Organosilica materials for use as adsorbents for oxygenate removal

Patent metadata

Field	Value
Publication number	US-10351639-B2
Application number	US-201515526521-A
Country	US
Kind code	B2
Filing date	Dec 11, 2015
Priority date	Dec 12, 2014
Publication date	Jul 16, 2019
Grant date	Jul 16, 2019

Abstract

This invention relates in certain aspects to a process for removing oxygenates from a stream, preferably a hydrocarbon stream comprising contacting an organosilica material with the hydrocarbon steam, where the organosilica material is a polymer of at least one monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 , wherein Z 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 6 alkyl group or an oxygen atom bonded to a silicon atom of another monomer.

First claim

What is claimed is:

1. A process to remove oxygenates from a hydrocarbon stream comprising contacting the hydrocarbon stream with an organosilica material that is a polymer of at least one monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I), wherein Z 1 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 6 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer.

2. The process of claim 1 further comprising:
(i) providing hydrocarbon stream comprising a polyolefin product stream, wherein the polyolefin product stream comprises polyolefin product and unreacted monomer;
(ii) quenching the polyolefin product stream with a quenching agent selected from water, a C 1 -C 8 alcohol, and combinations thereof, to produce a quenched polyolefin stream;
(iii) separating the quenched polyolefin stream into polyolefin product and a recycle stream; and
(iv) contacting at least a portion of the recycle stream with an adsorbent bed comprising the organosilica material to produce a treated recycle stream, wherein the recycle stream comprises quenching agent, one or more C 1 -C 40 oxygenates, and, optionally, one or more C 6 -C 12 conjugated or non-conjugated diene monomers, to remove the quenching agent and/or the C 1 -C 40 oxygenates.

3. The process of claim 1 , wherein Z 2 represents a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer.

4. The process of claim 1 , wherein Z 1 represents a hydrogen atom, methyl, ethyl or a bond to a silicon atom of another monomer and Z 2 represents a hydroxyl group, methyl, ethyl, ethoxy, methoxy, or an oxygen bonded to a silicon atom of another monomer.

5. The process of claim 1 , wherein the polymer further comprises a second distinct monomer of Formula [Z 1 OZ 2 SiCH 2 ] 3 (I).

6. The process of claim 1 , wherein the organosilica material further comprises at least one monomer selected from the group consisting of:
(i) a monomer of Formula Z 3 OZ 4 Z 5 Z 6 Si (II), wherein Z 3 represents a hydrogen atom or a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer; 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 C 1 -C 4 alkoxy group, a nitrogen-containing C 1 -C 10 alkyl group, a nitrogen-containing heteroaralkyl group, and a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer;
(ii) a monomer of Formula Z 7 Z 8 Z 9 Si—R—SiZ 7 Z 8 Z 9 (III), wherein Z 7 represents a hydroxyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another comonomer; Z 8 and Z 9 each independently represent a hydroxyl group, a C 1 -C 4 alkoxy group, a C 1 -C 4 alkyl group, or an oxygen bonded to a silicon atom of another monomer; and R 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, a nitrogen-containing C 2 -C 10 alkylene group, an optionally substituted C 6 -C 20 aralkyl and an optionally substituted C 4 -C 20 heterocycloalkyl group;
(iii) a trivalent metal oxide monomer of Formula M 1 (OZ 10 ) 3 (IV), wherein M 1 represents a Group 13 metal and Z 10 represents a hydrogen atom, a C 1 -C 6 alkyl or a bond to a silicon atom of another monomer;
(iv) a trivalent metal oxide monomer of Formula (Z 11 O) 2 M 2 -O—Si(OZ 12 ) 3 (V), wherein M 2 represents a Group 13 metal and Z 11 and Z 12 each independently represent a hydrogen atom, a C 1 -C 6 alkyl group, or a bond to a silicon atom of another monomer;
(v) a cyclic polyurea monomer of Formula

wherein each R 1 is a Z 13 OZ 14 Z 15 SiZ 16 group, wherein Z 13 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer unit; Z 14 and Z 15 each independently represent a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer unit; and Z 16 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea; and
(vi) any combinations thereof.

7. The process of claim 2 wherein the polyolefin product stream comprises a polymer comprising ethylene, propylene and, optionally, diene.

8. The process of claim 1 wherein the organosilica material further comprises at least one cyclic polyurea monomer of Formula:

where each R 1 is a Z 13 OZ 14 Z 15 SiZ 16 group, and Z 13 represents a hydrogen atom, a C 1 -C 4 alkyl group, or a bond to a silicon atom of another monomer unit; Z 14 and Z 15 each independently represent a hydroxyl group, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer unit; and Z 16 represents a C 1 -C 8 alkylene group bonded to a nitrogen atom of the cyclic polyurea.

9. The process of claim 2 , where the recycle stream has 50 wt % more C 4 -C 40 oxygenates than the treated recycle stream.

10. The process of claim 2 , where the adsorbent bed further comprises a zeolitic molecular sieve comprising a material selected from the group consisting of zeolite X, zeolite Y, zeolite A, faujasite, mordenite, ferrierite, and combinations thereof and is, optionally, binderless.

11. The process of claim 2 , where the adsorbent bed further comprises an alumina adsorbent and/or a silica adsorbent.

12. The process of claim 1 , wherein the organosilica material has:
(i) an average pore diameter between about 1.5 nm and about 25.0 nm;
(ii) a pore volume about 0.1 cm 3 /g to about 5.0 cm 3 /g; and/or
(iii) a surface area of about 200 m 2 /g to about 2,500 m 2 /g.

13. The process of claim 1 , wherein the organosilica material:
(i) has an X-Ray diffraction spectrum exhibiting substantially no peaks above 4 degrees 2θ; and/or
(ii) is made using substantially no added structure directing agent or porogen.

14. The process of claim 1 , where the hydrocarbon stream comprises one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, an isomer thereof or a polymer thereof.

15. The process of claim 2 , where the hydrocarbon stream comprises the effluent of a polymerization reactor.

16. The process of claim 2 , wherein the adsorbent bed comprises at least two adsorbents, wherein one adsorbent of the at least two adsorbents is the organosilica material.

17. The process of claim 2 , wherein the organosilica material adsorbent removes the one or more C 1 -C 40 oxygenates and, optionally at least one other adsorbent in the bed removes the quenching agent.

18. The process of claim 2 , wherein the organosilica material:
(i) has an X-Ray diffraction spectrum exhibiting substantially no peaks above 4 degrees 2θ; and/or
(ii) is made using substantially no added structure directing agent or porogen.

19. The process of claim 2 , wherein the one or more C 6 -C 12 non-conjugated diene monomers is present and selected from the group consisting of: pentadiene, methyl-pentadiene, hexadiene, methyl-hexadiene octadiene, heptadiene, norbornadiene, 5-vinyl-2-norbornene,

Assignees

• Exxonmobil Chemical Patents Inc
• Exxonmobil Res & Eng Co

Inventors

• Mertens Machteld M W
• Canich Jo Ann M
• Ho Suzzy C H
• Li Quanchang

Classifications

• B01D15/08

  Selective adsorption, e.g. chromatography · CPC title

• C08F6/005 Primary

  from solid polymers · CPC title

• C10G45/34

  characterised by the catalyst used · CPC title

• C10K1/32

  with selectively adsorptive solids, e.g. active carbon · CPC title

• B01J2220/86

  Sorbents applied to inner surfaces of columns or capillaries · CPC title