WO2013109371A1 - Procédé d'obtention de polyoléfines liquides - Google Patents

Procédé d'obtention de polyoléfines liquides Download PDF

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Publication number
WO2013109371A1
WO2013109371A1 PCT/US2012/069904 US2012069904W WO2013109371A1 WO 2013109371 A1 WO2013109371 A1 WO 2013109371A1 US 2012069904 W US2012069904 W US 2012069904W WO 2013109371 A1 WO2013109371 A1 WO 2013109371A1
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Prior art keywords
wash fluid
catalyst
reactor
liquid
filter
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PCT/US2012/069904
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English (en)
Inventor
Kenneth A. BAHLER
Aaron L. WETTERLIND
Patrick R. FORD
Derrick L. LATON
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Exxonmobil Chemical Patents Inc.
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Priority claimed from US13/351,338 external-priority patent/US20120165580A1/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Publication of WO2013109371A1 publication Critical patent/WO2013109371A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C10M2205/0225—Ethene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • Poly alpha-olefins comprise a class of hydrocarbons manufactured by the catalytic oligomerization (polymerization to low-molecular-weight products) of linear alpha- olefin (LAO) monomers. These typically range from 1-octene to 1-dodecene, although oligomeric copolymers of lower olefins such as ethylene and propylene may also be used, including copolymers of ethylene with higher olefins as described in U.S. Patent 4,956, 122 and the patents referred to therein. PAO products have achieved importance in the lubricating oil market.
  • PAO synthetic hydrocarbon fluids
  • HVI-PAO high viscosity index PAO
  • PAOs and HVI-PAOs of different viscosity grades may be produced using promoted BF 3 or AICI 3 catalysts.
  • PAOs have found commercial success in the lubricant field for their superiority to mineral based lubricants.
  • research efforts have led to PAO fluids exhibiting useful viscosities over a wide range of temperatures, i.e., improved viscosity index, while also showing lubricity, thermal and oxidative stability and pour point equal to or better than mineral oil.
  • These relatively new synthetic lubricants lower mechanical friction, enhancing mechanical efficiency over the full spectrum of mechanical loads and do so over a wider range of operating conditions than mineral oil lubricants.
  • This invention is directed toward an improved process to make a polyolefin product, and specifically an improved filter cake wash system.
  • a method for preparing a liquid polyolefin comprising: contacting a feedstock comprising at least one olefin monomer with a catalyst system to produce a reactor effluent stream; filtering the reactor effluent stream, washing a created filter cake with a warm wash fluid comprising at least one hydrocarbon liquid; separating at least a portion of the wash fluid off during and after the washing; sending said portion of the wash fluid through a distillation process; and recovering at least a portion of the liquid polyolefin that was trapped in the filter cake.
  • This process may further comprise the steps of, prior to filtering, contacting the reactor effluent stream with a deactivator to deactivate the residual catalyst to produce a deactivated reactor effluent stream, and contacting the deactivated reactor effluent stream with a sorbent, wherein the sorbent is capable of chemically and physically interacting with the residual catalyst. It may also comprise the steps of, after distilling the separated portion of the wash fluid, recycling the light olefins obtained from this wash fluid to the reactor for further conversion into product and / or recycling the heavy olefins obtained from this wash fluid to the filter for use as additional wash fluid.
  • FIG. 1 is a simplified flow diagram of the manufacturing process in an embodiment of the invention.
  • This invention is directed toward an improved process to make a polyolefin, and specifically an improved filter cake wash system. While several embodiments of the invention will be specifically described, various other modifications will be apparent to and could be readily made by those skilled in the art in possession of this disclosure without departing from the spirit and scope of the invention. Accordingly, it is not intended that the claims be limited to the examples or descriptions set forth but rather that the claims be construed as encompassing all features of patentable novelty in the present invention, including all features which would be treated as equivalents by those skilled in the art.
  • Polyolefins are manufactured by the catalytic oligomerization of olefins, preferably alpha-olefins, and preferably LAO monomers.
  • Useful alpha-olefins are typically selected from C5 to C30 alpha-olefins and any mixture thereof.
  • mixture of alpha-olefins, it is meant that at least two different alpha-olefins are present in the feed. In embodiments of the invention where the feed is a mixture, the feed may comprise anywhere from 2 to 25 different alpha-olefins.
  • the feed may comprise at least two, or at least three, or at least four, or at least five, or at least six, or at least seven, or at least eight, and so on, different feeds.
  • the embodiments of the invention may be further characterized by having no single alpha-olefin present in an amount greater than 80 wt%, or 60 wt%, or 50 wt%, or 49 wt%, or 40 wt%, or 33 wt%, or 30 wt%, or 25 wt%, or 20 wt%.
  • the amounts of a particular alpha-olefin present in a feed will be specified herein as percent by weight of the entire amount of alpha-olefin in the feed, unless otherwise specified.
  • the feed may also comprise an inert (with respect to the oligomerization reaction in question) material, such as a carrier, a solvent, or other olefin component that is not an alpha-olefin.
  • examples are propane, n-butane, iso-butane, cis- or trans-2-butenes, iso-butenes, and the like, that may be present with propylene or 1- butene feed.
