Coating methods using organosilica materials and uses thereof

• US 10,022,701 B2
• Filed: 12/11/2015
• Issued: 07/17/2018
• 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, Partridge, Randall D.
• Primary Examiner(s): Jones, Christopher P
• Application Number:
  US14/966,407
• Publication Number:
  US 20160167016A1
• Time in Patent Office: 949 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: 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

Methods for coating a substrate with a coating including an adsorbent material and a binder comprising an organosilica material which is a polymer comprising independent units of Formula [Z³Z⁴SiCH₂]₃ (I), wherein each Z³ represents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen atom bonded to a silicon atom of another unit or an active site on the substrate and each Z⁴ represents a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group, an oxygen atom bonded to a silicon atom of another unit or an active site on the substrate are provided. Methods of gas separation are also provided.

Claims

1. A method for coating a substrate, the method comprising:

(a) adding at least one compound of Formula [Z¹Z²SiCH₂]₃ (Ia) into an aqueous mixture that contains essentially no structure directing agent or porogen to form a solution, wherein each Z¹ represents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen atom bonded to a silicon atom of another compound and each Z² represents, a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group or an oxygen atom bonded to a silicon atom of another compound;

(b) adding an adsorbent material to the solution to form a slurry;

(c) coating the slurry onto a substrate;

(d) aging the slurry; and

(e) drying the slurry to obtain a coating comprising the adsorbent material and a binder comprising an organosilica material which is a polymer comprising independent units of Formula [Z³Z⁴SiCH₂]₃ (I), wherein each Z³ represents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen atom bonded to a silicon atom of another unit or an active site on the substrate and each Z⁴ represents a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group, an oxygen atom bonded to a silicon atom of another unit or an active site on the substrate.

2. The method of claim 1, wherein each Z¹ represents a C₁-C₂ alkoxy group.

3. The method of claim 2, wherein each Z² represents a C₁-C₄ alkoxy group.

4. The method of claim 3, wherein each Z² represents a C₁-C₂ alkoxy group.

5. The method of claim 1, wherein the at least one compound of Formula (Ia) is 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane.

6. The method of claim 1, wherein each Z³ represents a hydroxyl group, a C₁-C₂ alkoxy group, or an oxygen bonded to a silicon atom of another unit or an active site on the substrate, and Z⁴ represents a hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, or an oxygen bonded to a silicon atom of another unit or an active site on the substrate.

7. The method of claim 6, wherein each Z³ represents a hydroxyl group, ethoxy, or an oxygen bonded to a silicon atom of another unit or an active site on the substrate, and each Z⁴ represents a hydroxyl group, ethoxy, or an oxygen bonded to a silicon atom of another unit or an active site on the substrate.

8. The method of claim 1, further comprising adding to the aqueous mixture at least a second compound selected from the group consisting of:

(i) a further compound of Formula (Ia);

(ii) a compound of Formula R¹OR²R³R⁴Si (II), wherein each R¹ represents a C₁-C₄ alkyl group; and

R², R³, and R⁴ are each independently selected from the group consisting of a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing heteroalkyl group, and a nitrogen-containing optionally substituted heterocycloalkyl group;

(iii) a compound of Formula Z⁵Z⁶Z⁷Si—

R—

SiZ⁵Z⁶Z⁷ (III), wherein each Z⁵ independently represents a C₁-C₄ alkoxy group;

each Z⁶ and Z⁷ independently represent a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; 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) a compound of Formula M¹(OZ⁸)₃ (IV), wherein M¹ represents a Group 13 metal and each Z⁸ independently represents a C₁-C₆ alkyl;

(v) a compound of Formula (Z⁹O)₂M²-O—

Si(OZ¹⁰)₃ (V), wherein M² represents a Group 13 metal and Z⁹ and Z¹⁰ each independently represent a C₁-C₆ alkyl group; and

(vi) a cyclic compound of Formula

9. The method of claim 8, wherein are the second compound is a compound of Formula (Ia), wherein each Z¹ represents a C₁-C₂ alkoxy group and Z² represents C₁-C₂ alkoxy group or a C₁-C₂ alkyl group.

10. The method of claim 9, wherein the compound of Formula (Ia) is 1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane.

11. The method of claim 8, wherein the second compound is a compound of Formula (II), wherein each R¹ represents a C₁-C₂ alkyl group and R², R³, and R⁴ are each independently a C₁-C₂ alkyl group, C₁-C₂ alkoxy group, a nitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, or a nitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkyl group.

12. The method of claim 11, wherein the compound of Formula (II) is selected from the group consisting of tetraethyl orthosilicate, methyltriethoxysilane, (N,N-dimethyl-aminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 4-methyl-1-(3-triethoxysilylpropyl)-piperazine, 4-(2-(triethoxysilyl)ethyl)pyridine, 1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole, and (3-aminopropyl)triethoxysilane.

13. The method of claim 8, wherein the second compound is a compound of Formula (III), wherein each Z⁵ represents a C₁-C₂ alkoxy group;

each Z⁶ and Z⁷ independently represent a C₁-C₂ alkoxy group, or a C₁-C₂ alkyl group; and

R is selected from the group consisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄ alkynylene group, and a nitrogen-containing C₄-C₁₀ alkylene group.

