ORGANOSILICA MATERIALS AND USES THEREOF

• US 20160168333A1
• Filed: 12/11/2015
• Published: 06/16/2016
• 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: Calabro, David Charles, Benitez, Kiara M., Gupta, Himanshu, Gleeson, James William, Podsiadlo, Paul, Li, Quanchang, Zhang, Lei, Xu, Xiaochun, Weigel, Scott J., Lacy, Darryl Donald, Kaul, Bal, Lai, Wenyih Frank
• Granted Patent: US 10,022,700 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• 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 71/701 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: 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
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

Methods of preparing organosilica materials, which are a polymer comprising of at least one independent cyclic polyurea monomer of Formula

wherein each R¹ is a Z¹OZ²Z³SiZ⁴ group, wherein each Z¹ represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a silicon atom of another monomer unit; each Z² and Z³ independently represent a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group or an oxygen atom bonded to a silicon atom of another monomer unit; and each Z⁴ represents a C₁-C₈ alkylene group bonded to a nitrogen atom of the cyclic polyurea are 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 cyclic polyurea monomer of Formula

2. The organosilica material of claim 1, wherein each Z¹ represents a hydrogen atom, a C₁-C₂ alkyl group or a bond to a silicon atom of another monomer unit;

each Z² and Z³ independently represent a hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group or an oxygen atom bonded to a silicon atom of another monomer unit and each Z⁴ represents a C₁-C₄ alkylene group bonded to a nitrogen atom of the cyclic polyurea.

3. The organosilica material of claim 1, wherein each Z¹ represents a hydrogen atom, methyl or a bond to a silicon atom of another monomer unit;

each Z² and Z³ independently represent a hydroxyl group, methoxy or an oxygen atom bonded to a silicon atom of another monomer unit and each Z⁴ represents —

CH₂CH₂CH₂—

bonded to a nitrogen atom of the cyclic polyurea.

4. The organosilica material of claim 1, wherein at least one independent unit of Formula (II) is present, wherein each Z⁵ represents a hydrogen atom, a C₁-C₂ alkyl or a bond to a silicon atom of another comonomer, and each Z⁶ represents a hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group or an oxygen bonded to a silicon atom of another monomer.

5. The organosilica material of claim 4, wherein each Z⁵ represent a hydrogen atom, ethyl or a bond to a silicon atom of another monomer and each Z⁶ represents a hydroxyl group, methyl, ethoxy or an oxygen bonded to a silicon atom of another monomer.

6. The organosilica material of claim 4, wherein each Z⁵ represent a hydrogen atom, ethyl or a bond to a silicon atom of another monomer and each Z⁶ represents a hydroxyl group, ethoxy or an oxygen bonded to a silicon atom of another monomer.

7. The organosilica material of claim 4, wherein each Z⁵ represent a hydrogen atom, ethyl or a bond to a silicon atom of another monomer and each Z⁶ represents methyl.

8. The organosilica material of claim 1, wherein at least one independent unit of Formula (III) is present, wherein each Z⁷ represents a hydrogen atom, a C₁-C₂ alkyl group or a bond to a silicon atom of another comonomer;

and Z⁸, Z⁹ and Z¹⁰ are each independently selected from the group consisting of a hydroxyl group, 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, and an oxygen atom bonded to a silicon atom of another monomer.

9. The organosilica material of claim 8, wherein each Z⁷ represents a hydrogen atom, methyl, ethyl, or a bond to a silicon atom of another comonomer;

and Z⁸, Z⁹ and Z¹⁰ are each independently selected from the group consisting of a hydroxyl group, methoxy, ethoxy, methyl,

10. The organosilica material of claim 1, wherein at least one independent unit of Formula (IV) is present, wherein each Z¹¹ represents a hydroxyl group, C₁-C₂ alkoxy group or an oxygen bonded to a silicon atom of another comonomer;

each Z¹² and Z¹³ independently represent a hydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group or an oxygen bonded to a silicon atom of another monomer; and

each R² is selected from the group consisting a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄ alkynylene group and a nitrogen-containing C₄-C₁₀ alkyl group.