  • Other examples are the impurity internal olefins or vinylidene olefins that are present in the alpha-olefin feed.
  • Feeds may be advantageously selected from C 5 to C 30 , C5 to C24, C5 to Cis, C5 to Ci6, C5 to Ci4, Ce to C20, Ce to Ci8, Ce to Ci6, or Ce to C14 alpha-olefins, among other possible feed sources, such as any lower limit listed herein to any upper limit listed herein.
  • the feed will comprise at least one monomer selected from propylene, 1-butene, 1 -pentene, 1 -hexene to 1-heptene and at least one monomer selected from C12-C18 alpha-olefins.
  • the amount of ethylene in the feed is not more than 10 mol%.
  • one acceptable mixed feed is any mixture of 1 - hexene, 1-octene, 1-decene, 1 -dodecene, and 1-tetradecene.
  • Mixtures in all proportions may be used, e.g., from about 1 wt% to about 90 wt% 1-hexene, from about 1 wt% to about 90 wt% 1-octene, from about 1 wt% to about 90 wt% 1-decene, from about 1 wt% to about 90 wt% 1 -dodecene, and from about 1 wt% to about 90 wt% tetradecene.
  • 1 -hexene is present in the amount of about 1 wt%, 2 wt%, 3 wt%, 4 wt% or 5 wt% to about 10 wt% or 20 wt%
  • 1 -octene is present in the amount of 40 wt%, 50 wt%, or 60 wt% to about 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt%
  • 1 - decene is present in the amount of about 25 wt%, 30 wt%, 40 wt% or 50 wt% to about 60 wt%, 70 wt% or 75 wt%
  • 1 -dodecene is present in the amount of about 10 wt%, 20 wt%, 25 wt%, 30 wt% or 40 wt% to about 45 wt%, 50 wt% or 60 wt
  • Ranges from any lower limit to any higher limit just disclosed are contemplated, e.g., from about 3 wt% to about 10 wt% 1 -hexene or from about 2 wt% to about 20 wt% 1 -hexene, from about 40 to 95% 1-octene, from about 25 wt% to about 70 wt% 1 -decene or from about 40 wt% to about 70 wt% 1-decene, from about 10 wt% to about 45 wt% 1-dodecene or from about 25 wt% to about 50 wt% 1 -dodecene, and from about 5 wt% to about 30 wt% 1-tetradecene or from about 15 wt% to about 50 wt% 1 - tetradecene. Numerous other ranges are contemplated, such as ranges plus or minus 5% ( ⁇ 5%) from those specified in the examples.
  • the mixed feed (or mixture of alpha-olefins contacting the oligomerization catalyst and promoters) consists essentially of 1 -hexene, 1 - octene, 1-decene, 1-dodecene, and/or 1 -tetradecene, wherein the phrase "consists essentially of (or “consisting essentially of and the like) takes its ordinary meaning, so that no other alpha-olefin is present (or for that matter nothing else is present) that would affect the basic and novel features of the present invention.
  • the mixed feed consists of 1 -hexene, 1 -octene, 1-decene, 1 -dodecene, and/or 1 - tetradecene, meaning that no other olefin is present (allowing for inevitable impurities).
  • Another mixed feedstock useful in the present invention is a mixed feed of 1- hexene, 1-decene, and 1-tetradecene.
  • Mixtures in all proportions may be used, e.g., from about 1 wt% to about 90 wt% 1-hexene, from about 1 wt% to about 90 wt% 1-decene, and from about 1 wt% to about 90 wt% 1-tetradecene.
  • the 1-hexene is present in amounts of 1 wt%, 2 wt%, 3 wt%, 4 wt% or 5 wt% to about 10 wt%, 20 wt%, 25 wt% or 30 wt%
  • 1-decene is present in the amount of about 25 wt%, 30 wt%, 40 wt% or 50 wt% to about 60 wt%, 70 wt% or 75 wt%
  • 1-tetradecene is present in the amount of 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt% or 25 wt% to about 30 wt% or 40 wt%. Ranges from any lower limit to any higher limit just disclosed are contemplated.
  • Mixed feedstocks of two LAOs are also contemplated by the present invention.
  • Such two component feedstocks may be blends of 1-hexene and 1-decene, 1-hexene and 1- dodecene, 1-decene and 1-dodecene, 1-decene and 1-tetradecene, or 1-dodecene and 1- tetradecene.
  • either component may be present in amounts of 1 wt% to 99 wt%, with preferred ranges for both components being in the ranges of 10 wt% to 90 wt%, 15 wt% to 85 wt%, 20 wt% to 80 wt%, or 30 wt% to 70 wt%.
  • the olefin feed consists essentially of a single LAO such as 1-decene, 1-dodecene, or the like.
  • Particularly advantageous feedstocks include alpha-olefins derived from an ethylene growth process, from Fischer-Tropsch synthesis, from steam or thermal cracking processes, syn-gas synthesis, C 4 stream containing 1-butene from refinery operation, such as Raff- 1 or Raff-2 stream, and so forth.
  • the alpha-olefin made from ethylene growth processes contains only even-number olefins.
