Organosilica materials and uses thereof

Patent metadata

Field	Value
Publication number	US-10207249-B2
Application number	US-201514966383-A
Country	US
Kind code	B2
Filing date	Dec 11, 2015
Priority date	Dec 12, 2014
Publication date	Feb 19, 2019
Grant date	Feb 19, 2019

Abstract

Organosilica materials, which are a polymer of at least one independent monomer of Formula [Z 1 OZ 2 OSiCH 2 ] 3 (I), wherein Z 1 and Z 2 each independently represent a hydrogen atom, a C 1 -C 4 alkyl group or a bond to a silicon atom of another monomer and at least one other monomer is provided herein. Methods of preparing and processes of using the organosilica materials, e.g., for gas separation, color removal etc., are also provided herein.

First claim

What is claimed is:

1. An organosilica material, which is a polymer of at least one independent monomer unit of Formula [Z 1 OZ 2 OSiCH 2 ] 3 (I), wherein Z 1 and Z 2 each independently represent a hydrogen atom or a bond to a silicon atom of another monomer unit and at least one other monomer unit selected from the group consisting of:
(i) an independent unit of Formula Z 3 OZ 4 Z 5 Z 6 Si (II), wherein each Z 3 represents a hydrogen atom or a bond to a silicon atom of another monomer unit; and Z 4 , Z 5 and Z 6 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 4 alkyl group, a nitrogen-containing C 1 -C 10 alkyl group, a nitrogen-containing heteroaralkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer unit;
(ii) an independent unit of Formula Z 7 Z 8 Z 9 Si—R 1 —SiZ 7 Z 8 Z 9 (III), wherein each Z 7 independently represents a hydroxyl group or an oxygen bonded to a silicon atom of another monomer unit; each Z 8 and Z 9 independently represent a hydroxyl group, a C 1 -C 4 alkyl group or an oxygen bonded to a silicon atom of another monomer unit; and each R 1 represents a nitrogen-containing C 2 -C 10 alkylene group; and
(iii) a combination thereof.

2. The organosilica material of claim 1 , wherein Z 1 and Z 2 each independently represent a hydrogen atom or a bond to a silicon atom of another monomer unit.

3. The organosilica material of claim 1 , wherein at least one independent unit of Formula (II) is present, wherein each Z 3 represents a hydrogen atom or a bond to a silicon atom of another monomer unit; and Z 4 , Z 5 and Z 6 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 2 alkyl group, a nitrogen-containing C 4 -C 10 alkyl group, a nitrogen-containing C 4 -C 10 heteroaralkyl group, or a nitrogen-containing optionally substituted C 4 -C 10 heterocycloalkyl group.

4. The organosilica material of claim 3 , wherein each Z 3 represents a hydrogen atom or a bond to a silicon atom of another monomer unit; and Z 4 , Z 5 and Z 6 are each independently selected from the group consisting of a hydroxyl group,

and an oxygen bonded to a silicon atom of another monomer unit.

5. The organosilica material of claim 1 , wherein at least one independent unit of Formula (III) is present, wherein each Z 7 represents a hydroxyl group or an oxygen bonded to a silicon atom of another monomer unit; each Z 8 and Z 9 independently represent a hydroxyl group, a C 1 -C 2 alkyl group or an oxygen bonded to a silicon atom of another monomer unit; and each R 1 represents a nitrogen-containing C 4 -C 10 alkyl group.

