Adsorbent for heteroatom species removal and uses thereof

• US 10,183,272 B2
• Filed: 12/11/2015
• Issued: 01/22/2019
• Est. Priority Date: 12/12/2014
• Status: Active Grant

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Podsiadlo, Paul, Wu, Jianxin, Benitez, Kiara M., Li, Quanchang, Calabro, David Charles
• Primary Examiner(s): Robinson, Renee
• Application Number:
  US14/966,534
• Publication Number:
  US 20160167015A1
• Time in Patent Office: 1,138 Days
• CPC Class Codes: B01D 15/00 Separating processes involving the treatment of liquids with solid sorbents using liquid sorbents B01D11/00; ion exchange processes or materials, sorbent materials in general B01J, e.g. sorbents for chromatography B01J20/281; for investigating or analysing materials G01N30/00; Apparatus therefor
• CPC Class Codes: B01D 2253/20 Organic adsorbents
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2256/245 Methane
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/40 Nitrogen compounds
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/80 Water
• 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: B01D 53/04 with stationary adsorbents B01D53/025 takes precedence
• CPC Class Codes: B01D 53/0462 Temperature swing adsorption
• CPC Class Codes: B01D 53/047 Pressure swing adsorption
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 71/702 Polysilsesquioxanes or combination of silica with bridging organosilane groups
• CPC Class Codes: B01J 20/0229 Compounds of Fe
• CPC Class Codes: B01J 20/0237 Compounds of Cu
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/10 comprising silica or silicate
• CPC Class Codes: B01J 20/103 : comprising silica
• CPC Class Codes: B01J 20/16 : Alumino-silicates B01J20/12 takes precedence
• CPC Class Codes: B01J 20/18 : Synthetic zeolitic molecular sieves
• CPC Class Codes: B01J 20/22 : comprising organic material
• CPC Class Codes: B01J 20/223 : containing metals, e.g. organo-metallic compounds, coordination complexes
• CPC Class Codes: B01J 20/226 : Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• 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 20/264 : derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
• CPC Class Codes: B01J 20/28011 : Other properties, e.g. density, crush strength
• CPC Class Codes: B01J 20/28057 : Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28061 : being in the range 100-500 m2/g
• CPC Class Codes: B01J 20/28064 : being in the range 500-1000 m2/g
• CPC Class Codes: B01J 20/28066 : being more than 1000 m2/g
• CPC Class Codes: B01J 20/28069 : Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/28071 : being less than 0.5 ml/g
• CPC Class Codes: B01J 20/28073 : being in the range 0.5-1.0 ml/g
• CPC Class Codes: B01J 20/28076 : being more than 1.0 ml/g
• CPC Class Codes: B01J 20/28078 : Pore diameter
• CPC Class Codes: B01J 20/28083 : being in the range 2-50 nm, i.e. mesopores
• CPC Class Codes: B01J 20/286 : Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 20/3042 : Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
• CPC Class Codes: B01J 20/3204 : Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3212 : consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3236 : containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 20/3238 : containing any type of zeolite
• CPC Class Codes: B01J 20/3272 : Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 2220/86 : Sorbents applied to inner surfaces of columns or capillaries
• CPC Class Codes: B01J 23/44 : Palladium
• CPC Class Codes: B01J 29/0308 : Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
• CPC Class Codes: B01J 31/0274 : containing silicon ligands in coordination complexes B01J31/1608
• CPC Class Codes: B01J 35/615 : 100-500 m2/g
• CPC Class Codes: B01J 35/617 : 500-1000 m2/g
• CPC Class Codes: B01J 35/618 : more than 1000 m2/g
• CPC Class Codes: B01J 35/647 : 2-50 nm
• CPC Class Codes: B01J 37/0213 : Preparation of the impregnating solution
• CPC Class Codes: B01J 37/0236 : Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: C01B 37/00 : Compounds having molecular sieve properties but not having base-exchange properties
• CPC Class Codes: C07F 7/08 : Compounds having one or more C—Si linkages
• CPC Class Codes: C07F 7/0807 : comprising Si as a ring atom
• CPC Class Codes: C07F 7/081 : comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
• CPC Class Codes: C08F 2/00 : Processes of polymerisation
• CPC Class Codes: C08F 2/10 : Aqueous solvent
• CPC Class Codes: C08F 2/42 : using short-stopping agents
• CPC Class Codes: C08F 210/02 : Ethene
• CPC Class Codes: C08F 210/14 : Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 36/04 : conjugated
• CPC Class Codes: C08F 36/20 : unconjugated
• CPC Class Codes: C08F 4/027 : Polymers
• CPC Class Codes: C08F 4/64013 : NN
• CPC Class Codes: C08F 4/64048 : NO
• CPC Class Codes: C08F 4/64089 : NNN
• CPC Class Codes: C08F 4/64148 : NN(R)N
• CPC Class Codes: C08F 4/64158 : ONO
• CPC Class Codes: C08F 4/64189 : ONNO
• CPC Class Codes: C08F 4/64193 : OOOO
• CPC Class Codes: C08F 4/659 : Component covered by group C08F4/64 containing a transition metal-carbon bond C08F4/64003 - C08F4/64196 take precedence
• CPC Class Codes: C08F 4/65912 : in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 : supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65925 : two cyclopentadienyl rings being mutually non-bridged
• CPC Class Codes: C08F 4/65927 : two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: C08G 77/26 : nitrogen-containing groups
• CPC Class Codes: C08G 77/60 : in which all the silicon atoms are connected by linkages other than oxygen atoms
• CPC Class Codes: C10G 25/003 : Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 31/09 : by filtration
• CPC Class Codes: C10G 35/06 : characterised by the catalyst used
• CPC Class Codes: C10G 45/00 : Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• CPC Class Codes: C10G 45/04 : characterised by the catalyst used
• CPC Class Codes: C10G 45/34 : characterised by the catalyst used
• CPC Class Codes: C10G 45/44 : Hydrogenation of the aromatic hydrocarbons
• CPC Class Codes: C10G 45/46 : characterised by the catalyst used
• CPC Class Codes: C10G 45/52 : containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 45/60 : characterised by the catalyst used
• CPC Class Codes: C10G 45/64 : containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 47/02 : characterised by the catalyst used
• CPC Class Codes: C10G 50/00 : Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• CPC Class Codes: C10K 1/32 : with selectively adsorptive solids, e.g. active carbon
• CPC Class Codes: C10M 101/02 : Petroleum fractions
• CPC Class Codes: C23C 16/56 : After-treatment
• CPC Class Codes: Y02C 20/40 : of CO2