  • Alpha-olefins containing both even- and odd-number olefins can also be made from steam cracking or thermal cracking of wax, such as petroleum wax, Fischer-Tropsch wax, or any other readily available hydrocarbon wax.
  • Alpha-olefins can also be made in a Fischer-Tropsch synthesis process.
  • Alpha-olefins can also be made directly from syngas synthesis processes, which can produce significant amounts of C3-C15 alpha-olefins, containing both even- and odd-number olefins.
  • alpha-olefins containing other inert components including saturated hydrocarbons, internal or vinylidene olefins or aromatic diluents can also be used as feed.
  • the alpha-olefin would be reacted to give polymer and inert components that will be passed through the reactor unaffected.
  • the polymerization process is also a separation process.
  • the olefins used in the feed are co-fed into the reactor.
  • the olefins are fed separately into the reactor.
  • the catalyst/promoters may also be feed separately or together, with respect to each other and with respect to the alpha-olefin species.
  • the catalyst system may be any catalyst system capable of producing polyolefins.
  • Catalyst system is defined herein to mean a catalyst precursor/activator pair. When “catalyst system” is used to describe such a pair before activation, it means the unactivated catalyst (precatalyst) together with an activator and, optionally, a co-activator (such as a trialkyl aluminum compound). When it is used to describe such a pair after activation, it means the activated catalyst and the activator or other charge-balancing moiety. Furthermore, this activated "catalyst system” may optionally comprise the co-activator and/or other charge-balancing moiety.
  • the catalyst system contains at least one activated metallocene catalyst.
  • the catalyst system comprises a metallocene compound (selected from one or more compounds according to Formula 1, below) together with an activator, optionally a co-activator, and optionally a scavenger.
  • M is selected from Group 4 transition metals, preferably zirconium (Zr), hafnium (Hf), and titanium (Ti),
  • Li and L 2 are independently selected from cyclopentadienyl (“Cp”), indenyl, and fluorenyl, which may be substituted or unsubstituted, and which may be partially hydrogenated,
  • A is an optional bridging group which if present, is preferably selected from dialkylsilyl, dialkylmethyl, ethenyl (-CH 2 -CH 2 -), alkylethenyl (-CR2-CR2-), where alkyl can be independently hydrogen radical, Ci to Ci 6 alkyl radical or phenyl, tolyl, xylyl radical and the like, and
  • X a and X b are independently selected from halides, OR (R is an alkyl group, preferably selected from Ci to C5 straight or branched chain alkyl groups), hydrogen, Ci to Ci 6 alkyl or aryl groups, haloalkyl, and the like.
  • substitution to the ligand may be hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl.
  • substitution may also be within the ring giving heterocyclopentadienyl ligands, heteroindenyl ligands or heterotetrahydroindenyl ligands, each of which can additionally be substituted or unsubstituted.
  • hydrocarbyl radical is a Ci-Cioo radical that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic, and include substituted hydrocarbyl radicals, halocarbyl radicals, and substituted halocarbyl radicals, silylcarbyl radicals, and germylcarbyl radicals as these terms are defined below.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been substituted with at least one functional group.
  • Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one halogen (e.g., F, CI, Br, I) or halogen- containing group (e.g., CF 3 ).
  • halogen e.g., F, CI, Br, I
  • halogen- containing group e.g., CF 3
  • Substituted halocarbyl radicals are radicals in which at least one halocarbyl hydrogen or halogen atom has been substituted with at least one functional group.
  • Silylcarbyl radicals are groups in which the silyl functionality is bonded directly to the indicated atom or atoms.
  • Germylcarbyl radicals also called germylcarbyls
  • Polar radicals or polar groups are groups in which the heteroatom functionality is bonded directly to the indicated atom or atoms. They include heteroatoms of groups 1-17 of the Periodic Table either alone or connected to other elements by covalent or other interactions such as ionic, van der Waals forces, or hydrogen bonding.
  • Catalysts such as 1,2,3,4-tetramethylcyclopentadienylzirconium dichloride, 1,2,4- tri methylcyclopentadienylzirconium dichloride, or pentamethylcyclopentadienyl zirconium dichloride or their dialkyl analogs are preferred.
  • Certain bridged and bridged with substitution catalysts such as the di-halides or dialkyls of dimethylsilylbis[indenyl]zirconium or dimethylsilylbis[tetrahydro-indenyl]zirconium dimethylsilylbis[ 1 - methylindenyljzirconium or their hafnium analogs, etc. are also desirable.
  • Activators that may be used include aluminoxanes such as methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane, z ' so-butyl aluminoxane and the like, or non-coordinating anions (NCAs) such as Lewis acid activators including triphenyl boron, tris-perfluorophenyl boron, tris-perfluorophenyl aluminum and the like, or ionic activators including dimethylanilinium tetrakis perfluorophenyl borate, triphenyl carbonium tetrakis perfluorophenyl borate, dimethylanilinium tetrakis perfluorophenyl aluminate, and the like.
  • NCAs non-coordinating anions
  • a non-coordinating anion is an anion which either does not coordinate to the catalyst metal cation or that coordinates only weakly to the metal cation.
