Organosilica materials and uses thereof

• US 10,544,239 B2
• Filed: 12/11/2015
• Issued: 01/28/2020
• 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: Li, Quanchang, Calabro, David Charles, Afeworki, Mobae Amin, Weston, Simon Christopher, Mertens, Matcheld Maria Wilfried, Beutel, Tilman Wolfram, Lai, Wenyih Frank, Podsiadlo, Paul, Beeckman, Jean Willem Lodewijk
• Primary Examiner(s): Qian, Yun
• Application Number:
  US14/966,015
• Publication Number:
  US 20160229959A1
• Time in Patent Office: 1,509 Days
• Field of Search: None
• 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 2253/106 Silica or silicates
• CPC Class Codes: B01D 2253/204 Metal organic frameworks (MOF's)
• CPC Class Codes: B01D 2253/306 Surface area, e.g. BET-specific surface
• CPC Class Codes: B01D 2253/308 Pore size
• CPC Class Codes: B01D 2253/311 Porosity, e.g. pore volume
• CPC Class Codes: B01D 2256/245 Methane
• CPC Class Codes: B01D 2257/102 Nitrogen
• CPC Class Codes: B01D 2257/302 Sulfur oxides
• CPC Class Codes: B01D 2257/304 Hydrogen sulfide
• CPC Class Codes: B01D 2257/306 Organic sulfur compounds, e.g. mercaptans
• CPC Class Codes: B01D 2257/404 Nitrogen oxides other than dinitrogen oxide
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2257/702 Hydrocarbons
• 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 53/0462 Temperature swing adsorption
• CPC Class Codes: B01D 53/047 Pressure swing adsorption
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• 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 20/264 : 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 20/28069 : Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/28078 : Pore diameter
• 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 20/3236 : 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 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 29/0325 : Noble metals
• CPC Class Codes: B01J 31/06 : containing polymers organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691
• 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 35/633 : less than 0.5 ml/g
• CPC Class Codes: B01J 35/635 : 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/638 : more than 1.0 ml/g
• CPC Class Codes: B01J 35/643 : less than 2 nm
• CPC Class Codes: B01J 35/647 : 2-50 nm
• 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: C01B 39/00 : Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination treatment to modify the sorption properties, e.g. shaping using a binder, B01J20/10; treatment to modify the catalytic properties, e.g. combination of treatments to make the zeolites appropriate to their use as a catalyst, B01J29/04; treatment to improve the ion-exchange properties B01J39/14
• CPC Class Codes: C07F 7/00 : Compounds containing elements of Groups 4 or 14 of the Periodic Table
• CPC Class Codes: C08F 10/02 : Ethene
• 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 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: C08G 77/50 : by carbon linkages C08G77/485 takes precedence
• CPC Class Codes: C08G 77/58 : Metal-containing linkages C08G77/485 takes precedence
• 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 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 45/60 : 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: C10M 177/00 : Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
• CPC Class Codes: C10M 2203/1006 : used as base material
• CPC Class Codes: C10N 2070/00 : Specific manufacturing methods for lubricant compositions
• CPC Class Codes: Y02C 20/40 : of CO2

Abstract

Organosilica materials, which are a polymer of at least one independent monomer of Formula [Z¹OZ²OSiCH₂]₃ (I), wherein each Z¹ and Z² 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 trivalent metal oxide monomer are provided herein. Methods of preparing and processes of using the organosilica materials, e.g., for catalysis etc., are also provided herein.

Claims

1. An organosilica material, which is a polymer of at least one trivalent metal oxide monomer and at least one independent monomer of Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ represents a hydrogen atom, a C₁-C₄ alkyl group, a bond to a silicon atom of another monomer, or a combination thereof, and Z² represents a hydrogen atom, a C₁-C₄ alkyl group, a bond to a silicon atom of another monomer, or a combination thereof, wherein the organosilica material has an X-ray diffraction pattern with one peak between 1 and 3 degrees 2θ

and no peaks in the range of from 3 to 20 degrees 2θ

.

2. The organosilica material of claim 1, wherein Z¹ represents a hydrogen atom, a C₁-C₂ alkyl group, a bond to a silicon atom of another monomer, or a combination thereof, and Z² represents a hydrogen atom, a C1-C2 alkyl group, a bond to a silicon atom of another monomer, or a combination thereof.

3. The organosilica material of claim 1, wherein Z¹ represents a hydrogen atom, ethyl, a bond to a silicon atom of another monomer, or a combination thereof, and Z² represents a hydrogen atom, ethyl, a bond to a silicon atom of another monomer, or a combination thereof.