6. The organosilica material of claim 5 , wherein each Z 7 represents a hydroxyl group or an oxygen bonded to a silicon atom of another monomer unit; each Z 8 and Z 9 independently represent a hydroxyl group, methyl or an oxygen bonded to a silicon atom of another monomer unit; and each R 1 is selected from the group consisting of

7. The organosilica material of claim 1 further comprising a monomer unit selected from the group consisting of:
(i) an independent unit of Formula [Z 10 OZ 11 SiCH 2 ] 3 (IV), wherein each Z 10 represents a hydrogen atom or a bond to a silicon atom of another monomer unit and each Z 11 represents a hydroxyl group, a C 1 -C 6 alkyl group or an oxygen atom bonded to a silicon atom of another monomer unit;
(ii) an independent unit of Formula Z 12 OZ 13 Z 14 Z 15 Si (V), wherein each Z 12 represents a hydrogen atom or a bond to a silicon atom of another monomer unit; and Z 13 , Z 14 and Z 15 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 4 alkyl group, and an oxygen atom bonded to a silicon atom of another monomer unit;
(iii) an independent unit of Formula Z 16 Z 17 Z 18 Si—R 2 —SiZ 16 Z 17 Z 18 (VI), wherein each Z 16 independently represents a hydroxyl group or an oxygen bonded to a silicon atom of another monomer unit; each Z 17 and Z 18 independently represent a hydroxyl group, a C 1 -C 4 alkyl group or an oxygen bonded to a silicon atom of another monomer unit; and each R 2 is selected from the group consisting of a C 1 -C 8 alkylene group, a C 2 -C 8 alkenylene group, a C 2 -C 8 alkynylene group an optionally substituted C 6 -C 20 aralkyl and an optionally substituted C 4 -C 20 heterocycloalkyl group; and
(iv) a combination thereof.

8. The organosilica material of claim 1 , wherein the organosilica has an average pore diameter between about 2.0 nm and about 25.0 nm.

9. The organosilica material of claim 1 , wherein the organosilica material has a total surface area of about 500 m 2 /g to about 2000 m 2 /g.

10. The organosilica material of claim 1 , wherein the organosilica material has a pore volume of about 3.0 cm 3 /g to about 10 cm 3 /g.

11. The organosilica material of claim 1 , further comprising at least one catalytic metal incorporated within the pores of the material.

12. The organosilica material of claim 11 , wherein the catalytic metal is selected from the group consisting of a Group 6 element, a Group 8 element, a Group 9 element, a Group 10 element and a combination thereof.

13. The organosilica material of claim 1 made using essentially no structure directing agent or porogen.

14. A gas separation process comprising contacting a gas mixture containing at least one contaminant with the organosilica material of claim 1 .

15. The process of claim 14 , wherein the gas mixture comprises CH 4 and the at least one contaminant is CO 2 and/or H 2 S.

16. The process of claim 14 , wherein the process comprises PSA, TSA, PPSA, PTSA, RCPSA, RCTSA, RC-PPSA or RC-PTSA.

17. A process for selectively separating a contaminant from a feed gas mixture, the process comprising:
a) contacting the feed gas mixture under sorption conditions with the organosilica material of claim 1 ;
b) adsorbing the contaminant into/onto the organosilica material;
c) subjecting the organosilica material of claim 1 to desorption conditions by which at least a portion of the sorbed contaminant is desorbed; and
d) retrieving a contaminant-rich product stream that has a higher mol % of contaminant than the feed gas mixture.

18. The process of claim 17 , wherein the feed gas mixture comprises CH 4 .

19. The process of claim 17 , wherein the contaminant is CO 2 and/or H 2 S.

Assignees

• Li Quanchang
• Kamakoti Preeti
• Calabro David Charles
• Lee Mary Kathryn
• Cundy Stephen M
• Mao Kanmi
• Shah Matu J
• Peiffer Dennis George
• Leta Daniel P
• Exxonmobil Res & Eng Co

Inventors

• Li Quanchang
• Kamakoti Preeti
• Calabro David Charles
• Lee Mary Kathryn
• Cundy Stephen M
• Mao Kanmi
• Shah Matu J
• Peiffer Dennis George
• Leta Daniel P

Classifications

• B01J20/262

  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 title

• B01J23/44

  Palladium · CPC title

• B01J20/06

  comprising oxides or hydroxides of metals not provided for in group B01J20/04 · CPC title

• B01J20/3272

  Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds · CPC title

• B01J20/264

  derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers · CPC title