Epoxy-amine acid gas adsorption-desorption polymers and oligomers, processes for preparing same, and uses thereof

• US 8,557,027 B2
• Filed: 12/21/2011
• Issued: 10/15/2013
• Est. Priority Date: 12/22/2010
• Status: Expired due to Fees

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Peiffer, Dennis G., Calabro, David C., Li, Quanchang, Afeworki, Mobae, Cundy, Stephen M.
• Primary Examiner(s): LAWRENCE JR, FRANK M
• Application Number:
  US13/332,576
• Publication Number:
  US 20120160097A1
• Time in Patent Office: 664 Days
• Field of Search: 95/96, 95/97, 951/39, 951/48, 959/00, 961/08, 423/220, 423/228, 423/230, 502400-402, 502/439
• US Class Current: 95/139
• CPC Class Codes: B01D 2253/202 Polymeric adsorbents
• CPC Class Codes: B01D 2253/311 Porosity, e.g. pore volume
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• 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: B01J 20/262 obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G
• CPC Class Codes: B01J 20/267 Cross-linked polymers
• CPC Class Codes: B01J 20/28069 Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

This disclosure involves an adsorption-desorption material, e.g., crosslinked epoxy-amine material having an M_w from about 500 to about 1×10⁶, a total pore volume from about 0.2 cc/g to about 2.0 cc/g, and a CO₂ adsorption capacity of at least about 0.2 millimoles CO₂ per gram of crosslinked material, and/or linear epoxy-amine material having an M_w from about 160 to about 1×10⁶, a total pore volume from about 0.2 cc/g to about 2.0 cc/g, and a CO₂ adsorption capacity of at least about 0.2 millimoles CO₂ per gram of linear material. This disclosure also involves processes for preparing the crosslinked epoxy-amine materials and linear epoxy-amine materials, as well as selective removal of CO₂ and/or other acid gases from a gaseous stream using the epoxy-amine materials.

Claims

1. An acid gas adsorption-desorption material comprising a crosslinked epoxy-amine material having a weight average molecular weight of from about 500 to about 1×

10⁶, a total pore volume of from about 0.2 cubic centimeters per gram (cc/g) to about 2.0 cc/g, and an adsorption capacity of at least about 0.2 millimoles of CO₂ adsorbed per gram of adsorption-desorption material.

2. The acid gas adsorption-desorption material of claim 1 wherein said crosslinked epoxy-amine material is produced by reacting at least one epoxy functional compound, said at least one epoxy functional compound comprising a diepoxy functional compound, a triepoxy functional compound, a tetraepoxy functional compound, or mixtures thereof, with at least one amine, said at least one amine comprising a linear amine, a branched amine, a polyamine, or mixtures thereof, under conditions sufficient to produce said crosslinked epoxy-amine material.

3. The acid gas adsorption-desorption material of claim 2 wherein a monoepoxy functional compound is added to the reaction mixture.

4. The acid gas adsorption-desorption material of claim 2 wherein said at least one amine is comprised of a primary amine, a secondary amine, or mixtures thereof, and said crosslinked epoxy-amine material is comprised of a linear polyamine, a branched polyamine, or mixtures thereof.

5. The acid gas adsorption-desorption material of claim 2 wherein said at least one diepoxy functional compound is selected from the group consisting of:

diglycidyl hexadecyl ether, and 1,2-epoxy-3-phenoxypropane;

said at least one triepoxy functional compound is selected from the group consisting of;

triphenylolmethane triglycidyl ether, and trimethylolpropane triglycidyl ether;

said at least one tetraepoxy functional compound is selected from the group consisting of;

tetraphenylolethane glycidyl ether; and

mixtures thereof; and

said at least one amine is selected from the group consisting of;

propylenediamine, tetraethylenepentaamine, polyethyleneimines, and mixtures thereof.

6. The acid gas adsorption-desorption material of claim 3 wherein said monoepoxy functional compound is selected from the group consisting of:

tetraphenylolethane glycidyl ether, bisphenol A (2,3-dihydroxypropyl glycidyl ether), dodecyl glycidyl ether, tetradecyl glycidyl ether, tert-butyl glycidyl ether, and glycidyl 2,2,3,3,4,4,5,5-octafluoropentyl glycidyl ether.

7. The acid gas adsorption-desorption material of claim 1 wherein said crosslinked epoxy-amine material is DEO (diethyleneoxide)-polyethyleneimine.