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.

Claims

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 [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² 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 [Z³OZ⁴SiCH₂]₃ (II), wherein each Z³ represents a hydrogen atom, or a bond to a silicon atom of another monomer unit and Z⁴ represents a C₁-C₆ alkyl group;

(ii) an independent unit of Formula Z⁵OZ⁶Z⁷Z⁸Si (III), wherein Z⁵ represents a hydrogen atom, or a bond to a silicon atom of another monomer unit; and

Z⁶, Z⁷, and Z⁸ are each independently selected from the group consisting of a hydroxyl group, a C₁-C₄ alkyl group, a nitrogen-containing C₁-C₁₀ 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 Z⁹Z¹⁰Z¹¹Si—

R—

SiZ⁹Z¹⁰Z¹¹ (IV), wherein each Z⁹ independently represents a hydroxyl group, or an oxygen atom bonded to a silicon atom of another monomer unit;

each Z¹⁰ and Z¹¹ independently represent a hydroxyl group, a C₁-C₄ alkyl group, or an oxygen atom bonded to a silicon atom of another monomer unit; and

R is selected from the group consisting a C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, a nitrogen-containing C₁-C₁₀ alkylene group, an optionally substituted C₆-C₂₀ aralkyl, and an optionally substituted C₄-C₂₀ heterocycloalkyl group;

(iv) an independent cyclic polyurea monomer unit of Formula

2. The adsorbent material of claim 1, wherein Z¹ and Z² 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 Z¹ and Z² 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 Z³ represents a hydrogen atom, or a bond to a silicon atom of a siloxane monomer unit;

and each Z⁴ represents a C₁-C₂ alkyl group.

5. The adsorbent material of claim 4, wherein each Z³ represents a hydrogen atom, or a bond to a silicon atom of another siloxane monomer unit;

and each Z⁴ represents methyl.

6. The adsorbent material of claim 1, wherein at least one independent unit of Formula (III) is present, wherein Z⁵ represents a hydrogen atom, or a bond to a silicon atom of another monomer unit;

and Z⁶, Z⁷, and Z⁸ are each independently selected from the group consisting of a hydroxyl group, a C₁-C₂ alkyl group, a nitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containing C₄-C₁₀ heteroalkyl group, a nitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer unit.

7. The adsorbent material of claim 6, wherein Z⁵ represents a hydrogen atom or a bond to a silicon atom of another monomer unit;

and Z⁶, Z⁷, and Z⁸ 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 Z⁹ represents a hydroxyl group or an oxygen atom bonded to a silicon atom of another monomer unit;

each Z¹⁰ and Z¹¹ independently represent a hydroxyl group, a C₁-C₂ 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 C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄ alkynylene group, a nitrogen-containing C₄-C₁₀ alkylene group, an optionally substituted C₆-C₁₀ aralkyl and an optionally substituted C₄-C₁₂ heterocycloalkyl group.

9. The adsorbent material of claim 8, wherein each Z⁹ represents a hydroxyl group or an oxygen atom bonded to a silicon atom of another monomer unit;

each Z¹⁰ and Z¹¹ 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 —

CH₂—

, —

CH₂CH₂—

, —

HC═

CH—

,

10. The adsorbent material of claim 1, wherein at least one independent unit of Formula (V) is present, wherein each X¹ represents a hydrogen atom, or a bond to a silicon atom of another monomer unit;

X² and X³ each independently represent a hydroxyl group, a C₁-C₂ alkyl group or an oxygen atom bonded to a silicon atom of another monomer unit; and

each X⁴ represents a C₁-C₄ alkylene group bonded to a nitrogen atom of the cyclic compound.

11. The adsorbent material of claim 10, wherein each X¹ represents a hydrogen atom or a bond to a silicon atom of another monomer unit;

X² and X³ each independently represent a hydroxyl group or an oxygen atom bonded to a silicon atom of another monomer unit and each X⁴ represents —

CH₂CH₂CH₂—

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 M¹ is Al or B and each Z¹² 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 M² is Al or B and Z¹³ and Z¹⁴ 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.