WO2021183330A1 - Compositions de cire comprenant des dimères d'oléfines linéaires hydrogénées ou partiellement hydrogénées et procédés de production correspondants - Google Patents

Compositions de cire comprenant des dimères d'oléfines linéaires hydrogénées ou partiellement hydrogénées et procédés de production correspondants Download PDF

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WO2021183330A1
WO2021183330A1 PCT/US2021/020532 US2021020532W WO2021183330A1 WO 2021183330 A1 WO2021183330 A1 WO 2021183330A1 US 2021020532 W US2021020532 W US 2021020532W WO 2021183330 A1 WO2021183330 A1 WO 2021183330A1
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Prior art keywords
olefin
linear
partially
hydrocarbon substance
dimer
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PCT/US2021/020532
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English (en)
Inventor
Roxana PEREZ VELEZ
Alexander V. ZABULA
Anatoly I. Kramer
Elizabeth A. TURNER
Helge Jaensch
Jeffrey C. BUNQUIN
Javier Guzman
Madelyn Bekker
Emiel De Smit
John S. COLEMAN
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Exxonmobil Chemical Patents Inc.
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Publication of WO2021183330A1 publication Critical patent/WO2021183330A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • Waxes are hydrophobic organic substances that occur in petroleum or other oleaginous materials, and may be produced synthetically in a reactor or biosynthetically by plants and animals. Waxes are usually malleable solids at room temperature, which may comprise one or more higher alkanes, lipids and/or oils, or unsaturated variants thereof.
  • Wax compositions include natural waxes, synthetic waxes and vegetable waxes.
  • Traditional wax compositions in common use include, for example, paraffin wax (e.g., slack wax), beeswax, and hydrogenated vegetable oils (e.g., soy wax). Petroleum-derived paraffinic waxes are particularly prevalent.
  • Non-conventional waxes particularly Fischer-Tropsch and hydrogenated vegetable waxes
  • Wax blends may also be used in certain instances.
  • Waxes of various types are in demand for making items such as, for example, candles, coatings, inks, cosmetics, paints, rubber, electrical components and electronics, plastics, adhesives (e.g., hot melt adhesives), lubricants (e.g., polyvinyl chloride (PVC) extrusion lubricants), surfactants, paper sizings, synthetic drilling fluids, separating agents, food additives, pharmaceutical agents, and many other purposes.
  • Factors that may dictate the suitability of a wax composition for an intended application include, for example, viscosity, density, melting point, congealing point, and burning properties, as well as secondary performance factors influenced by these parameters.
  • wax compositions having a wide range of physical properties may be desirable for use in various types of applications, there is not presently a ready way of producing high-quality synthetic wax compositions, particularly with the ability to tune melting points and other physical properties needed for addressing certain application-specific needs.
  • the present disclosure provides processes for making wax compositions.
  • the processes comprise: providing a hydrocarbon substance comprising at least one linear olefin dimer, the at least one linear olefin dimer being formed from a first linear alpha olefin having m carbon atoms and a second linear alpha olefin having n carbon atoms in the presence of a metal carbene catalyst, the first linear alpha olefin and the second linear alpha olefin being the same or different, and the linear olefin dimer comprising two carbon atoms less than a sum of m and n; wherein m and n are independently selected integers each ranging from about 12 to about 100; contacting the hydrocarbon substance with a hydrogenation catalyst under hydrogenation reaction conditions; and hydrogenating at least a portion of the at least one linear olefin dimer to form an at least partially paraffinic hydrocarbon substance comprising at least one linear paraffin.
  • the present disclosure provides wax compositions that are at least partially hydrogenated.
  • the wax compositions comprise: an at least partially paraffinic hydrocarbon substance comprising a hydrogenated or partially hydrogenated reaction product of a hydrocarbon substance comprising at least one linear olefin dimer, the at least one linear olefin dimer being formed from a first linear alpha olefin having m carbon atoms and a second linear alpha olefin having n carbon atoms in the presence of a metal carbene catalyst, the first linear alpha olefin and the second linear alpha olefin being the same or different, and the at least one linear olefin dimer comprising two carbon atoms less than a sum of m and n; wherein m and n are independently selected integers each ranging from about 12 to about 1000; and wherein the at least partially paraffinic hydrocarbon substance has an increased melting point or kinematic viscosity relative to the hydrocarbon substance.
