Organosilica materials for use as adsorbents for oxygenate removal

• US 10,351,639 B2
• Filed: 12/11/2015
• Issued: 07/16/2019
• 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: Mertens, Machteld M. W., Canich, Jo Ann M., Ho, Suzzy C. H., Li, Quanchang
• Primary Examiner(s): Lee, Rip A
• Application Number:
  US15/526,521
• Publication Number:
  US 20170313791A1
• Time in Patent Office: 1,313 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 15/08 Selective adsorption, e.g. chromatography
• CPC Class Codes: B01D 2253/108 Zeolites
• 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 2257/7022 Aliphatic 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 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• 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 23/44 : Palladium
• CPC Class Codes: B01J 31/0274 : containing silicon ligands in coordination complexes B01J31/1608
• 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: 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 6/005 : from solid polymers
• 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: C10G 57/02 : with polymerisation
• 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 20/582 : Recycling of unreacted starting or intermediate materials

Abstract

This invention relates in certain aspects to a process for removing oxygenates from a stream, preferably a hydrocarbon stream comprising contacting an organosilica material with the hydrocarbon steam, where the organosilica material is a polymer of at least one monomer of Formula [Z¹OZ²SiCH₂]₃, wherein Z¹ represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a silicon atom of another monomer and Z² represents a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₆ alkyl group or an oxygen atom bonded to a silicon atom of another monomer.

Claims

1. A process to remove oxygenates from a hydrocarbon stream comprising contacting the hydrocarbon stream with an organosilica material that is a polymer of at least one monomer of Formula [Z¹OZ²SiCH₂]₃ (I), wherein Z¹ represents a hydrogen atom, a C₁-C₄ alkyl group, or a bond to a silicon atom of another monomer and Z² represents a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₆ alkyl group, or an oxygen atom bonded to a silicon atom of another monomer.

2. The process of claim 1 further comprising:

(i) providing hydrocarbon stream comprising a polyolefin product stream, wherein the polyolefin product stream comprises polyolefin product and unreacted monomer;

(ii) quenching the polyolefin product stream with a quenching agent selected from water, a C₁-C₈ alcohol, and combinations thereof, to produce a quenched polyolefin stream;

(iii) separating the quenched polyolefin stream into polyolefin product and a recycle stream; and

(iv) contacting at least a portion of the recycle stream with an adsorbent bed comprising the organosilica material to produce a treated recycle stream, wherein the recycle stream comprises quenching agent, one or more C₁-C₄₀ oxygenates, and, optionally, one or more C₆-C₁₂ conjugated or non-conjugated diene monomers, to remove the quenching agent and/or the C₁-C₄₀ oxygenates.

3. The process of claim 1, wherein Z² represents a hydroxyl group, a C₁-C₄ alkoxy group, or an oxygen atom bonded to a silicon atom of another monomer.

4. The process of claim 1, wherein Z¹ represents a hydrogen atom, methyl, ethyl or a bond to a silicon atom of another monomer and Z² represents a hydroxyl group, methyl, ethyl, ethoxy, methoxy, or an oxygen bonded to a silicon atom of another monomer.

5. The process of claim 1, wherein the polymer further comprises a second distinct monomer of Formula [Z¹OZ²SiCH₂]₃ (I).

6. The process of claim 1, wherein the organosilica material further comprises at least one monomer selected from the group consisting of:

(i) a monomer of Formula Z³OZ⁴Z⁵Z⁶Si (II), wherein Z³ represents a hydrogen atom or a C₁-C₄ alkyl group, or a bond to a silicon atom of another monomer; and

Z⁴, Z⁵ and Z⁶ are each independently 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, and a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer;

(ii) a monomer of Formula Z⁷Z⁸Z⁹Si—

R—

SiZ⁷Z⁸Z⁹ (III), wherein Z⁷ represents a hydroxyl group, a C₁-C₄ alkoxy group, or an oxygen atom bonded to a silicon atom of another comonomer;