  • An NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer, can displace it from the catalyst center.
  • Any metal or metalloid that can form a compatible, weakly coordinating complex with the catalyst metal cation may be used or contained in the NCA.
  • Suitable metals include, but are not limited to, aluminum, gold, and platinum.
  • Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.
  • NCAs comprises stoichiometric activators, which can be either neutral or ionic.
  • stoichiometric activators can be either neutral or ionic.
  • ionic activator, and stoichiometric ionic activator can be used interchangeably.
  • neutral stoichiometric activator and Lewis acid activator can be used interchangeably.
  • a co-activator is a compound capable of alkylating the transition metal complex, such that when used in combination with an activator, an active catalyst is formed.
  • Co- activators include aluminoxanes such as methyl aluminoxane, modified aluminoxanes such as modified methyl aluminoxane, and trialkyl aluminums such as trimethyl aluminum, tri- isobutyl aluminum, triethyl aluminum, and tri-isopropyl aluminum, tri-n-hexyl aluminum, tri- n-octyl aluminum, tri-n-decyl aluminum or tri-n-dodecyl aluminum.
  • Co-activators are typically used in combination with Lewis acid activators and ionic activators when the pre- catalyst is not a dihydrocarbyl or dihydride complex. Sometimes co-activators are also used as scavengers to deactivate impurities in feed or reactors.
  • the range of methylalumoxane used is typically in the range of 0.1 milligram (mg) to 500 mg/g of alpha- olefin feed. A more preferred range is from 0.05 mg to 10 mg/g of alpha-olefin feed.
  • the molar ratios of the aluminum to metallocene (Al/M molar ration) range are from 2 to 4000, preferably 10 to 2000, more preferably 50 to 1000, preferably 100 to 500.
  • the metallocene use is typically in the range of 0.01 microgram to 500 micrograms of metallocene component per gram of alpha-olefin feed, preferably 0.1 microgram to 100 microgram of metallocene component per gram of alpha-olefin feed.
  • the molar ratio of the NCA activator to metallocene is in the range from 0.1 to 10, preferably 0.5 to 5, preferably 0.5 to 3. If a co-activator of alkylaluminum compound is used, the molar ratio of the Al to metallocene is in the range from 1 to 1000, preferably 2 to 500, preferably 4 to 400.
  • Other components used in the reactor system can include inert solvent, catalyst diluent, etc. These components can also be recycled during the operation.
  • polymerization reaction conditions may generally be determined by one of ordinary skill in the art in possession of this disclosure, typical conditions are discussed below. While it is recognized that oligomerization generally refers to the conversion of monomers to a finite degree of polymerization, the terms "polymerization” and “oligomerization” are used interchangeably in this disclosure and the advantages of this invention are useful in either type of reaction.
  • the polymerization process will typically occur in a homogeneous or colloidal solution process.
  • this involves polymerization in a continuous reactor in which the starting feed, catalyst materials, and polymer formed are agitated to reduce or avoid concentration or temperature gradients.
  • the process can be advantageously carried out in a conventional continuous stirred tank reactor (CSTR), a batch reactor, or plug flow reactor, or more than one reactor operated in series or parallel.
  • CSTR continuous stirred tank reactor
  • a typical CSTR has an internal agitator at the bottom of the reactor to continuously mix the reactor contents.
  • constant movement of the reactor contents in a tank reactor may be achieved by other means that do not require an internal agitator, such as spray nozzles or a combination of spray nozzles and internal baffles.
  • temperature may be controlled in any reactor by balancing the heat of polymerization with reactor cooling via reactor jackets or cooling coils, a cooled side-stream of reactant to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers, or solvent), or any combination of these methods.
  • Adiabatic reactors with pre-chilled feeds may also be used.
  • the optimal reactor temperature depends on the catalyst used and the product desired. Higher temperatures tend to give lower molecular weights and lower temperatures tend to give higher molecular weights, however this is not an absolute rule.
  • the reactor temperature can vary between about 0°C and about 300°C, preferably from about 10°C to about 250°C, and most preferably from about 25°C to about 230°C.
  • MWD molecular weight distribution
  • multiple reactors are used in series or in parallel, it is also useful to keep the temperature constant if narrow MWD is desired.
  • the second reactor temperature can be higher than the first reactor temperature. In parallel reactor operation, the temperatures of the two reactors are independent. One can also affect MWD of the products by using two different types of metallocene catalysts.
  • the pressure in any reactor can vary typically from about 0.1 atmosphere to 100 atmosphere (10 kPa to 10,100 kPa), preferably from 0.5 atm to 75 atm (50 kPa to 7600 kPa), and most preferably from 1.0 atm to 50 atm (101 kPa to 5066 kPa).
  • the reaction can be carried out under the atmosphere of nitrogen or hydrogen.
  • a small amount of hydrogen may be added to the reactor to improve the catalyst productivity.
  • the amount of hydrogen is preferred to be kept at a high enough level to improve catalyst productivity, but not high enough to introduce hydrogenation of olefins, especially the feed olefins because the conversion of alpha-olefins into saturated paraffins is very detrimental to the efficiency of the process.