4. The organosilica material of claim 1, wherein the at least one trivalent metal oxide monomer is

(i) an independent unit of formula M¹(OZ³)₃ (II), wherein M¹ represents a Group 13 metal and Z³ represents a hydrogen atom, a C₁-C₆ alkyl, a bond to a silicon atom of another monomer, or a combination thereof;

or

(ii) an independent unit of formula (Z⁴O)₂M²-O—

Si(OZ⁵)₃ (III), wherein M² represents a Group 13 metal and Z⁴ represents a hydrogen atom, a C₁-C₆ alkyl group, a bond to a silicon atom of another monomer, or a combination thereof, and Z⁵ represents a hydrogen atom, a C₁-C₆ alkyl group, a bond to a silicon atom of another monomer, or a combination thereof.

5. The organosilica material of claim 4, wherein at least one unit of formula (II) is present, wherein M¹ is Al or B and Z³ represents a hydrogen atom, a C₁-C₄ alkyl group, a bond to a silicon atom or another monomer, or a combination thereof.

6. The organosilica material of claim 4, wherein at least one unit of formula (III) is present, wherein M² is Al or B;

and Z⁴ represents a hydrogen atom, a C₁-C₄ alkyl group, a bond to a silicon atom of another monomer, or a combination thereof.

7. The organosilica material of claim 4, wherein the at least one other trivalent metal oxide monomer is the independent unit of formula M¹(OZ³)₃ (II), wherein M¹ is a Group 13 metal and Z³ represents a combination of a hydrogen atom and a bond to a silicon atom of another monomer.

8. The organosilica material of claim 4, wherein the at least one other trivalent metal oxide monomer is an independent unit of formula M¹(OZ³)₃ (II), wherein M¹ is Al and Z³ represents a combination of a hydrogen atom and a bond to a silicon atom of another monomer.

9. The organosilica material of claim 1 further comprising a monomer selected from the group consisting of:

(i) an independent unit of formula [Z⁶OZ⁷SiCH₂]₃ (IV), wherein Z⁶ represents a hydrogen atom, a C₁-C₄ alkyl group, a bond to a silicon atom of another monomer, or a combination thereof, and Z⁷ represents a hydroxyl group, a C₁-C₆ alkyl group, an oxygen atom bonded to a silicon atom of another monomer, or a combination thereof;

(ii) an independent unit of formula Z⁸OZ⁹Z¹⁰Z¹¹Si (V), wherein Z⁸ represents a hydrogen atom or a C₁-C₄ alkyl group, a bond to a silicon atom of another monomer, or a combination thereof;

Z⁹ is selected from the group consisting of a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing heteroaralkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, an oxygen atom bonded to a silicon atom of another monomer, or a combination thereof;

Z¹⁰ is selected from the group consisting of a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing heteroaralkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, an oxygen atom bonded to a silicon atom of another monomer, or a combination thereof; and

Z¹¹ is selected from the group consisting of a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing heteroaralkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, an oxygen atom bonded to a silicon atom of another monomer, or a combination thereof; and

(iii) an independent unit of formula Z ¹²Z¹³Z¹⁴Si—

R—

SiZ¹²Z¹³Z¹⁴ (VI), wherein Z¹² represents a hydroxyl group, a C₁-C₄ alkoxy group, an oxygen atom bonded to a silicon atom of another comonomer, or a combination thereof, Z¹³ represents a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group, an oxygen bonded to a silicon atom of another monomer, or a combination thereof;

Z14 represents a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group, an oxygen bonded to a silicon atom of another monomer, or a combination thereof; and

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

(iv) a combination thereof.

10. The organosilica material of claim 1, wherein the organosilica has an average pore diameter between about 1.5 nm and about 20.0 nm.

11. The organosilica material of claim 1, wherein the organosilica material has a total surface area of about 200 m²/g to about 2500 m²/g.

12. The organosilica material of claim 1, wherein the organosilica material has a pore volume about 0.1 cm³/g to about 5.0 cm³/g.

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

14. The organosilica material of claim 13, 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.

15. The organosilica material of claim 14, wherein the catalytic metal is Group 10 element.

16. The organosilica material of claim 14, wherein the catalytic metal is the Group 10 element of palladium.

17. The organosilica material of claim 1 made using no added structure directing agent or porogen.

18. The organosilica material of claim 1, wherein Z¹ represents a combination of a hydrogen atom and a bond to a silicon atom of another monomer and Z² represents a combination of a hydrogen atom and a bond to a silicon atom of another monomer.

19. The organosilica material of claim 1, further comprising an independent unit of formula Z⁸OZ⁹Z¹⁰Z¹¹Si (V), wherein Z⁸ represents a combination of a hydrogen atom and a bond to a silicon atom of another monomer, Z⁹ represents a combination of a hydroxyl group and a bond to an oxygen atom bonded to a silicon atom of another monomer, Z¹⁰ represents a combination of a hydroxyl group and a bond to an oxygen atom bonded to a silicon atom of another monomer, and Z¹¹ represents a combination of a hydroxyl group and a bond to an oxygen atom bonded to a silicon atom of another monomer.