Sulfur terminated organosilica materials and uses thereof

• US 10,179,839 B2
• Filed: 11/03/2017
• Issued: 01/15/2019
• Est. Priority Date: 11/18/2016
• Status: Expired due to Fees

• Current Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Research & Engineering Company (Exxon Mobil Corporation)
• Inventors: Falkowski, Joseph M., Afeworki, Mobae, Calabro, David C., Griffin, David A., Weston, Simon C.
• Primary Examiner(s): Loewe, Robert S
• Application Number:
  US15/802,680
• Publication Number:
  US 20180142066A1
• Time in Patent Office: 438 Days
• Field of Search: None
• CPC Class Codes: B01J 20/223 containing metals, e.g. organo-metallic compounds, coordination complexes
• 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 23/50 Silver
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 27/043 with iron group metals or platinum group metals
• CPC Class Codes: B01J 31/069 Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups nitrogen containing groups on mineral substrates B01J31/0254; organometallic polymers B01J31/123; coordination complexes immobilised on an inorganic support B01J31/1616; coordination polymers, e.g. metal-organic frameworks B01J31/1691
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/399 homogeneously throughout the support particle
• CPC Class Codes: B01J 35/613 10-100 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/344 of electromagnetic wave energy
• CPC Class Codes: C07C 15/00 Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
• CPC Class Codes: C07C 2523/50 Silver
• CPC Class Codes: C07C 2531/06 containing polymers
• CPC Class Codes: C07C 5/10 of aromatic six-membered rings
• 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: C08G 77/02 Polysilicates
• CPC Class Codes: C08G 77/18 to alkoxy or aryloxy groups
• CPC Class Codes: C08J 2201/0504 : the liquid phase being aqueous
• CPC Class Codes: C08J 2205/022 : Hydrogel, i.e. a gel containing an aqueous composition
• CPC Class Codes: C08J 2205/042 : Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
• CPC Class Codes: C08J 2205/10 : Rigid foams
• CPC Class Codes: C08J 2383/02 : Polysilicates
• CPC Class Codes: C08J 9/286 : the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
• CPC Class Codes: C10G 25/003 : Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 49/04 : containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof

Abstract

Provided herein are compositions and methods for use of an organosilica material comprising a copolymer of at least one monomer of Formula [R¹R²SiCH₂]₃ (I), wherein, R¹ represents a C₁-C₄ alkoxy group; and R² is a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; and at least one other monomer of Formula [(Z¹O)_xZ²_3-xSi—Z³—SZ⁴] (II), wherein, Z¹ represents a hydrolysable functional group; Z² represents a C₁-C₁₀ alkyl or aryl group; Z³ represents a C₂-C₁₁ cyclic or linear hydrocarbon; Z⁴ is either H or O₃H; and x represents any one of integers 1, 2, and 3. The composition may be used as a support material to covalently attach transition metal cations, as a sorbent for olefin/paraffin separations, as a catalyst support for hydrogenation reactions, as a precursor for highly dispersed metal nanoparticles, or as a polar sorbent for crude feeds.

Claims

1. An organosilica material comprising a copolymer of

at least one monomer of Formula [R¹R²SiCH₂]₃ (I), wherein:

R¹ represents a C₁-C₄ alkoxy group; and

R² is a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; and

at least one other monomer of Formula [(Z¹O)_xZ²_3-xSi—

Z³—

SZ⁴] (II), wherein;

Z¹ represents a hydrolysable functional group;

Z² represents a C₁-C₁₀ alkyl or aryl group;

Z³ represents a C₂-C₁₁ cyclic or linear hydrocarbon;

Z⁴ is either H or O₃H; and

x represents any one of integers 1, 2, and 3.

2. The organosilica material of claim 1, wherein Z³ has incorporated within the C₂-C₁₁ cyclic or linear hydrocarbon (a) an amine, (b) an ether, (c) a heteroatom, (d) a combination of any of (a), (b), and (c), or none of (a), (b), and (c), provided that Si and S remain bonded to a carbon atom.

3. The organosilica material of claim 1, further comprising a catalyst metal.

4. The organosilica material of claim 3, wherein the catalyst metal comprises a transition metal, a metal oxide, a metal sulphide, or mixtures thereof.