  • FIG. 1 is a flow diagram of a process for producing wax compositions comprising partially hydrogenated linear olefin dimers.
  • FIG. 2 is a flow diagram of a first variant of a process for producing wax compositions comprising linear paraffins formed from hydrogenated linear olefin dimers.
  • FIG. 3 is a flow diagram of a second variant of a process for producing wax compositions comprising linear paraffins formed from hydrogenated linear olefin dimers.
  • FIG. 4 is a flow diagram of a process for producing wax compositions comprising a blend of linear olefin dimers and linear paraffins formed from hydrogenated linear olefin dimers.
  • FIG. 5 is a graph depicting the melting points of various linear olefin dimers and the corresponding linear paraffins obtained following hydrogenation.
  • FIG. 6 is a graph depicting the melting points of C 26 -C 46 linear olefin dimers after undergoing variable extents of hydrogenation.
  • FIG. 7 is a graph depicting the kinematic viscosity (measured at 100°C, Kv100) of C 26 -C 46 linear olefin dimers after undergoing variable extents of hydrogenation.
  • the present disclosure relates to wax compositions and, more specifically, wax compositions comprising at least partially hydrogenated linear olefin dimers and methods for production thereof.
  • linear alpha olefins may be suitable precursors for forming high-quality wax compositions and/or blends thereof.
  • wax compositions having tunable melting points and viscosities may be realized by producing linear paraffins from linear olefin dimers formed from linear alpha olefins having about 12 carbons or more, particularly by controlling the temperature and the space velocity of the hydrogenation reaction used to produce the linear paraffins from the linear olefin dimers.
  • Full or partial conversion of the linear olefin dimers to a paraffinic wax or partially paraffinic wax may afford wax compositions having melting points and viscosity values that may vary continuously based upon the extent of hydrogenation occurring to produce a reaction product.
  • the linear olefin dimers, the corresponding linear paraffins formed from the linear olefin dimers, or blends of the linear olefin dimers and linear paraffins, optionally in combination with other reaction products and/or with other blending waxes or additives, may comprise high-quality wax compositions that may be suitable for a variety of applications.
  • the melting points of the wax compositions described herein may be tailored by selecting the chain length of the linear alpha olefins used to form the linear olefin dimers and/or by adjusting the extent of unsaturation present in the wax compositions resulting after hydrogenation.
  • wax compositions that are fully saturated through hydrogenation have the highest melting point for a given carbon chain length
  • wax compositions that have had none of their unsaturation removed through hydrogenation have the lowest melting point for a given carbon chain length.
  • Blends of linear olefin dimers and linear paraffins produced therefrom may afford a spectrum of continuously variable melting points between these two extremes. Other physical properties may vary similarly.
  • Blends of different linear olefin dimers and/or linear paraffins formed from LAOs having different carbon chain lengths may similarly afford advantageous melting point variability in the disclosure herein.
  • a hydrocarbon substance comprising a linear olefin dimer, a hydrogenated or partially hydrogenated reaction product of the linear olefin dimer, or any combination thereof, may provide wax compositions having melting points of about 25°C or greater, wherein the linear olefin dimers are formed from linear alpha olefins having about 12 carbons or more, such as about 12 carbons to about 100 carbons, more particularly about 12 carbons to about 30 carbons or about 12 carbons to about 26 carbons.
  • partially hydrogenated means that at least some olefinic bonds remain in the reaction product obtained from hydrogenating linear olefin dimers. That is, a mixture of unhydrogenated linear olefin dimers and linear paraffins may be present.
  • a feed comprising LAOs having about 12 to about 30 carbons may be used in combination with a small amount of a feed comprising C 30 to C 100 LAOs.
  • Suitable sources of linear alpha olefins used as a feed for producing linear olefin dimers may include those obtained from ethylene dimerization, alcohol dehydration, renewable LAOs (e.g., biomass-derived hydrocarbon compounds, such as biomass-derived lactones, unsaturated acids, ethano1, or the like), or blends of one or more of such sources, or combination thereof.
  • Feeds comprising higher linear alpha olefins, such as linear alpha olefins having 18 carbons or more, may have a significant content of internal olefins and/or branched olefins.
