethanol, and 1-(butylamino)-ethanol, 1-methylamino-3-buten-2-ol, 2-methylamino-3-buten-1-ol, 1-ethylamino-3-buten-2-ol, 2-ethylamino-3-buten-1-ol, 1-propylamino-3-buten-2-ol, 2-propylamino-3-buten-1-ol, 1-butylamino-3-buten-2-ol, and 2-butylamino-3-buten-1-ol;

the solvent of step (II) comprises water, an alkanol, a glycol or a mixture of any two or more thereof;

the concentration of CO2 of vapor effluent (i) is about 0.005 to 0.1 mole percent;

the concentration of alkanolamine in vapor effluent (i) is less than 5.0 ppmv; and

vapor effluent (iii) is recycled to an epoxidation process wherein butadiene is contacted with an oxygen-containing gas in the presence of a silver catalyst.

7. Process according to claim 6 wherein the alkanolamine is monoethanolamine.

8. Process according to claim 6 wherein the alkanolamine is 2-amino-2-methyl-1-propanol.

9. Process according to claim 6 wherein the alkanolamine is 2-(ethylamino)-ethanol.

10. Process according to claim 6 wherein the alkanolamine is 1-amino-3-buten-2-ol or 2-amino-3-buten-1-ol.

11. Process according to claim 6 wherein the liquid solution of alkanolamine comprises a solution of at least one primary or secondary alkanolamine in a solvent is selected from the group consisting of butanol, pentanol, hexanol, ethylene glycol, propylene glycol, butylene glycol, 1-butene-3,4-diol, and 2-butene-1,4-diol.

12. Process according to claim 6 wherein the liquid solution of alkanolamine comprises a solution of at least one primary or secondary alkanolamine in water.

13. Process according to claim 4 wherein the concentration range of alkanolamine or mixture of alkanolamines is 7 to 65 weight percent alkanolamine.

14. The process of claim 4 wherein the alkanolamine is monoethanolamine or a mixture of monoethanolamine and 1-(2-hydroxyethylamino)-3-buten-2-ol and the concentration of the alkanolamine is 10 to 45 weight percent.

15. Process according to claim 14 wherein the concentration of alkanolamine is 12 to 35 weight percent in water.

16. Process according to claim 4 wherein the alkanolamine is 2-amino-2-methyl-1-propanol and the solution concentration is 15 to 40 weight percent in water.

17. Process according to claim 4 wherein the alkanolamine solution flow rate is set to give a carbon dioxide:

alkanolamine molar ratio within said carbon dioxide absorption zone of 0.25 to 1.0 moles carbon dioxide per mole of alkanolamine.

18. Process according to claim 4 wherein the alkanolamine solution flow rate is set to give a carbon dioxide:

alkanolamine molar ratio of 0.25 to 0.65 moles/mole, and wherein said alkanolamine is monoethanolamine or a mixture of monoethanolamine and 1-(2-hydroxyethylamino)-3-buten-2-ol.

19. Process according to claim 4 wherein the alkanolamine solution flow rate is set to give a carbon dioxide:

alkanolamine molar ratio of 0.35 to 0.45 moles/mole, and wherein said alkanolamine is monoethanolamine or a mixture of monoethanolamine and 1-(2-hydroxyethylamino)-3-buten-2-ol.

20. Process according to claim 4 wherein the alkanolamine solution flow rate is set to give a carbon dioxide:

alkanolamine molar ratio of 0.35 to 0.7 moles/mole, and wherein said alkanolamine is 2-amino-2-methyl-1-propanol.

21. Process according to claim 4 wherein the pressures of the first and second absorption vessels are within the range of about 0.2-0.9 MPa.

22. Process for the removal of carbon dioxide from a butadiene epoxidation effluent recycle gas stream comprising about 3 to 15 mole percent butadiene, about 8 to 25 mole percent oxygen, about 55 to 88 mole percent inert diluent gas and about 0.5 to 10 mole percent carbon dioxide which comprises the steps of:

(I) feeding the gas stream to an absorption vessel wherein the gas stream is intimately contacted with a liquid solution of an alkanolamine at a pressure of about 0.1 to 1 MPa and a temperature of about 20 to 65°

C. to obtain;

(i) a vapor effluent comprising butadiene, oxygen, inert diluent gas and about 0.005 to 0.5 mole percent carbon dioxide from the upper section of the absorption vessel; and

(ii) a liquid effluent comprising the alkanolamine solution and carbon dioxide-alkanolamine adduct from the lower section of the absorption vessel; and

(II) subjecting liquid effluent (ii) to an alkanolamine reclamation process which comprises feeding liquid effluent (II) to the lower section of a column wherein the liquid is heated at a temperature of about 90 to 165°

C. to obtain;

(iii) a vapor effluent comprising carbon dioxide from the upper section of

(iv) a liquid effluent comprising the alkanolamine solution substantially free of carbon dioxide-alkanolamine adduct from the lower section of the column;

wherein butadiene is 1,3-butadiene.

23. Process according to claim 22 wherein the liquid solution of alkanolamine comprises a solution of at least one primary or secondary alkanolamine in water, an alkanol, a glycol or a mixture of any two or more thereof wherein the alkanolamine is selected from the group consisting of monoethanolamine, 2-amino-2-methyl-1-propanol, 3-amino-3-methyl-2-pentanol, 2,3-dimethyl-3-amino-1-butanol, 2-amino-2-ethyl-1-butanol, 2-amino-2-methyl-3-pentanol, 2-amino-2-methyl-1-butanol, 2-amino-2-methyl-1-pentanol, 3-amino-3-methyl-1-butanol, 3-amino-3-methyl-2-butanol, 2-amino-2,3-dimethyl-1-butanol, 1-amino-3-buten-2-ol, 2-amino-3-buten-1-ol, 1-aminobutan-2-ol, 2-amino-butan-1-ol, diethanolamine, 2-(ethylamino)-ethanol, 2-(methylamino)ethanol, 2-(propylamino)ethanol, 2-(isopropyl-amino)ethanol;

2-(butylamino)-ethanol, 1-(ethylamino)ethanol, 1-(methylamino)-ethanol, 1-(propylamino)ethanol, 1-(isopropylamino)-ethanol, and 1-(butylamino)-ethanol, 1-methylamino-3-buten-2-ol, 2-methylamino-3-buten-1-ol, 1-ethylamino-3-buten-2-ol, 2-ethylamino-3-buten-1-ol, 1-propylamino-3-buten-2-ol, 2-propylamino-3-buten-1-ol, 1-butylamino-3-buten-2-ol, and 2-butylamino-3-buten-1-ol.

24. Process according to claim 22 wherein step (II) comprises subjecting liquid effluent (ii) to an alkanolamine reclamation process which comprises heating liquid effluent (ii) at a temperature of about 65 to 90°

C. and at a pressure of 0.1 to 0.35 Mpa to remove dissolved gases from the liquid and then feeding the liquid to the lower section of a column wherein the liquid is heated at a temperature of about 90 to 165°

C.