5. The organosilica material of claim 3, wherein the catalyst metal is incorporated as dispersed metal particles.

6. The organosilica material of claim 3, wherein the catalyst metal comprises silver.

7. The organosilica material of claim 1, wherein the at least one monomer of Formula [R¹R²SiCH₂]₃ (I) is 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃).

8. The organosilica material of claim 1, wherein the at least one other monomer of Formula [(Z¹O)_xZ²_3-xSi—

Z³—

SZ⁴] (II) is 3-(triethoxysilyl)propane-1-thiol.

9. A method for separation of olefins from paraffins comprising:

contacting a hydrocarbon stream comprising olefins and paraffins with an adsorbent bed to produce a paraffins rich stream,

wherein the adsorbent bed comprises;

(i) an organosilica material support, which is a copolymer of at least one monomer of Formula [R¹R²SiCH₂]₃ (I), wherein R¹ represents a C₁-C₄ alkoxy group and R² is a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group, and at least one other monomer of Formula [(Z¹O)_xZ²_3-xSi—

Z³—

SZ⁴] (II), wherein Z¹ represents a hydrolysable functional group;

Z² represents a C₁-C₁₀ alkyl or aryl group;

Z³ represents a C₂-C₁₁ cyclic or linear hydrocarbon, wherein Z³ has incorporated within the C₂-C₁₁ cyclic or linear hydrocarbon (a) an amine, (b) an ether, (c) a heteroatom, (d) a combination of any of (a), (b), and (c), or none of (a), (b), and (c), provided that Si and S remain bonded to a carbon atom;

Z⁴ is either H or O₃H; and

x represents any one of integers 1, 2, and 3;

(ii) at least one catalyst metal.

10. The method of claim 9, wherein the at least one catalyst metal is silver.

11. The method of claim 9, wherein the at least one catalyst metal is copper.

12. A hydrogenation process for a hydrocarbon feedstream comprising:

contacting a hydrocarbon feedstream with a hydrogenation catalyst in the presence of a hydrogen-containing treat gas in a reaction stage operated under effective hydrogenation conditions,

wherein the hydrogenation catalyst comprises;

(i) an organosilica material support, which is a copolymer of at least one monomer of Formula [R¹R²SiCH₂]₃ (I), wherein R¹ represents a C₁-C₄ alkoxy group and R² is a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group, and at least one other monomer of Formula [(Z¹O)_xZ²_3-xSi—

Z³—

SZ⁴] (II), wherein Z¹ represents a hydrolysable functional group;

Z² represents a C₁-C₁₀ alkyl or aryl group;

Z³ represents a C₂-C₁₁ cyclic or linear hydrocarbon, wherein Z³ has incorporated within the C₂-C₁₁ cyclic or linear hydrocarbon (a) an amine, (b) an ether, (c) a heteroatom, (d) a combination of any of (a), (b), and (c), or none of (a), (b), and (c), provided that Si and S remain bonded to a carbon atom;

Z⁴ is either H or O₃H; and

x represents any one of integers 1, 2, and 3;

(ii) at least one catalyst metal.

13. The process of claim 12, wherein the organosilica material support further comprises a surface metal on a surface of the organosilica material, the surface metal including aluminum.

14. The process of claim 12, wherein the organosilica material support further comprises an aluminum component, the aluminum component being provided within an aqueous mixture used to form the organosilica material.

15. A method for separation of polar organic compounds from a hydrocarbon feed comprising:

contacting the hydrocarbon stream comprising polar organic compounds with an adsorbent bed to produce a hydrocarbon stream with a reduced concentration of polar organic compounds,

wherein the adsorbent bed comprises an organosilica material support, which is a copolymer of at least one monomer of Formula [R¹R²SiCH₂]₃ (I), wherein R¹ represents a C₁-C₄ alkoxy group and R² is a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group, and at least one other monomer of Formula [(Z¹O)_xZ²_3-xSi—

Z³—

SZ⁴] (II), wherein Z¹ represents a hydrolysable functional group;

Z² represents a C₁-C₁₀ alkyl or aryl group;

Z³ represents a C₂-C₁₁ cyclic or linear hydrocarbon, wherein Z³ has incorporated within the C₂-C₁₁ cyclic or linear hydrocarbon (a) an amine, (b) an ether, (c) a heteroatom, (d) a combination of any of (a), (b), and (c), or none of (a), (b), and (c), provided that Si and S remain bonded to a carbon atom;

Z⁴ is either H or O₃H; and

x represents any one of integers 1, 2, and 3.