  • the amount of hydrogen partial pressure is preferably less than 200 psi (1379 kPa), preferably less than 150 psi (1034 kPa), preferably less than 100 psi (689 kPa), preferably less than 50 psi (345 kPa), preferably less than 25 psi (172 kPa), preferably less than 10 psi (69 kPa), preferably less than 5 psi (34 kPa), and preferably less than 1 psi (6.9 kPa).
  • the concentration of hydrogen in the reactant phase is less than 200 ppm, preferably less than 100 ppm, preferably less than 50 ppm, preferably less than 10 ppm, and preferably less than 1 ppm.
  • the reaction time or reactor residence time is usually dependent on the catalyst used, amount of catalyst system used, and desired conversion level. Usually the amount of catalyst system used is determinative. Higher catalyst loading tends to gives higher conversion in a shorter reaction time. However, at a point, high catalyst loading also makes it difficult to manage reaction heat or temperature and makes the process uneconomical. Therefore, it is useful to choose a catalyst with maximum catalyst productivity to minimize the amount of catalyst system needed. Desirable residence times may be determined by one of ordinary skill in the art in possession of this disclosure, and will typically range from 1 minute to 20 hours, or more typically 5 minutes to 10 hours. See, for instance, U.S. Patent 5,705,577 for typical process conditions.
  • the reaction process comprises contacting olefin monomers with the catalyst system, preferably in a suitable diluent, solvent, recycle, or mixture thereof, and allowing the reaction to occur for a sufficient time to produce the desired polymers or oligomers.
  • suitable diluents or solvents include both aliphatic and aromatic hydrocarbons. Aromatics such as benzene, toluene, xylenes, ethylbenzene, propylbenzene, cumene, t-butylbenzene are suitable.
  • Alkanes such as hexane, heptane, pentane, isopentane, and octane, NorparTM fluids or IsoparTM fluids from ExxonMobil Chemical Company in Houston, Texas are also suitable.
  • Toluene is a preferred substance for dissolving catalyst components.
  • NorparTM fluids, IsoparTM fluids, or hexanes (or mixtures thereof) are preferred as reaction diluents. Oftentimes, a mixture of toluene and NorparTM or IsoparTM fluids is used as a diluent or solvent.
  • the reactor effluent is withdrawn from the reactor, see FIG. 1.
  • the reactor effluent comprises at least one liquid polyolefin, residual catalyst, and unreacted olefin monomer, and may further comprise compounds considered inerts such as internal olefins, branched olefins, and paraffins that entered the system via the feedstock or reaction in the reactor.
  • the term "residual catalyst” as used herein will include unreacted catalyst precursor, if any, unreacted activated catalyst and various forms of the catalyst which may be formed during the reaction, as well as any unused co-activator.
  • the reactor effluent may also contain one or more other diluents or solvents, and scavengers added to the reactor.
  • the reactor effluent may be treated to deactivate the residual catalyst and, if necessary, any co-activator and scavenger. Deactivation is typically accomplished by introduction of air, CO 2 , water or other deactivator. This may be either in an adjacent deactivation vessel or the deactivation agent may be fed into the effluent pipe under conditions of static mixing.
  • the reactor effluent comprising the deactivated residual catalyst may be referred to as "deactivated effluent.”
  • removal of the residual catalyst from the deactivated effluent begins in the mix tank, see FIG. 1.
  • At least one sorbent having an active surface area and pore volume capable of adsorbing the catalyst components is mixed with the deactivated effluent.
  • suitable solid sorbents are natural or synthetic clay, modified clay, diatomaceous earth, activated charcoal, silica gel, alumina, aluminosilicate, zeolites, molecular sieves, cellulose material, metal oxides or metal salts, such as calcium oxides, magnesium oxides, titanium oxides, zirconium oxides, aluminum oxides, activated or treated in appropriate manners.
  • the sorbent should have a surface area greater than 0.1 m 2 / gram and a pore volume of greater than 0.01 cc/gram.
  • the sorbent may have both chemical and physical active sites to interact with the catalyst components.
  • Such solid sorbents having surface hydroxyl or oxygen groups thereon yield chemical reactions with the catalyst components thereby providing strong sorption of the catalyst components and facilitating the high degree of catalyst removal.
  • the sorbent may also act as catalyst poison to deactivate the polymerization reaction. If the sorbent contains a sufficient amount of water or oxygen on its molecular surface, no extra catalyst deactivator may be needed prior to treating the reactor effluent with the solid sorbent.
  • the sorbent may be introduced to the deactivated effluent in either dry form or it may be pre-blended with a hydrocarbon fluid to form a sorbent slurry.
  • the hydrocarbon fluid may be any suitable non-reactive hydrocarbon fluid.
  • a "non-reactive hydrocarbon fluid" as used herein is a fluid that does not react with the sorbent or any components of the deactivated effluent stream.
  • the hydrocarbon fluid may be any C5 to C30 fluid, and is preferably selected to correspond to one of the fluids that was used either as a feedstock to the reactor or a catalyst diluent.
  • a filter system such as a membrane filter or any suitable commercial filter, which may be packed with filter aide or other solid material which functions both as filter aide and an additional catalyst sorbent.
