Adsorbent for heteroatom species removal and uses thereof

Patent metadata

Field	Value
Publication number	US-10183272-B2
Application number	US-201514966534-A
Country	US
Kind code	B2
Filing date	Dec 11, 2015
Priority date	Dec 12, 2014
Publication date	Jan 22, 2019
Grant date	Jan 22, 2019

Abstract

Adsorbent materials including a porous material support and about 0.5 wt. % to about 30 wt. % of a Group 8 metal ion are provide herein. Methods of making the adsorbent material and processes of using the adsorbent material, e.g., for heteroatom species separation, are also provided herein.

First claim

What is claimed is:

1. An adsorbent material comprising:
a porous material support; wherein the porous material support includes an organosilica material, which is a polymer comprising independent units of a monomer 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
about 0.5 wt. % to about 30 wt. % of a Group 8 metal ion,
wherein the organosilica material further comprises at least one other monomer unit selected from the group consisting of:
(i) an independent unit of Formula [Z 3 OZ 4 SiCH 2 ] 3 (II), wherein each Z 3 represents a hydrogen atom, or a bond to a silicon atom of another monomer unit and Z 4 represents a C 1 -C 6 alkyl group;
(ii) an independent unit of Formula Z 5 OZ 6 Z 7 Z 8 Si (III), wherein Z 5 represents a hydrogen atom, or a bond to a silicon atom of another monomer unit; and Z 6 , Z 7 , and Z 8 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 heteroalkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer unit;
(iii) an independent unit of Formula Z 9 Z 10 Z 11 Si—R—SiZ 9 Z 10 Z 11 (IV), wherein each Z 9 independently represents a hydroxyl group, or an oxygen atom bonded to a silicon atom of another monomer unit; each Z 10 and Z 11 independently represent a hydroxyl group, a C 1 -C 4 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer unit; and R is selected from the group consisting 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 1 -C 10 alkylene group, an optionally substituted C 6 -C 20 aralkyl, and an optionally substituted C 4 -C 20 heterocycloalkyl group;
(iv) an independent cyclic polyurea monomer unit of Formula

wherein each R 1 independently is a X 1 OX 2 X 3 SiX 4 group, wherein each X 1 represents a hydrogen atom, or a bond to a silicon atom of another monomer unit; X 2 and X 3 each independently represent a hydroxyl group, a C 1 -C 4 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer unit; and each X 4 represents a C alkylene group bonded to a nitrogen atom of the cyclic polyurea
(v) an independent unit of Formula M 1 (OZ 12 ) 3 (VI), wherein M 1 represents a Group 13 metal and each Z 12 independently represents a hydrogen atom, or a bond to a silicon atom of another monomer unit;
(vi) an independent unit of Formula (Z 13 O) 2 M 2 -O—Si(OZ 14 ) 3 (VII), wherein M 2 represents a Group 13 metal and Z 13 and Z 14 each independently represent a hydrogen atom, or a bond to a silicon atom of another monomer unit; and
(vii) a combination thereof.

2. The adsorbent 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 adsorbent 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.

4. The adsorbent 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 a siloxane monomer unit; and each Z 4 represents a C 1 -C 2 alkyl group.

5. The adsorbent material of claim 4 , wherein each Z 3 represents a hydrogen atom, or a bond to a silicon atom of another siloxane monomer unit; and each Z 4 represents methyl.

6. The adsorbent material of claim 1 , wherein at least one independent unit of Formula (III) is present, wherein Z 5 represents a hydrogen atom, or a bond to a silicon atom of another monomer unit; and Z 6 , Z 7 , and Z 8 are each independently selected from the group consisting of a hydroxyl group, a C 1 -C 2 alkyl group, a nitrogen-containing C 3 -C 10 alkyl group, a nitrogen-containing C 4 -C 10 heteroalkyl group, a nitrogen-containing optionally substituted C 4 -C 10 heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer unit.

7. The adsorbent material of claim 6 , wherein Z 5 represents a hydrogen atom or a bond to a silicon atom of another monomer unit; and Z 6 , Z 7 , and Z 8 are each independently selected from the group consisting of a hydroxyl group, methyl,

8. The adsorbent material of claim 1 , wherein at least one independent unit of Formula (IV) is present, wherein each Z 9 represents a hydroxyl group or an oxygen atom bonded to a silicon atom of another monomer unit; each Z 10 and Z 11 independently represent a hydroxyl group, a C 1 -C 2 alkyl group, or an oxygen atom bonded to a silicon atom of another monomer unit; and R is selected from the group consisting of a C 1 -C 4 alkylene group, a C 2 -C 4 alkenylene group, a C 2 -C 4 alkynylene group, a nitrogen-containing C 4 -C 10 alkylene group, an optionally substituted C 6 -C 10 aralkyl and an optionally substituted C 4 -C 12 heterocycloalkyl group.

9. The adsorbent material of claim 8 , wherein each Z 9 represents a hydroxyl group or an oxygen atom bonded to a silicon atom of another monomer unit; each Z 10 and Z 11 independently represent a hydroxyl group, methyl, or an oxygen atom bonded to a silicon atom of another monomer unit; and R is selected from the group consisting of —CH 2 —, —CH 2 CH 2 —, —HC═CH—,

10. The adsorbent material of claim 1 , wherein at least one independent unit of Formula (V) is present, wherein each X 1 represents a hydrogen atom, or a bond to a silicon atom of another monomer unit; X 2 and X 3 each independently represent a hydroxyl group, a C 1 -C 2 alkyl group or an oxygen atom bonded to a silicon atom of another monomer unit; and each X 4 represents a C 1 -C 4 alkylene group bonded to a nitrogen atom of the cyclic compound.

11. The adsorbent material of claim 10 , wherein each X 1 represents a hydrogen atom or a bond to a silicon atom of another monomer unit; X 2 and X 3 each independently represent a hydroxyl group or an oxygen atom bonded to a silicon atom of another monomer unit and each X 4 represents —CH 2 CH 2 CH 2 — bonded to a nitrogen atom of the cyclic polyurea.

12. The adsorbent material of claim 1 , wherein at least one independent unit of Formula (VI) is present, wherein M 1 is Al or B and each Z 12 independently represents a hydrogen atom or a bond to a silicon atom or another monomer unit.

13. The adsorbent material of claim 1 , wherein at least one independent unit of Formula (VII) is present, wherein M 2 is Al or B and Z 13 and Z 14 each independently represent a hydrogen atom or a bond to a silicon atom of another monomer unit.

14. The adsorbent material of claim 1 , wherein the Group 8 metal ion is present in amount of about 1.0 wt. % to about 15 wt. %.

15. The adsorbent material of claim 1 , wherein the Group 8 metal ion is ferrous iron, ferric iron or a combination thereof.

Assignees

• Exxonmobil Res & Eng Co

Inventors

• Podsiadlo Paul
• Wu Jianxin
• Benitez Kiara M
• Li Quanchang
• Calabro David Charles

Classifications

• B01D2256/245

  Methane · CPC title

• B01J20/28066

  being more than 1000 m2/g · CPC title

• C08F4/64048

  NO · CPC title

• B01J20/3042

  Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent · CPC title

• B01J2220/86

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