Organosilica materials and uses thereof

• US 10,207,249 B2
• Filed: 12/11/2015
• Issued: 02/19/2019
• Est. Priority Date: 12/12/2014
• Status: Expired due to Fees

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• 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.
• Primary Examiner(s): Jones, Christopher P
• Application Number:
  US14/966,383
• Publication Number:
  US 20160168174A1
• Time in Patent Office: 1,166 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 2257/404 Nitrogen oxides other than dinitrogen oxide
• 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 71/701 Polydimethylsiloxane
• 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 2231/641 : Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
• CPC Class Codes: B01J 2231/646 : of aromatic or heteroaromatic rings
• CPC Class Codes: B01J 23/42 : Platinum
• 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 31/125 : Cyclic siloxanes
• CPC Class Codes: B01J 31/127 : the siloxane units, e.g. silsesquioxane units, being grafted onto other polymers or inorganic supports, e.g. via an organic linker
• 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: B01J 37/036 : to form a gel or a cogel
• CPC Class Codes: C01B 37/00 : Compounds having molecular sieve properties but not having base-exchange properties
• CPC Class Codes: C07C 7/12 : by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
• CPC Class Codes: C07C 9/04 : Methane production by treatment of sewage C02F11/04; natural gas, synthetic natural gas C10L3/06
• 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: C10L 2290/542 : Adsorption of impurities during preparation or upgrading of a fuel
• CPC Class Codes: C10L 3/101 : Removal of contaminants
• CPC Class Codes: C10L 3/103 : Sulfur containing contaminants
• CPC Class Codes: C10L 3/104 : Carbon dioxide
• CPC Class Codes: C10M 101/02 : Petroleum fractions
• CPC Class Codes: C23C 16/56 : After-treatment
• CPC Class Codes: Y02C 20/40 : of CO2
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

Organosilica materials, which are a polymer of at least one independent monomer of Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² each independently represent a hydrogen atom, a C₁-C₄ 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.

Claims

1. An organosilica material, which is a polymer of at least one independent monomer unit 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 at least one other monomer unit selected from the group consisting of:

(i) an independent unit of Formula Z³OZ⁴Z⁵Z⁶Si (II), wherein each Z³ represents a hydrogen atom or a bond to a silicon atom of another monomer unit; and

Z⁴, Z⁵ and Z⁶ 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 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 Z⁷Z⁸Z⁹Si—

R¹—

SiZ⁷Z⁸Z⁹ (III), wherein each Z⁷ independently represents a hydroxyl group or an oxygen bonded to a silicon atom of another monomer unit;

each Z⁸ and Z⁹ independently represent a hydroxyl group, a C₁-C₄ alkyl group or an oxygen bonded to a silicon atom of another monomer unit; and

each R¹ represents a nitrogen-containing C₂-C₁₀ alkylene group; and

(iii) a combination thereof.

2. The organosilica 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 organosilica 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 another monomer unit;

and Z⁴, Z⁵ and Z⁶ are each independently selected from the group consisting of a hydroxyl group, a C₁-C₂ alkyl group, a nitrogen-containing C₄-C₁₀ alkyl group, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, or a nitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkyl group.

4. The organosilica material of claim 3, wherein each Z³ represents a hydrogen atom or a bond to a silicon atom of another monomer unit;

and Z⁴, Z⁵ and Z⁶ are each independently selected from the group consisting of a hydroxyl group,

5. The organosilica material of claim 1, wherein at least one independent unit of Formula (III) is present, wherein each Z⁷ represents a hydroxyl group or an oxygen bonded to a silicon atom of another monomer unit;

each Z⁸ and Z⁹ independently represent a hydroxyl group, a C₁-C₂ alkyl group or an oxygen bonded to a silicon atom of another monomer unit; and

each R¹ represents a nitrogen-containing C₄-C₁₀ alkyl group.

6. The organosilica material of claim 5, wherein each Z⁷ represents a hydroxyl group or an oxygen bonded to a silicon atom of another monomer unit;

each Z⁸ and Z⁹ independently represent a hydroxyl group, methyl or an oxygen bonded to a silicon atom of another monomer unit; and

each R¹ 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 [Z¹⁰OZ¹¹SiCH₂]₃ (IV), wherein each Z¹⁰ represents a hydrogen atom or a bond to a silicon atom of another monomer unit and each Z¹¹ represents a hydroxyl group, a C₁-C₆ alkyl group or an oxygen atom bonded to a silicon atom of another monomer unit;

(ii) an independent unit of Formula Z¹²OZ¹³Z¹⁴Z¹⁵Si (V), wherein each Z¹² represents a hydrogen atom or a bond to a silicon atom of another monomer unit; and

Z¹³, Z¹⁴ and Z¹⁵ are each independently selected from the group consisting of a hydroxyl group, a C₁-C₄ alkyl group, and an oxygen atom bonded to a silicon atom of another monomer unit;

(iii) an independent unit of Formula Z¹⁶Z¹⁷Z¹⁸Si—

R²—

SiZ¹⁶Z¹⁷Z¹⁸ (VI), wherein each Z¹⁶ independently represents a hydroxyl group or an oxygen bonded to a silicon atom of another monomer unit;

each Z¹⁷ and Z¹⁸ independently represent a hydroxyl group, a C₁-C₄ alkyl group or an oxygen bonded to a silicon atom of another monomer unit; and

each R² is selected from the group consisting of a C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group an optionally substituted C₆-C₂₀ aralkyl and an optionally substituted C₄-C₂₀ 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 m²/g to about 2000 m²/g.

10. The organosilica material of claim 1, wherein the organosilica material has a pore volume of about 3.0 cm³/g to about 10 cm³/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 CH₄ and the at least one contaminant is CO₂ and/or H₂S.

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 CH₄.

19. The process of claim 17, wherein the contaminant is CO₂ and/or H₂S.