  • suitable filtering systems include a filter drum or a solid filter bed.
  • a useful filter system is a pressure leaf filter, such as a FU DA® pressure leaf filter drum. The individual filter leafs are precoated with a sorbent prior to introduction of the deactivated effluent.
  • Precoating is done with a sorbent slurry which settles on the filter leafs as the slurry vertically flows through the drum.
  • the slurry is a blend of a solid sorbent and a hydrocarbon fluid.
  • the solid sorbent may or may not be identical to the solid sorbent used in the mix tank in the first step of catalyst removal.
  • Particularly preferred sorbents include silica, alumina, activated alumina, di-atomaceous earth filter aid, zeolites of different pore size, MCM41, natural or synthetic clay materials, micro crystalline material or powdered cellulose material with hydroxyl group.
  • the sorbent can be used by itself or mixed with other sorbents.
  • the hydrocarbon fluid in the sorbent slurry may be any inert C5 to C30 fluid, and is preferably selected to correspond to one of the fluids that was used either as a feedstock to the reactor or a catalyst diluent.
  • the hydrocarbon fluid used in the sorbent slurry is the same as used in the mix tank and is also unreactive with the sorbent and components of the deactivated effluent stream.
  • Filtering may be either a continuous or batch operation.
  • the factors to consider in determining optimal mode include a) type of filter; b) filter capacity; c) reactor capacity; d) reactor operation mode; and e) mix tank capacity, and such determination can be made by one of ordinary skill in the art in possession of this disclosure.
  • the filtered liquid flows from a discharge valve at the bottom of the filter drum.
  • the filtered liquid contains polyolefin product, unreacted monomers, hydrocarbon liquids used as diluents, catalyst deactivator, and/or sorbent slurry liquid.
  • the filtered liquid may also contain inerts introduced via the feedstream or unintentionally generated in the reactor.
  • the filter cake even after draining the filtered liquid, may appear dry, due to the highly sorbent nature of the solids, the cake may actually contain up to 75% liquid. This liquid will have a fractional content about equivalent to the liquid exiting the reactor. Thus, if the reactor effluent is 90 vol% polyolefin product and 10 vol% other materials, the liquid trapped in the filter cake will also be about 90 vol% polyolefin product. Thus, prior to removal of the filter cake from the filter, the filter cake is washed with a wash fluid to recover this product. The wash fluid forces the liquid out of the filter cake, in effect replacing this liquid comprising polyolefin product in the filter cake with the wash fluid.
  • a warm wash stream instead of a hot stream, is used.
  • warm is defined as a temperature of about 25°C to 60°C, although temperatures within plus or minus 5°C of this range are contemplated.
  • the warm wash stream provides an advantage over known processes in that the filter cake remains at a lower temperature, providing for safer, easier, and more efficient disposal.
  • a wash fluid distillation process (see FIG. 1) is added. This wash fluid distillation may comprise a distillation tower, flash drum, nitrogen sparging, and / or any other suitable equipment and process steps known to one skilled in the art to be useful in distillation processes.
  • a portion of the used wash fluid is taken off and sent through this wash fluid distillation which comprises heating the wash fluid to an appropriate temperature to cause at least a portion of the fluid to flash overhead.
  • This distillation separates the lower flash point olefins from the heavier olefins and polyolefin product. At least a portion of the lower flash point olefins may be recycled back into the reactor for further conversion into product. At least a portion of the heavier olefins and polyolefin product stream may be sent to the main distillation facility to separate the product quality polyolefins from the remaining olefins. The remaining olefins from the main distillation may then be cooled and sent back to the filter drum as wash fluid.
  • This wash fluid distillation improves and optimizes the process in several ways. First, it optimizes the recovery of polyolefin product from the filter cake and the utilization of preferred feedstocks and wash fluids, as not only is polyolefin product recovered from the wash fluid, but both the light and heavy olefins recovered from the wash fluid may be recycled to the reactor and / or filter. Second, in an embodiment of the invention, the wash fluid starts out as 100% pure or nearly 100% pure olefin monomer, and is a monomer with a flash point above the threshold of what requires any special environmental waste classification.
  • the fluid As the wash fluid is used and building up in the filter cake, the fluid is continuously absorbing olefins from the effluent, which may include low flash point unreacted olefins from the feedstocks.
  • the wash fluid distillation where wash fluid is continuously taken off and lower flash point olefins are removed during the course of the wash, allows the concentration of the wash fluid, including the concentration of lower flash point olefins, to reach a steady state.
  • This steady state concentration can be set such that it stays below a threshold that will require the filter cake on disposal to have any special environmental waste classification.
  • This steady state concentration depends on the particular wash fluids used and other factors, and can be set and controlled by one of ordinary skill in the art in possession of this disclosure.
  • the wash fluid prior to use is at least one hydrocarbon liquid and may be any C5 to C30 fluid; and is preferably selected to correspond to a fluid or monomer that forms part of the feedstock to the reactor, and preferably feedstocks with higher flash points.
  • the wash fluid prior to use is 100% C14, 100% C 12 , or 100% Cio.