  • Metathesis of internal and/or branched olefins in a feed comprising linear alpha olefins may lead to the formation of branched olefin dimers and/or a hydrogenated reaction product thereof, which may also be suitably present in the wax compositions disclosed herein.
  • the melting points of the wax compositions described herein may be adjusted depending upon the extent of unsaturation present and/or the amount of branching present, thereby allowing tailoring to be realized for particular applications.
  • the wax compositions of the present disclosure may be formed by reacting at least one linear alpha olefin with a metal carbene catalyst, which may afford formation of the linear olefin dimer by a metathesis reaction and commensurate loss of ethylene.
  • a metal carbene catalyst which may afford formation of the linear olefin dimer by a metathesis reaction and commensurate loss of ethylene.
  • a single linear alpha olefin may self-dimerize to form the linear olefin dimers or two different linear alpha olefins may form asymmetrical linear olefin dimers. Mixtures of linear olefin dimers having different carbon chain lengths may also be formed in this manner.
  • linear olefin dimers may comprise two carbon atoms less than a total number of carbon atoms in the linear alpha olefins from which they were produced (as a result of ethylene loss).
  • linear olefin dimers may be formed through olefin metathesis in a continuous mode, such as in a continuous stirred tank reactor (CSTR) or tubular reactor, which may be compatible with continuous production line processes for distilling and/or hydrogenating the linear olefin dimers to afford wax compositions having a desired extent of unsaturation for melting point and/or viscosity adjustment.
  • CSTR continuous stirred tank reactor
  • tubular reactor which may be compatible with continuous production line processes for distilling and/or hydrogenating the linear olefin dimers to afford wax compositions having a desired extent of unsaturation for melting point and/or viscosity adjustment.
  • CSTRs may include CSTRs or CSTRs in series, stirred tank reactors (STRs) or STRs in series, tubular reactors, staged bubble column reactors, tubular reactors with co-current gas/liquid flows, tubular reactors with periodic gas/liquid separation, and the like.
  • CSTRs may facilitate ready addition and mixing of the catalyst, thus allowing dispersion of the catalyst through the volume of the feed, which may be of high viscosity.
  • the ready catalyst dispersion may be especially advantageous, since the catalyst is often used at a concentration of only a few ppm in the reaction mixture.
  • the extent of hydrogenation may be readily controlled by modifying the hydrogenation conditions to afford direct variation of the physical properties of the wax compositions.
  • the new numbering scheme for groups of the Periodic Table is used.
  • the groups (columns) are numbered sequentially from left to right from 1 through 18, excluding the f-block elements (lanthanides and actinides).
  • the term “transition metal” refers to any atom from groups 3-12 of the Periodic Table, inclusive of the lanthanides and actinide elements.
  • hydrocarbon refers to a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different numbers of carbon atoms.
  • C n refers to hydrocarbon(s) or a hydrocarbyl group having n carbon atom(s) per molecule or group, wherein n is a positive integer.
  • Such hydrocarbon compounds may be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, or aromatic.
  • hydrocarbyl and “hydrocarbyl group” are used interchangeably herein.
  • hydrocarbyl group refers to any C 1 -C 100 hydrocarbon group bearing at least one unfilled valence position when removed from a parent compound.
  • Optional heteroatom substitution may be present in a hydrocarbyl group.
  • alkyl refers to a hydrocarbyl group having no unsaturated carbon-carbon bonds.
  • alkenyl refers to a hydrocarbyl group having a carbon-carbon double bond.
  • alkene and olefin are used synonymously herein.
  • alkenic and olefinic are used synonymously herein. Unless otherwise noted, all possible geometric isomers are encompassed by these terms.
  • substituted refers to replacement of at least one hydrogen atom or carbon atom of a hydrocarbon or hydrocarbyl group with a heteroatom or heteroatom functional group.
  • Heteroatoms may include, but are not limited to, B, O, N, S, P, F, C1, Br, I, Si, Pb, Ge, Sn, As, Sb, Se, and Te.
  • Suitable hydrocarbyl R groups may include alky1, alkeny1, alkyny1, ary1, heteroary1, cycloalky1, heterocycly1, and the like, any of which may be optionally substituted.
  • hydrocarbyl refers to replacement of at least one hydrogen atom or carbon atom in a hydrocarbyl group with a heteroatom or heteroatom functional group. Unless otherwise specified, any of the hydrocarbyl groups herein may be optionally substituted.