11. The organosilica material of claim 10, wherein each independently represents a hydroxyl group, methoxy, ethoxy or an oxygen bonded to a silicon atom of another monomer;

each Z¹² and Z¹³ independently represent a hydroxyl group, methoxy, ethoxy, methyl or an oxygen bonded to a silicon atom of another monomer; and

each R² is selected from the group consisting of —

CH₂—

, —

CH₂CH₂—

, —

HC═

CH—

,

12. The organosilica material of claim 1, wherein at least one independent unit of Formula (V) is present, wherein M¹ is Al or B and each Z¹⁴ independently represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a silicon atom or another monomer.

13. The organosilica material of claim 1, wherein at least one independent unit of Formula (VI) is present, wherein M² is Al or B;

and each Z¹⁵ and each Z¹⁶ independently represent a hydrogen atom, a C₁-C₄ alkyl group or a bond to a silicon atom of another monomer.

14. The organosilica material of claim 1, wherein the organosilica material is mesoporous and has an average pore diameter of about 2.0 nm to about 25.0 nm.

15. 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.

16. The organosilica material of claim 1, wherein the organosilica material has a pore volume about 0.2 cm³/g to about 3.0 cm³/g.

17. A method for preparing the organosilica material of claim 1, the method comprising:

(a) providing an aqueous mixture that contains essentially no structure directing agent and/or porogen,

(b) adding at least one cyclic compound of Formula

18. The method of claim 17, wherein each X¹ represents a C₁-C₂ alkyl group;

each X² and X³ 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 17, wherein the at least one compound of Formula (Ia) is tris(3-trimethoxysilylpropyl)isocyanurate.

20. The method of claim 17 further comprising adding to the aqueous mixture at least one compound selected from the group consisting of

(i) a compound of Formula [X⁵OX⁶SiCH₂]₃ (IIa), wherein each X⁵ represents a C₁-C₄ alkyl group and each X⁶ represents a C₁-C₄ alkyl group or a C₁-C₄ alkoxy group;

(ii) a compound of Formula X⁷OX⁸X⁹X¹⁰Si (IIIa), wherein each X⁷ represents a C₁-C₆ alkyl group; and

X⁸, X⁹ and X¹⁰ are each independently selected from the group consisting of a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing heteroaralkyl group, and a nitrogen-containing optionally substituted heterocycloalkyl group;

(iii) a compound of Formula X¹¹X¹²X¹³Si—

R⁴—

SiX¹¹X¹²X¹³ (IVa), wherein each X¹¹ representsa C₁-C₄ alkoxy group;

each X¹² and X¹³ independently represent a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; and

each R⁴ 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; and

(iv) a source of a trivalent metal oxide.

21. The method of claim 20, wherein the at least one compound is a compound of Formula (IIa), wherein each X⁵ represents a C₁-C₂ alkyl group and each X⁶ represents a C₁-C₂ alkyl group or a C₁-C₂ alkoxy group.

22. The method of claim 20, wherein the compound of Formula (IIa) is 1,1,3,3,5,5-hexaethoxy-1,3,5-trisalacyclohexane or 1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane.

23. The method of claim 20, wherein the at least one compound is a compound of Formula (IIIa), wherein each X⁷ is a C₁-C₂ alkyl group;

and X⁸, X⁹ and X¹⁰ are each independently selected from the group consisting of a C₁-C₂ alkyl group, a 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.

24. The method of claim 23, wherein the compound of Formula (IIIa) is selected from the group consisting of tetraethyl orthosilicate or methyltriethoxysilane, (N,N-dimethylaminopropyl)trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 4-methyl-1-(3-triethoxysilylpropyl)-piperazine, 4-(2-(triethoxysily)ethyl)pyridine, 1-(3-(triethoxysilyl)propyl)-4, 5-dihydro-1H-imidazole, and (3-aminopropyl)triethoxysilane.

25. The method of claim 20, wherein the at least one compound is a compound of Formula (IVa), wherein each X¹¹ represents a C₁-C₂ alkoxy group;

each X¹² and X¹³ independently represent a C₁-C₂ alkoxy group or a C₁-C₂ alkyl group; and

each R⁴ is selected from the group consisting a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄ alkynylene group, and a nitrogen-containing C₄-C₁₀ alkylene group.

26. The method of claim 25, wherein the compound of Formula (IVa) 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[(methyldiethoxysilyl)propyl]amine, and bis[(methyldimethoxysilyl)propyl]-N-methylamine.

