Membrane fabrication methods using organosilica materials and uses thereof

• US 10,576,453 B2
• Filed: 12/11/2015
• Issued: 03/03/2020
• 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, Bhandari, Dhaval Ajit, McCool, Benjamin A.
• Primary Examiner(s): McDonald, Katherine Zalasky
• Application Number:
  US14/966,445
• Publication Number:
  US 20160168485A1
• Time in Patent Office: 1,544 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 2257/504 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 53/0462 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: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 69/108 Inorganic support material
• 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 20/262 : 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 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: 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

Abstract

Methods for fabricating a membrane with 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 support 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 support are provided. Methods of removing a contaminant from a hydrocarbon stream are also provided.

Claims

1. A method for fabricating a membrane, the method comprising:

(a) adding at least one cyclic compound of Formula [Z¹Z²SiCH₂]₃ (Ia) into an aqueous mixture to form a solution, wherein the aqueous mixture and the solution contain essentially no structure directing agent or porogen and wherein the aqueous mixture comprises an acid and has a pH from about 0.01 to about 6.0, each Z¹ represents a C₁-C₄ alkoxy group and each Z² represents, a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group;

wherein the solution contains about 5.1 to about 5.4 wt. % of the compound of Formula (Ia) based on the total weight of the solution;

adding a C₁-C₄ alcohol to the solution;

(b) coating the solution onto a support, wherein the support is a ceramic support, a polymer support, a mixed-matrix support, a metallic support, a silica support, a carbon support, a liquid/facilitated transport support, a zeolite support, or combinations thereof, to form a coated support;

(c) aging the coated support; and

(d) drying the coated support to obtain a membrane comprising an organosilica material which is a polymer comprising independent units of Formula [Z³Z⁴SiCH₂]₃ (I), wherein each Z³ represents a hydroxyl group or an oxygen atom bonded to a silicon atom of another unit or an active site on the support and each Z⁴ represents a hydroxyl group or an oxygen atom bonded to a silicon atom of another unit or an active site on the support, wherein the organosilica material has an X-ray diffraction spectrum exhibiting substantially no peaks above 6 degrees 2θ

.

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, 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 C₁C₄ 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 Z¹⁰each independently represent a C₁-C₆ alkyl group;

(vi) a cyclic compound of Formula

7. The method of claim 6, wherein the second compound is a compound of Formula (Ia), wherein each Z¹ represents a C₁-C₂ alkoxy group and each Z² represents C₁-C₂ alkoxy group or a C₁-C₂ alkyl group.

8. The method of claim 7, wherein the compound of Formula (Ia) is 1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane.

9. The method of claim 6, 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.

10. The method of claim 9, 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-(triethoxysily)ethyl)pyridine, 1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole, and (3-aminopropyl)triethoxysilane.

11. The method of claim 6, wherein the second compound is a compound of Formula (III), wherein 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.

12. The method of claim 11, 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.

13. The method of claim 6, wherein the second compound is a compound of Formula (IV), wherein M¹ is Al or B and each Z⁸ represents a C₁-C₄ alkyl group.

14. The method of claim 6, wherein 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.

15. The method of claim 13, wherein the second compound is selected from the group consisting of aluminum trimethoxide, aluminum triethoxide, aluminum isopropoxide, and aluminum-tri-sec-butoxide.

16. The method of claim 6, 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.

17. The method of claim 16, wherein the compound of Formula (VI) is tris(3-trimethoxysilylpropyl)isocyanurate.

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

19. The method of claim 18, wherein the base is ammonium hydroxide or a metal hydroxide.

20. The method of claim 1, wherein the acid is an inorganic acid.

21. The method of claim 1, wherein the inorganic acid is hydrochloric acid.

22. The method of claim 1, wherein the coated support is aged for up to 144 hours at a temperature of about room temperature 20°

C. to about 200°

C.

23. The method of claim 1, wherein the coated support is dried at a temperature of about 15°

C. to about 200°

C.

24. The method of claim 1, wherein step (c) comprises aging the coated support in the presence of water.

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

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

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

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

29. The method of claim 1, wherein the alcohol is ethanol.

30. The method of claim 1, wherein the membrane is no more than about 1 μ

m in thickness.

31. A membrane made according to the method of claim 1.

32. A method of removing microcarbon residue from a crude oil, the method comprising filtering a crude oil through the membrane of claim 31.

33. The method of claim 32, wherein membrane flux is 0.5 to 50 Gallons/ft²/day (GFD).

34. The method of claim 32, wherein microcarbon residue wt. % content of a permeate product stream is less than about 10% to about 90% of microcarbon residue wt. % content of a hydrocarbon feed stream.