Z⁸ and Z⁹ each independently represent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group, or an oxygen bonded to a silicon atom of another monomer; 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;

(iii) a trivalent metal oxide monomer of Formula M¹(OZ¹⁰)₃ (IV), wherein M¹ represents a Group 13 metal and Z¹⁰ represents a hydrogen atom, a C₁-C₆ alkyl or a bond to a silicon atom of another monomer;

(iv) a trivalent metal oxide monomer of Formula (Z¹¹O)₂M²-O—

Si(OZ¹²)₃ (V), wherein M² represents a Group 13 metal and Z¹¹ and Z¹² each independently represent a hydrogen atom, a C₁-C₆ alkyl group, or a bond to a silicon atom of another monomer;

(v) a cyclic polyurea monomer of Formula

7. The process of claim 2 wherein the polyolefin product stream comprises a polymer comprising ethylene, propylene and, optionally, diene.

8. The process of claim 1 wherein the organosilica material further comprises at least one cyclic polyurea monomer of Formula:

9. The process of claim 2, where the recycle stream has 50 wt % more C₄-C₄₀ oxygenates than the treated recycle stream.

10. The process of claim 2, where the adsorbent bed further comprises a zeolitic molecular sieve comprising a material selected from the group consisting of zeolite X, zeolite Y, zeolite A, faujasite, mordenite, ferrierite, and combinations thereof and is, optionally, binderless.

11. The process of claim 2, where the adsorbent bed further comprises an alumina adsorbent and/or a silica adsorbent.

12. The process of claim 1, wherein the organosilica material has:

(i) an average pore diameter between about 1.5 nm and about 25.0 nm;

(ii) a pore volume about 0.1 cm³/g to about 5.0 cm³/g; and

/or

(iii) a surface area of about 200 m²/g to about 2,500 m²/g.

13. The process of claim 1, wherein the organosilica material:

(i) has an X-Ray diffraction spectrum exhibiting substantially no peaks above 4 degrees 2θ

; and

/or

(ii) is made using substantially no added structure directing agent or porogen.

14. The process of claim 1, where the hydrocarbon stream comprises one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, an isomer thereof or a polymer thereof.

15. The process of claim 2, where the hydrocarbon stream comprises the effluent of a polymerization reactor.

16. The process of claim 2, wherein the adsorbent bed comprises at least two adsorbents, wherein one adsorbent of the at least two adsorbents is the organosilica material.

17. The process of claim 2, wherein the organosilica material adsorbent removes the one or more C₁-C₄₀ oxygenates and, optionally at least one other adsorbent in the bed removes the quenching agent.

18. The process of claim 2, wherein the organosilica material:

(i) has an X-Ray diffraction spectrum exhibiting substantially no peaks above 4 degrees 2θ

; and

/or

(ii) is made using substantially no added structure directing agent or porogen.

19. The process of claim 2, wherein the one or more C₆-C₁₂ non-conjugated diene monomers is present and selected from the group consisting of:

pentadiene, methyl-pentadiene, hexadiene, methyl-hexadiene octadiene, heptadiene, norbornadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, and combinations thereof.

20. The process of claim 2, wherein the treated recycle stream, after contact with the adsorbent bed, comprises 10 ppm or less C₄-C₄₀ oxygenates.

21. The process of claim 2, further comprising regenerating the adsorbent bed by heating the adsorbent bed to a temperature in the range of from about 150 to about 400°

C.

22. The process of claim 21, further comprising subjecting the adsorbent bed to a hot diluent wash prior to and/or after regeneration.

23. The process of claim 21, further comprising sparging the adsorbent bed with hot nitrogen prior to and/or after regeneration.

24. The process of claim 2, wherein when the recycle stream is in contact with the adsorbent bed, from about 70 wt % to about 99 wt % of C₁₈ oxygenates are absorbed and from about 10 wt % to about 45 wt % of non-conjugated dienes are absorbed by the adsorbent bed.

25. The process of claim 2, wherein the residence time of the recycle stream with the adsorbent is within the range of from about 5 to about 20 minutes.