  • linear and linear hydrocarbon refer to a hydrocarbon or hydrocarbyl group having a continuous carbon chain without side chain branching.
  • linear alpha olefin refers to an alkenic hydrocarbon bearing a carbon-carbon double bond at a terminal (end) carbon atom of the main carbon chain.
  • IO internal olefin
  • branch branched and branched hydrocarbon refer to a hydrocarbon or hydrocarbyl group having a linear main carbon chain in which a hydrocarbyl side chain extends from the linear main carbon chain.
  • unbranched refers to a straight-chain hydrocarbon or hydrocarbyl group.
  • branched olefin (BO) refers to an alkenic hydrocarbon having a carbon- carbon double bond at any position and a hydrocarbyl side chain at any position along the main carbon chain.
  • the terms “self-metathesis” and “self-dimerization” refer to formation of an olefin dimer from two of the same type of olefin molecule.
  • the term “blend” refers to a mixture of two or more components, such as two or more LAOs or two or more linear olefin dimers and/or a hydrogenated reaction product thereof.
  • methods of the present disclosure may comprise: providing a hydrocarbon substance comprising at least one linear olefin dimer, the at least one linear olefin dimer being formed from a first linear alpha olefin having m carbon atoms (LAO C m ) and a second linear alpha olefin having n carbon atoms (LAO C n ) in the presence of a metal carbene catalyst; contacting the hydrocarbon substance with a hydrogenation catalyst under hydrogenation reaction conditions; and hydrogenating at least a portion of the at least one linear olefin dimer to form an at least partially paraffinic hydrocarbon substance comprising at least one linear paraffin.
  • LAO C m first linear alpha olefin having m carbon atoms
  • LAO C n second linear alpha olefin having n carbon atoms
  • the first linear alpha olefin and the second linear alpha olefin are the same or different, and the linear olefin dimer comprises two carbon atoms less than a sum of m and n.
  • Variables m and n are independently selected integers each ranging from about 12 to about 100, such as about 12 to about 30 or about 12 to about 26, and wherein m and n may be the same or different.
  • the at least partially paraffinic hydrocarbon substance comprises a hydrogenated or partially hydrogenated reaction product of the hydrocarbon substance comprising the at least one linear olefin dimer.
  • the at least one linear olefin dimer may be formed from an olefmic feed comprising one or more LAOs.
  • the olefmic feed may comprise linear alpha olefins comprising about 12 to about 30 carbons, along with a minority co-feed comprising linear alpha olefins comprising about 30 to about 100 carbons (e.g., about 5 wt% to about 30 wt%, based on the total weight of the olefmic feed).
  • Olefmic feeds comprising higher linear alpha olefins may have relatively small amounts of linear alpha olefins (e.g., about 30 wt% or less), with the remainder of the feed comprising branched olefins or internal olefins.
  • the hydrogenation conditions may be sufficient to hydrogenate substantially all of the at least one linear olefin dimer to afford the corresponding linear paraffins, thereby forming a fully paraffinic hydrocarbon substance as the wax composition.
  • the hydrogenation conditions may be sufficient to hydrogenate a portion of the least one linear olefin dimer to leave at least some unsaturation in the at least partially paraffinic hydrocarbon substance.
  • the at least partially paraffinic hydrocarbon substance may have a degree of unsaturation sufficient to increase the melting point or the kinematic viscosity relative to the hydrocarbon substance prior to hydrogenation.
  • the hydrocarbon substance may further comprise one or more branched olefin dimers, which may lead to formation of the corresponding branched paraffins following hydrogenation.
  • the one or more branched olefin dimers may comprise a dimerized reaction product of an internal olefin and the first linear alpha olefin or the second linear alpha olefin, a self-dimerized reaction product of the internal olefin, a dimerized reaction product of a branched olefin and the first linear alpha or the second linear alpha olefin, a self-dimerized reaction product of the branched olefin, a dimerized reaction product of the internal olefin and the branched olefin, or any combination thereof.
  • Each of the one or more branched olefin dimers and the corresponding branched paraffins comprises at least two carbon atoms less than a sum of the number of carbon atoms in a first olefin and a second olefin from which the one or more branched olefins in the dimerized reaction product were formed. If ethylene is lost during dimerization, as is the case for unbranched linear alpha olefins, the one or more branched olefin dimers have two carbon atoms less than a sum of the number of carbon atoms in the first olefin and the second olefin.