  • the wash fluid prior to use comprises 90 vol% to 100 vol% CM, 90 vol % to 100 vol% C 12 , 90 vol% to 100 vol% C 10 , or 90 vol% to 100 vol% of any mixture of these monomers.
  • the wash fluid prior to use comprises 90 vol% to 100 vol% of any C5 to C30 hydrocarbon fluid and may also contain a minor amount of other fluids such as C2-C5 hydrocarbons, inert liquids such as those in any of the reactors, byproducts formed in the reaction, or water.
  • the wash fluid prior to use contains no more than 5.0 vol% of water, no more than 1.0 vol% of water, or no more than 0.1 vol% of water.
  • the steady state concentration of the wash fluid is at least 50 wt%, at least 55 wt%, at least 60 wt%, or at least 65 wt% of at least one hydrocarbon liquid selected from the group comprising C 14 , C 12 , or C 10 .
  • the steady state concentration of the wash fluid is less than 20 wt%, preferably less than 15 wt%, preferably less than 10 wt%, preferably less than 7.5 wt%, and preferably less than 5 wt% polyolefin product.
  • the steady state concentration of the wash fluid is less than 10 wt%, preferably less than 5 wt%, preferably less than 2.5 wt%, preferably less than 1 wt%, and preferably less than 0.5 wt% of C2-C6 hydrocarbons.
  • wash fluids in addition to those disclosed above are contemplated as suitable for this invention.
  • the wash fluid may comprise water or steam in whole or in part, but additional equipment would be required, for example, equipment to treat the used water and an oil / water separator.
  • additional equipment would be required, for example, equipment to treat the used water and an oil / water separator.
  • nitrogen or a heavier hydrocarbon stream than what is disclosed above may also be used as wash fluids, although these options may also require additional equipment and / or process steps recognizable to one of ordinary skill in the art, such as additional heating and cooling facilities, compression facilities, etc.
  • the remaining filter cake solids comprise a blend of inert catalyst material and sorbent and residual hydrocarbon liquid.
  • the remaining solids may be disposed of or the sorbent may be reactivated to remove the inert catalyst and returned to the system for further separation of catalyst from the reactor effluent.
  • Prior to disposal of the used filter cake it is preferable to remove as much of the valuable polyolefin and used wash fluid as possible.
  • the amount of polyolefin product remaining in the filter cake after washing is less than 20 wt%, preferably less than 15 wt%, preferably less than 10 wt%, preferably less than 7.5 wt%, or preferably no more than 5 wt%.
  • the polymer product may have a high degree of unsaturation according to the bromine number as measured by ASTM Dl 159, or an equivalent method.
  • the heavy oligomer fraction may be subjected to a hydro finishing step to reduce the bromine number, usually to less than 3, less than 2, or less than 1, depending on hydrofinishing conditions and the desired application. Details on typical hydrogenation processes can be found in many published patents and literatures.
  • the isolated polyolefin products will naturally have very low bromine number or degree of unsaturation and the product can be used directly in many applications without a separate hydrogenation step.
  • the light fraction as separated directly from the reactor effluent or further fractionated from the initially separated light fraction, contains unreacted olefin monomers.
  • This light fraction can be recycled, with or without any purge, into the polymerization reactor for further conversion into lube product.
  • This fraction as is, or the appropriated fractions, can also be recycled into the polymerization reactor after passing through a feed pre-treatment column containing the typical polar component removing agents, such as activated alumina, molecular sieve, or other active sorbents.
  • This pre-treatment column can remove any impurity from the catalyst residue or other impurities.
  • this fraction can be combined with fresh feed olefins before the feed purification column.
  • the oligomerization product comprises a liquid polyolefin.
  • the types of liquid polyolefins produced may include ethylene-alpha-olefin copolymer or terpolymer, homopolymer/copolymer/terpolymer of other alpha-olefins, linear alpha olefin (LAO) homopolymer/copolymer/terpolymer, etc.
  • polymers include PAOs, poly- l-decene, copolymer or terpolymer or multi-component liquid polymer of C3 to C24, terpolymer of C 8 , C 10 , C12-LAO, copolymer of Ce and C 12 or Ce and C14, copolymer of C 4 and C12 or C 4 and C 14 , ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-propylene-butene terpolymer, ethylene-propylene- hexene terpolymer, etc.
  • any of the polyolefins produced have an M w (weight average molecular weight) of 100,000 or less, preferably between 200 and 80,000, more preferably between 250 and 60,000, more preferably between 280 and 50,000, and most preferably between 336 and 40,000 g/mol.
  • M w 's include those from 224 to 55, 100, preferably from 392 to 30,000, more preferably 800 to 24,000, and most preferably 2,000 to 37,500 g/mol.
  • M w 's include 224 to about 6790, and preferably 224 to about 2720).
  • any of the polyolefins produced by the method herein have a number average molecular weight (M n ) of 50,000 or less, more preferably between 200 and 40,000, more preferably between 250 and 30,000, or most preferably between 500 and 20,000 g/mol. More preferred M n ranges include 280 to 10,000, 280 to 4,000, 200 to 20,900, 280 to 10,000, 200 to 7000, 200 to 2000, 280 to 2900, 280 to 1700, and 200 to 500.