8. The acid gas adsorption-desorption material of claim 1 wherein said crosslinked epoxy-amine material has a formula selected from:

{[CH₂CH₂NH]_x[CH₂CHOH(R)CHOHCH₂](NHCH₂CH₂)_y}_n

wherein x is an integer greater than about 1.0, y is an integer greater than about 0, and n is an integer equal to or greater than about 1.0, the CH₂CH₂NH and NHCH₂CH₂ groups can be linear or branched, and R is the same or different and is an alkyl or aryl moiety.

9. The acid gas adsorption-desorption material of claim 2 wherein said crosslinked epoxy-amine material is produced by adding a crosslinking agent selected from 2,4-bis(chloromethyl)-1,3,5-trimethylbenzene, 2,4,6-tris-(chloromethyl)-mesitylene, 1,3,5-tris-chloromethyl-2,4,6-trimethylbenzene, and mixtures thereof, to the reaction mixture of the epoxy functional compound and the amine.

10. The acid gas adsorption-desorption material of claim 1 wherein said crosslinked epoxy-amine material has an average particle diameter of from about 0.1 microns to about 500 microns.

11. An acid gas adsorption-desorption material comprising a linear epoxy-amine material having a weight average molecular weight of from about 140 to about 1×

10⁶, a total pore volume of from about 0.2 cubic centimeters per gram (cc/g) to about 2.0 cc/g, and an adsorption capacity of at least about 0.2 millimoles of CO₂ adsorbed per gram of adsorption-desorption material.

12. The acid gas adsorption-desorption material of claim 11 wherein said linear epoxy-amine material is produced by reacting at least one epoxy functional compound, said at least one epoxy functional compound comprising a diepoxy functional compound, a triepoxy functional compound, a tetraepoxy functional compound, or mixtures thereof, with at least one amine, said at least one amine comprising a linear amine, a branched amine, a polyamine, or mixtures thereof, under conditions sufficient to produce said linear epoxy-amine material.

13. The acid gas adsorption-desorption material of claim 12 wherein a monoepoxy functional compound is added to the reaction mixture.

14. The acid gas adsorption-desorption material of claim 12 wherein said at least one amine is comprised of a primary amine, a secondary amine, or mixtures thereof, and said linear epoxy-amine material is comprised of a linear polyamine, branched polyamine, or mixtures thereof.

15. The acid gas adsorption-desorption material of claim 12 wherein said at least one diepoxy functional compound is selected from the group consisting of:

diglycidyl hexadecyl ether, and 1,2-epoxy-3-phenoxypropane;

said at least one triepoxy functional compound is selected from the group consisting of;

triphenylolmethane triglycidyl ether, and trimethylolpropane triglycidyl ether;

said at least one tetraepoxy functional compound is selected from the group consisting of;

tetraphenylolethane glycidyl ether; and

mixtures thereof; and

said at least one amine is selected from the group consisting of;

propylenediamine, tetraethylenepentaamine, linear polyethyleneimines, and mixtures thereof.

16. The acid gas adsorption-desorption material of claim 13 wherein said monoepoxy functional compound is selected from the group consisting of:

tetraphenylolethane glycidyl ether, bisphenol A (2,3-dihydroxypropyl glycidyl ether), dodecyl glycidyl ether, tetradecyl glycidyl ether, tert-butyl glycidyl ether, and glycidyl 2,2,3,3,4,4,5,5-octafluoropentyl glycidyl ether.

17. The acid gas adsorption-desorption material of claim 11 wherein said linear epoxy-amine material has a formula selected from:

{[CH₂CH₂NH]_x[CH₂CHOH(R)CHOHCH₂](NHCH₂CH₂)_y}_n

wherein x is an integer greater than about 1.0, y is an integer greater than about 0, and n is an integer equal to or greater than about 1.0, the CH₂CH₂NH and NHCH₂CH₂ groups can be linear or branched, and R is the same or different and is an alkyl or aryl moiety.

18. The acid gas adsorption-desorption material of claim 11 wherein said linear epoxy-amine material has an average particle diameter of from about 0.1 microns to about 500 microns.

19. The acid gas adsorption-desorption material of claim 11 wherein said linear epoxy-amine material comprises a crosslinkable material.

20. A process for preparing an acid gas adsorption-desorption material comprising a crosslinked epoxy-amine material having a weight average molecular weight of from about 500 to about 1×

10⁶, a total pore volume of from about 0.2 cubic centimeters per gram (cc/g) to about 2.0 cc/g, and an adsorption capacity of at least about 0.2 millimoles of CO₂ adsorbed per gram of adsorption-desorption material;

said process comprising (i) reacting at least one epoxy material with at least one amine material under conditions sufficient to produce an epoxy-amine material, and (ii) crosslinking said epoxy-amine material under conditions sufficient to produce said crosslinked epoxy-amine material.