  • the one or more branched olefin dimers typically comprise a minor component of the wax compositions disclosed herein.
  • the at least partially paraffinic hydrocarbon substance formed according to the disclosure herein may comprise a hydrogenated or partially hydrogenated reaction product of the one or more branched olefin dimers.
  • Linear alpha olefins which also may be referred to as terminal olefins or terminal alkenes, suitable for use in the present disclosure may be isolated from a petroleum refinery stream.
  • linear alpha olefins may be synthesized by several processes starting from low molecular weight feedstock materials, such as via oligomerization of ethylene or through byproduct isolation from the Fischer-Tropsch synthesis. Biomass-derived linear alpha olefins and linear alpha olefins from other sources may also be used in the disclosure herein.
  • Linear alpha olefins are composed of a linear hydrocarbon chain, and have a chemical formula of C x H 2x (x is an integer greater than or equal to 2, particularly an even integer greater than or equal to 3 or greater than or equal to 4) with a double bond between C-1 and C-2.
  • the linear olefin dimers of the present disclosure may be formed by dimerization of the first linear alpha olefin having m carbon atoms (LAO Cm) and the second linear alpha olefin having n carbon atoms (LAO C n ) in the presence of a metal carbene catalyst. Dimerization may occur through metathesis, wherein a molecule of ethylene is collectively lost from the first linear alpha olefin and the second linear alpha olefin, and the resulting linear olefin dimer possesses two carbon atoms less than a sum of m and n.
  • a linear paraffin formed from the linear olefin dimer as a hydrogenated reaction product similarly has two carbon atoms less than a sum of m and n. Larger carbon fragments may be lost when internal olefins or branched olefins undergo metathesis.
  • the linear olefin dimers of the present disclosure may have a structure represented by Formula 1 wherein R 1 and R 2 are independently selected normal alkyl groups having from about 10 to about 98 carbon atoms.
  • R 1 and R 2 may be independently selected normal alkyl groups having from about 10 to about 24 carbon atoms or about 10 to about 28 carbon atoms.
  • R 1 and R 2 may be of the same length or different lengths, resulting from selection of first and second LAOs that are the same or different, respectively.
  • the hydrocarbon substance employed in the disclosure herein may have a melting point of at least about 10°C, or at least about 15°C, or least about 20°C, or least about 25°C before hydrogenation, and the at least partially paraffinic hydrocarbon substance may have a higher melting point after hydrogenation.
  • the hydrocarbon substance employed in the disclosure herein may have a melting point of at least about 20°C, at least about 25°C, at least about 30°C, at least about 40°C, or at least about 60°C before hydrogenation, and the at least partially paraffinic hydrocarbon substance may have a higher melting point after hydrogenation.
  • the melting point may vary based upon the number of carbon atoms in the linear olefin dimer and the extent of unsaturation following hydrogenation. Wax compositions formed according to the disclosure herein that are fully saturated (substantially all linear olefin dimers hydrogenated to the corresponding linear paraffins) have higher melting points than that of fully unsaturated linear olefin dimers.
  • Partially hydrogenated wax compositions and/or wax compositions obtained by blending a desired proportion of linear olefin dimers and linear paraffins formed from linear olefin dimers may allow tunable, intermediate melting points in between these two extremes to be formed (i.e., between the melting point of the linear olefin dimers and the higher melting point of the corresponding linear paraffins).
  • the melting point may be about 25 °C or greater, or about 30°C or greater, or about 40°C or greater, or about 60°C or greater, or about 80°C or greater, or about 100°C or greater, or about 120°C or greater, or about 140°C or greater.
  • the melting point of the wax compositions is about 180°C or lower. More preferably, the melting point of the wax compositions may range from about 10°C to about 140°C, or from about 25°C to about 140°C, or from about 40°C to about 140°C.
  • kinematic viscosity at 100°C of the wax compositions of the present disclosure may range from about 2 cSt to about 20 cSt, or from about 4 cSt to about 15 cSt, or from about 6 cSt to about 10 cSt, alternately from about 3 cSt to about 10 cSt, or from about 3.5 cSt to about 4 cSt.