  • M n number average molecular weight
  • any of the polyolefins produced have a molecular weight dispersity (M w /M n , or MWD) of greater than 1 and less than 5, preferably less than 4, more preferably less than 3, more preferably less than 2.5, and most preferably less than 2.
  • any polyolefin produced may have a pour point, as measured by ASTM D 97, of less than 10°C, preferably less than 0°C, preferably less than -10°C, preferably less than -20°C, preferably less than -25°C, preferably less than -30°C, preferably less than -35°C, preferably less than -50°C, and most preferably less than -70°C.
  • any polyolefin produced may have a kinematic viscosity at 40°C from about 4 to about 80,000 cSt, as measured by ASTM D 445, preferably from about 5 cSt to about 50,000 cSt.
  • any polyolefin produced may have a kinematic viscosity at 100°C, as measured by ASTM D 445, from about 1.5 cSt to about 5,000 cSt, from about 2 cSt to about 3,000 cSt, from about 3 cSt to about 1,000 cSt, from about 2 cSt to about 500 cSt, from about 8 cSt to 500 cSt, and from 3.2 cSt to 300 cSt.
  • M w and M n were measured by GPC using polystyrene as the calibration standard.
  • V is kinematic viscosity measured at 100°C according to ASTM D 445
  • a and B are constants which vary slightly depending on the type of olefin feeds.
  • M n 344.96 x (V) 0 4921 .
  • KV Kinematic viscosity
  • Oligomer distribution was determined by using the Hewlett Packard (HP) 5890 Series II Plus GC, equipped with flame ionization detector (FID) and capillary column.
  • HP Hewlett Packard
  • FID flame ionization detector
  • the lubricating oils or greases of the present invention are particularly preferred as lubricants of rolling element bearings (e.g., ball bearings), gears, circulation lubrication systems, hydraulics, gas or liquid compressors (such as reciprocating, rotary and turbo-type air compressors, gas turbine compressors, or refrigerator compressors), vacuum pump or metal working machinery, as well as electrical applications, such as for lubrication of electrical switch that produces an electrical arc during on-off cycling or for electrical connectors.
  • rolling element bearings e.g., ball bearings
  • gears e.g., circulation lubrication systems
  • hydraulics e.g., gas or liquid compressors (such as reciprocating, rotary and turbo-type air compressors, gas turbine compressors, or refrigerator compressors), vacuum pump or metal working machinery, as well as electrical applications, such as for lubrication of electrical switch that produces an electrical arc during on-off cycling or for electrical connectors.
  • gas or liquid compressors such as reciprocating, rotary and turbo-type air compressors,
  • the lubricant or grease components disclosed in this invention are most suitable for applications in industrial machinery where one of more the following characteristics are desirable: wide temperature range, stable and reliable operation, superior protection, extended operation period, energy efficient. These oils are characterized by an excellent balance of performance properties including superior high and low temperature viscosities, flowability, excellent foam properties, shear stability, improved anti-wear characteristics, thermal and oxidative stability, low friction, and low traction.
  • gear oils may find utility as gear oils, bearing oils, circulating oils, compressor oils, hydraulic oils, turbine oils, greases for all kinds of machinery, as well as in other applications, for example, in wet clutch systems, blower bearings, wind turbine gear box, coal pulverizer drives, cooling tower gearboxes, kiln drives, paper machine drives and rotary screw compressors.

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Abstract

L'invention porte sur un procédé de préparation d'une polyoléfine liquide qui comprend la mise en contact d'une charge de départ comportant au moins un monomère oléfinique avec un système catalyseur afin de produire un courant d'effluent de réacteur, la filtration du courant d'effluent de réacteur, le lavage d'un gâteau de filtration formé avec un fluide de lavage tiède comportant au moins un hydrocarbure liquide, la séparation d'au moins une partie du fluide de lavage pendant le lavage, l'envoi de ladite partie du fluide de lavage dans un procédé de distillation et la récupération d'au moins une partie de la polyoléfine liquide qui était dans le gâteau de filtration. Le système catalyseur contient au moins un catalyseur métallocène activé. Le courant d'effluent de réacteur comporte au moins une polyoléfine liquide, du catalyseur résiduel et un monomère oléfinique n'ayant pas réagi.
PCT/US2012/069904 2012-01-17 2012-12-14 Procédé d'obtention de polyoléfines liquides WO2013109371A1 (fr)

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WO2016105226A1 (fr) 2014-12-23 2016-06-30 Public Joint Stock Company "Sibur Holding" Procédés de précipitation de polymère et catalyseur organométallique désactivé dans une réaction d'oligomérisation d'oléfine

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US5705577A (en) 1992-12-17 1998-01-06 Exxon Chemical Patents Inc. Dilute process for the polymerization of ethylene/α-olefin copolymer using metallocene catalyst systems
WO2007011973A1 (fr) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Procede pour produire des polyalphaolefines de faible viscosite
WO2007011832A1 (fr) 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Produits lubrifiants obtenus d'alimentations d'alpha-olefines melangees
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