14. The method of claim 13, wherein the compound of Formula (III) is selected from the group consisting of 1,2-bis(methyldiethoxysilyl)ethane, bis(triethoxysilyl)methane, 1,2-bis-(triethoxysilyl)ethylene, N,N′

-bis[(3-trimethoxysilyl)propyl]ethylenediamine, bis[(methyl-diethoxysilyl)propyl]amine, and bis[(methyldimethoxysilyl)propyl]-N-methylamine.

15. The method of claim 8, the second compound is a compound of Formula (IV), wherein M¹ is Al or B and each Z⁸ represents a C₁-C₄ alkyl group.

16. The method of claim 8, the second compound is a compound of Formula (V), wherein M² is Al or B;

and Z⁹ and Z¹⁰ each independently represent a C₁-C₄ alkyl group.

17. The method of claim 15, wherein the second compound is selected from the group consisting of aluminum trimethoxide, aluminum triethoxide, aluminum isopropoxide, and aluminum-tri-sec-butoxide.

18. The method of claim 8, wherein the second compound is a compound of Formula (VI), wherein each X¹ represents a C₁-C₂ alkyl group;

X² and X³ each independently represent a C₁-C₂ alkyl group or a C₁-C₂ alkoxy group; and

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

19. The method of claim 18, wherein the compound of Formula (VI) is tris(3-trimethoxysilylpropyl)isocyanurate.

20. The method of claim 1, wherein the aqueous mixture comprises a base and has a pH from about 8 to about 15.

21. The method of claim 20, wherein the base is ammonium hydroxide or a metal hydroxide.

22. The method of claim 1, wherein the aqueous mixture comprises an acid and has a pH from about 0.01 to about 6.0.

23. The method of claim 22, wherein the acid is an inorganic acid.

24. The method of claim 23, wherein the inorganic acid is hydrochloric acid.

25. The method of claim 1, wherein the slurry is aged in step (d) for up to 24 hours at a temperature of about 20°

C. to about 125°

C.

26. The method of claim 1, wherein the slurry is dried at a temperature of about 70°

C. to about 150°

C.

27. The method of claim 1, wherein step (c) is repeated one or more times to produce a thicker coating.

28. The method of claim 1, further comprising pre-treating the substrate.

29. The method of claim 28, wherein pre-treating the substrate comprises applying a solution comprising an oxidizing agent and an inorganic acid to the substrate.

30. The method of claim 29, wherein the oxidizing agent is hydrogen peroxide.

31. The method of claim 29, wherein the inorganic acid is sulfuric acid.

32. The method of claim 1, wherein the organosilica material has an average pore diameter of about 2.0 nm to about 25.0 nm.

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

34. The method of claim 1, wherein the organosilica material has a pore volume of 0.1 cm³/g about 3.0 cm³/g.

35. The method of claim 1 further comprising agitating the slurry before coating.

36. The method of claim 1, wherein the adsorbent material is selected from the group consisting of a microporous adsorbent material, a mesoporous adsorbent material, an analogous periodic mesoporous adsorbent material, a metal oxide, a carbon, and a combination thereof.

37. The method of claim 1, wherein the adsorbent material is a zeolite.

38. The method of claim 37, wherein the zeolite is selected from the group consisting of a cationic form of zeolite A, Y, dealuminized Y, or Linde L;

chabazite;

erionite;

mordenite;

zeolite Beta;

a ZSM-type zeolite;

MCM-22;

MCM-49;

Nu-87;

UTD-1;

CIT-5;

EMC-2; and

Cloverite.

39. The method of claim 1, wherein the solution is stirred for at least 18 hours before adding the adsorbent material.

40. The method of claim 1, further comprising adding a C₁-C₄ alcohol to the solution.

41. The method of claim 39, wherein the C₁-C₄ alcohol is ethanol.

42. The method of claim 1, further comprising adding an additional amount of the compound of Formula (Ia) to the slurry.

43. The method of claim 42, wherein the compound of Formula (Ia) is 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane.

44. The method of claim 1, further comprising supplying a purge gas to the substrate after coating.

45. The method of claim 44, wherein the purge gas is an inert gas.

46. The method of claim 45, wherein the inert gas is nitrogen.

47. The method of claim 1, wherein the substrate is selected from the group consisting of a capillary tube, a microchannel, a monolith, a spherical silica particle and a silicon wafer.

48. The method of claim 1, wherein the method does not comprise a calcination step.

49. The method of claim 1, wherein the coating has a thickness of up to about 150 μ

m.

50. The method of claim 48, wherein the coating comprises about 1% to about 50% organosilica material as a binder.

51. An organosilica material-coated substrate made according to claim 1.

52. A gas separation process comprising contacting a gas mixture comprising CH₄ and at least one contaminant selected from the group consisting CO₂, H₂O, H₂S, NO_x, and SO_x with the organosilica material-coated substrate of claim 51.

53. The gas separation process of claim 52, wherein the process comprises PSA, TSA, PPSA, PTSA, RCPSA, RCTSA, RCPPSA or RCPTSA.