  • the foregoing viscosities may be particularly applicable to paraffinic hydrocarbon substances having a melting point of about 100°C or below; paraffinic hydrocarbon substances having higher melting points may exhibit higher viscosity values. Brookfield viscosity values of about 10 cP to about 300 cP at 125°C may be realized in some cases.
  • the at least partially paraffinic hydrocarbon substances formed according to the present disclosure may have a total linear olefin dimer and/or linear paraffin content of about 70 wt% or more, or about 80 wt% or more, or about 90 wt% or more, or about 95 wt% or more, or even 100 wt%, based on total weight, provided that at least some linear paraffins are present.
  • the linear olefin dimer and linear paraffin content may depend upon the amount of branched olefins and internal olefins present in the feed, wherein feeds comprising significant quantities of these species may afford higher amounts of branched olefin dimers and branched paraffins.
  • the at least partially paraffinic hydrocarbon substance formed according to the present disclosure may have a total branched olefin dimer and branched paraffin content of about 30 wt% or less, or about 20 wt% or less, or about 10 wt% or less, or about 5 wt% or less, or about 2 wt% or less, or about 1 wt% or less, or about 0.5 wt% or less, or about 0.1 wt% or less, based on the total weight.
  • At least partially paraffinic hydrocarbon substances formed according to the present disclosure from feeds comprising higher amounts of branched and/or internal olefins may have a total branched olefin dimers and branched paraffins content of about 50 wt% to about 70 wt%, based on total weight.
  • Petroleum slack wax is a generic term for a byproduct of a petroleum refining process that contains oil and wax.
  • Slack wax is a complex combination of hydrocarbons obtained from a petroleum fraction by solvent crystallization (i.e., dewaxing) or as a distillation fraction from a waxy crude.
  • Slack wax is substantially comprised of saturated straight and branched chain hydrocarbons that predominantly have carbon numbers of about C 20 or greater. Slack wax is often in abundance where petroleum is processed, so it can be obtained cheaply.
  • a blending wax may be used in the disclosure herein to tailor the properties of wax compositions comprising the at least partially paraffinic hydrocarbon substance. Any amount of the blending wax ranging from about 0.1 wt% to about 99.9 wt% may be present in combination with the at least partially paraffinic hydrocarbon substance.
  • the blending wax may be a wax formed from a linear olefin dimer and/or hydrogenated reaction product thereof that has a different number of carbon atoms than a primary wax in the wax composition.
  • different wax types such as slack wax, may comprise a blending wax in the wax compositions described herein.
  • Certain wax compositions described herein may comprise slack wax with a free oil content of at least 2 wt%, or at least 3 wt% or at least 5 wt%.
  • the free oil content of the slack wax may be about 35 wt% or less or about 20 wt% or less.
  • Suitable ranges of free oil in slack wax may include 2 wt% to 20 wt%, 10 wt% to 20 wt%, or 3 wt% to 20 wt%.
  • Slack waxes suitable for use in the disclosure herein may have a melting point in a range of about 43°C to about 66°C, for example from 50°C to about 53°C.
  • Slack waxes generally can have a color ranging from white to brown.
  • suitable blending waxes may include, for example, petroleum slack wax, fully refined wax, semi-refined wax, scale wax, stearic acid wax, soft wax and/or foots oi1, microcrystalline wax, beeswax, vegetable-based waxes such as soy and palm wax, synthetic waxes such as C 20+ LAO waxes and Fischer-Tropsch waxes, and various combinations thereof.
  • Other types of blending wax may be suitable as well.
  • the blending wax may have a degree of unsaturation differing from that of the hydrocarbon substance formed by metathesis of the first linear alpha olefin and the second linear alpha olefin.
  • Linear olefin dimers in the disclosure herein may be synthesized through dimerization of one or more linear alpha olefins, such as C 12 to C 100 linear alpha olefins, particularly C 12 to C 30 linear alpha olefins or C 12 to C26 linear alpha olefins, in the presence of a metal carbene catalyst.
  • an olefmic feed comprising C 30 + LAOs may be used as a co-feed in combination with a majority olefmic feed comprising C 12 to C 30 LAOs.
  • the linear alpha olefins used for forming the linear olefin dimers may be of the same or different chain lengths.
  • the linear alpha olefins may be predominately of the same chain length.
  • the linear alpha olefins may comprise a blend of two or more C 12 to C 30 linear alpha olefins, particularly linear alpha olefins having an even number of carbon atoms within this range.