21. The process of claim 20 which is carried out in the presence of at least one porogen.

22. The process of claim 21 wherein said at least one porogen is selected from the group consisting of:

xylene, toluene, and polyvinylpyrrolidinone.

23. A process for preparing an acid gas adsorption-desorption material comprising a linear epoxy-amine material having a weight average molecular weight of from about 140 to about 1×

10⁶, a total pore volume of from about 0.2 cubic centimeters per gram (cc/g) to about 2.0 cc/g, and an adsorption capacity of at least about 0.2 millimoles of CO₂ adsorbed per gram of adsorption-desorption material;

said process comprising reacting an epoxy material with an amine material under conditions sufficient to produce said linear epoxy-amine material.

24. The process of claim 23 which is carried out in the presence of at least one porogen.

25. The process of claim 23 wherein said at least one porogen is selected from the group consisting of xylene, toluene, and polyvinylpyrrolidinone.

26. A method for adsorption-desorption of an acid gas comprising:

contacting a gas mixture containing at least one acid gas with an adsorbent material under conditions sufficient to cause adsorption of at least a portion of said acid gas, said adsorbent material selected from the group consisting of;

(i) a crossiiriked epoxy-amine material having a weight average molecular weight of from about 500 to about 1×

10⁶, a total pore volume of from about 0.2 cubic centimeters per gram cc/g) to about 2.0 cc/g, and an adsorption capacity of at least about 0.2 millimoles of CO₂ adsorbed per gram of adsorbent material, and (ii) a linear epoxy-amine material having a weight average molecular weight of from about 140 to about 1×

10⁶, and an adsorption capacity of at least about 0.2 millimoles of CO₂ adsorbed per gram of adsorbent material; and

treating said adsorbent material under conditions sufficient to cause desorption of at least a portion of said acid gas.

27. The method of claim 26 wherein said acid gas comprises CO₂.

28. The method of claim 26 wherein the adsorption is carried out at a pressure of about 0.1 bar to about 300 bar, and a temperature greater than about 80°

C.

29. The method of claim 28 wherein the desorption is carried out at a pressure of about 50 millibar to about 75 bar, and a temperature greater than about 80°

C.

30. The method of claim 26 wherein the method is comprised of at least one process selected from the group consisting of:

temperature swing adsorption, pressure swing adsorption, partial pressure swing adsorption, or by the use of a sweeping or purge gas, or any combination thereof.

31. The method of claim 26 wherein the gas mixture comprises CO₂ and at least one gas selected from the group consisting of:

hydrocarbons, carbon monoxide, H₂, O₂, N₂, and combinations thereof.

32. The method of claim 31 wherein the gas mixture further comprises at least one hydrocarbon selected from the group consisting of:

naphtha, methane, ethane, ethene, and combinations thereof.

33. A method of separating carbon dioxide from a gas mixture comprising;

providing at least one adsorption zone comprising an adsorbent, said adsorbent selected from the group consisting of;

(i) a cross linked epoxy-amine material having a weight average molecular weight of from about 500 to about 1×

10⁶, a total pore volume of from about 0.2 cubic centimeters per gram (cc/g) to about 2.0 cc/g, and an adsorption capacity of at least about 0.2 millimoles of CO₂ adsorbed per gram of adsorbent material, and (ii) a linear epoxy-amine material having a weight average molecular weight of from about 140 to about 1×

10⁶, and an adsorption capacity of at least about 0.2 millimoles of CO₂ adsorbed per gram of adsorbent material;

passing said gas mixture comprising at least carbon dioxide through said at least one adsorption zone, wherein said adsorbent adsorbs at least part of the carbon dioxide from the mixture to provide a carbon dioxide-depleted gas; and

regenerating said adsorbent by desorbing a carbon dioxide-rich gas.

34. The method of claim 33 wherein the adsorption is carried out at a pressure of about 0.1 bar to about 300 bar, and a temperature greater than about 80°

C.

35. The method of claim 34 wherein the desorption is carried out at a pressure of about 50 millibar to about 75 bar, and a temperature greater than about 80°

C.

36. The method of claim 35 wherein the passing and regenerating steps are carried out under essentially isothermal conditions.