27. The method of claim 20, wherein the source of a trivalent metal oxide is at least one of:

(i) a compound of Formula M³(OX¹⁴)₃ (Va), wherein M³ represents a Group 13 metal and each X¹⁴ represents a C₁-C₆ alkyl;

or

(ii)a compound of Formula (X¹⁵O)²M⁴-O—

Si(OX¹⁶)₃ (VIa), wherein M⁴ represents a Group 13 metal and each X¹⁵ and each X¹⁶ independently a C₁-C₆ alkyl group.

28. The method of claim 27, wherein the source of trivalent metal is a compound of formula (Va), wherein M³ is Al or B and each X¹⁴ represents a C₁-C₄ alkyl group.

29. The method of claim 27, wherein the source of trivalent metal is a compound of formula (VIa), wherein M⁴ is Al or B;

and each X¹⁵ and each X¹⁶ independently represent a C₁-C₄ alkyl.

30. The method of claim 17, wherein the aqueous mixture comprises a base and has a pH from about 9 to about 14.

31. The method of claim 30, wherein the base is ammonium hydroxide or a metal hydroxide.

32. The method of claim 17, wherein the aqueous mixture comprises an acid and has a pH from about 0.3 to about 4.5.

33. The method of claim 32, wherein the acid is an inorganic acid.

34. The method of claim 33, wherein the acid is hydrochloric acid.

35. The method of claim 17, wherein the solution is aged in step (c) for up to 150 hours at a temperature of about 50°

C. to about 200°

C.

36. The method of claim 17, wherein the pre-product is dried at a temperature of about 70°

C. to about 200°

C.

37. An organosilica material obtainable by the method of claim 17.

38. A method for reducing impurities in a liquid hydrocarbon product comprising contacting the liquid hydrocarbon product with the organosilica material of claim 1.

39. The method of claim 38, wherein the liquid hydrocarbon product comprises diesel fuel, jet fuel, gasoline fuel and/or lube base stock.

40. The method of claim 38, wherein the impurities comprise polar compounds and/or aromatic compounds.

41. The method of claim 40, wherein the polar compounds comprise nitrogen-containing compounds and/or sulfur-containing compounds.

42. The method of claim 40, wherein the aromatic compounds comprise single ring aromatics, double ring aromatics, and/or multi-ring aromatics.

43. The method of claim 38, wherein the liquid hydrocarbon product comprises diesel fuel.

44. The method of claim 43, wherein at least about 0.1 wt. % of the multi-ring aromatics are removed from the diesel fuel.

45. The method of claim 43, wherein the diesel fuel is contacted with the organosilica material at a temperature of about 18°

C. to about 200°

C. and/or a pressure of about 5 psi to about 100 psi.

46. The method of claim 43, wherein the diesel fuel comprises less than or equal to about 50 ppm sulfur.

47. The method of claim 43, wherein the diesel fuel has a color level of less than or equal to 3.0 as measured according to D6045 ASTM following contact with the organosilica material.

48. The method of claim 38, wherein the organosilica material has selectivity of at least 1.3 for multi-ring aromatics compared to total ring aromatics.

49. The method of claim 38, wherein the organosilica material is packed into a column and the liquid hydrocarbon product is contacted therein.

50. The method of claim 43, wherein the diesel fuel is contacted with the organosilica material following hydrotreatment of the diesel fuel.

51. A method for improving color in a diesel fuel product comprising contacting the diesel fuel product with the organosilica material of claim 1 resulting in an improved color diesel fuel product.

52. The method of claim 51, wherein the diesel fuel product is contacted with the organosilica material at a temperature of about 18°

C. to about 80°

C. and/or a pressure of about 5 psi to about 16 psi.

53. The method of claim 51, wherein the diesel fuel product is contacted with the organosilica material following hydrotreatment of the diesel fuel.

54. The method of claim 51, wherein the diesel fuel product has a color level of at least about 5.0 as measured according to D6045 ASTM prior to contact with the organosilica material.

55. The method of claim 51, wherein the improved color diesel fuel product has a color level of less than or equal to about 3.0 as measured according to D6045 ASTM.

56. The method of claim 51, wherein the organosilica material is packed into a column.