  • Such linear olefin dimers may be suitable for forming the wax compositions disclosed herein. Linear olefin dimers of either type may undergo subsequent hydrogenation to form an at least partially paraffinic hydrocarbon substance suitable for use in the disclosure herein.
  • Processes for forming linear olefin dimers according to the present disclosure may comprise: providing an olefmic feed in a reactor, the olefmic feed comprising a first linear alpha olefin having m carbon atoms (LAO C m ) and a second linear alpha olefin having n carbon atoms (LAO C n ), the first linear alpha olefin and the second linear alpha olefin being the same or different, wherein m and n are independently selected integers each ranging from about 12 to about 100, or about 12 to about 30 or about 12 to about 26, and the olefmic feed optionally comprising one or more internal olefins and/or one or more branched olefins; contacting the olefmic feed with a metal carbene catalyst in the reactor; forming ethylene and a hydrocarbon substance comprising a linear olefin dimer in the reactor, the linear olefin dimer
  • Wax compositions comprising the hydrocarbon substance may be suitable for use in various applications.
  • the hydrocarbon substance may undergo full or partial hydrogenation to afford an at least partially paraffinic hydrocarbon substance having physical properties tailored for a particular application, such as increased melting point and kinematic viscosity, for example, as discussed herein.
  • Reaction 1 illustrates the general structure for a pair of LAOs and their subsequent dimerization to form a linear olefin dimer via metathesis. Subsequent hydrogenation to form the corresponding linear paraffin, i.e., a hydrogenated reaction product of the linear olefin dimer, is also shown in Reaction 1.
  • R 1 and R 2 are independently selected alkyl groups having from about 10 to about 98 carbon atoms, such as about 10 to about 28 or about 10 to about 24 carbon atoms.
  • the R 1 and R 2 groups in each LAO may be of the same length, or they may be of differing lengths.
  • the olefmic feed used to form the one or more linear olefin dimers may be purified to remove one or more contaminants therefrom. Purification may mitigate the presence of one or more contaminants therein (e.g., oxygenates, moisture, metals, heteroatoms, and any combination thereof), particularly during metal carbene catalyst preforming of a dimerization process.
  • contaminants therein e.g., oxygenates, moisture, metals, heteroatoms, and any combination thereof
  • Purifying may comprise contacting the feed with an adsorbent, sparging the feed with an inert gas, or any combination thereof in the same or different location(s), and further optionally removing spent catalyst from the reaction product through a column packed with a solid adsorbent, and purifying the linear olefin dimer(s) from light species and unreacted feed by distillation and/or falling-film evaporation, thereby limiting the quantity of contaminants returned to the metathesis reaction upon recycling the feed.
  • purification of the olefmic feed may also involve contacting the olefmic feed in a melt phase with an adsorbent for removal of the one or more contaminants.
  • Suitable examples of adsorbents for the removal of the one or more contaminants may include zeolite molecular sieves, modified activated aluminas, mixtures thereof, and non- regenerable metal oxide/sulfide products. Adsorbent selection may depend on the specific impurities to be removed and the olefmic feed in which they are contained.
  • the adsorbent may be pre-activated with an inert gas (e.g., N 2 ) at a temperature of about 200°C to about 300°C (or from about 220°C to about 280°C, or from about 240°C to about 260°C), and/or for a period of time of about 2 hours (or about 4 hours, or about 6 hours, or about 8 hours, or about 10 hours, or about 12 hours, or about 24 hours).
  • AZ-300 adsorbent manufactured by Honeywell-UOP
  • a homogenous combination of modified activated alumina and molecular sieve adsorbents may afford complementary performance characteristics of both materials.
  • AZ-300 adsorbent has high capacity for light acid gases and a broad range of polar molecules. Though AZ-300 adsorbent contains zeolite, it does not typically require a preload step when processing unsaturated streams. The elimination of the preload process, while retaining the effective removal of polar compounds, provides a time-efficient process.
  • the purification process may also include sparging of the olefmic feed with a stream of inert gas (e.g., Ar or N 2 ) to remove oxygen.
  • Suitable olefmic feeds described herein are not considered to be particularly limited. In some process configurations, the olefmic feed may comprise one or more C 12 to C 30 alpha olefins.
  • Suitable alpha olefins may include, but are not limited to C 12 + alpha olefins, Cm alpha olefins, Cm alpha olefins, C 18+ alpha olefins, C 20+ alpha olefins, C 24+ alpha olefins, or C 26+ alpha olefins, such as 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1 -tricosene, 1 -tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, 1-non
  • Internal olefins, branched olefins, and the like may also comprise at least a portion of the olefmic feed in various process implementations. Internal olefins and/or branched olefins may undergo dimerization in combination with alpha olefins in some process configurations.
  • the olefmic feed may comprise 25 wt% to 100 wt% linear alpha olefins or about 70 wt% to about 100 wt% linear alpha olefins, 0 wt% to 75 wt% or 0 wt% about 30 wt% internal olefins, and 0 wt% to 75 wt% or about 0 wt% to about 30 wt% branched olefins, based on a total weight of the olefmic feed.
  • the olefmic feed may comprise 85 wt% to 100 wt% linear alpha olefins, 0 wt% to 15 wt% internal olefins, and 0 wt% to 15 wt% branched olefins, based on a total weight of the olefmic feed. Any amount specifying 0 wt. % is inclusive of non-zero amounts of a specified component. [0058]
  • the purified olefmic feed may be further transferred to another reactor for additional processing by olefin metathesis. Alternately, the olefmic feed may undergo metathesis in the same reactor in which it was purified.
  • the metathesis process of the present disclosure may be carried out in a continuous mode or in batch reactors, such as stirred-batch reactors, via a batch or semi-batch production mode.
  • the at least partially paraffinic hydrocarbon substances of the present disclosure may be prepared in a continuous production mode, at any conventional plant equipped with various process equipment such as continuous stirred-tank reactors (CSTRs), stirred-tank reactors equipped with an online catalyst injection mechanism, and/or stirred batch reactors, separators, condensers, compressors, and the like.
  • CSTRs continuous stirred-tank reactors
  • stirred-tank reactors equipped with an online catalyst injection mechanism and/or stirred batch reactors, separators, condensers, compressors, and the like.
  • suitable reactors for the formation of linear olefin dimers of the present disclosure may include CSTR or CSTRs in series, STR or STRs in series, tubular reactors, staged bubble column reactors, tubular reactors with co-current gas/liquid flow, tubular reactors with periodic gas/liquid separation, the like, or any combination thereof.
  • the metathesis reaction may be carried out in a CSTR, since such reactors may achieve ready catalyst dispersion of the low-abundance catalyst.
  • One of ordinary skill in the art will be familiar with such equipment and be able to utilize the same for carrying out the methods disclosed herein.
  • methods according to the present disclosure may comprise: forming the linear olefin dimer in a continuous mode, wherein the linear olefin dimer has a structure represented by Formula 1.
  • Such methods of the present disclosure may provide wax compositions in good to excellent yield (such as 40 wt% to 100 wt%, or 45 wt% to 95 wt%, or 50 wt% to 90 wt%), wherein about 30% to about 100% of the olefinic feed is converted into ethylene and linear olefin dimers.
  • Purified olefinic feed may pass from a purification reactor to a dimerization reactor (i.e., metathesis reactor), such as a CSTR or CSTRs in series, STR or STRs in series, tubular reactor, staged bubble column reactor, tubular reactors with co-current gas/liquid flow, tubular reactors with periodic gas/liquid separation, the like, or any combination thereof, wherein the metal carbene catalyst may be provided as a solid or as a solution or slurry in paraffinic wax or unreactive liquid hydrocarbon solvents, such as toluene.
  • a dimerization reactor i.e., metathesis reactor
  • the metal carbene catalyst may be provided as a solid or as a solution or slurry in paraffinic wax or unreactive liquid hydrocarbon solvents, such as toluene.
  • suitable solvents can be aromatic solvents (e.g ., toluene) or a paraffinic solvent (e.g., cyclohexane, ISOPARTM M).
  • the metal carbene catalyst may be provided as a homogeneous catalyst solution.
  • Metal carbene catalysts may also be suitably provided in suspension/slurry using, for example, a hydrogenated linear olefin dimer (e.g., a C 24 -C 60 hydrogenated linear olefin dimer), a low viscosity polyalphaolefin (PAO), and/or a combination thereof.
  • a hydrogenated linear olefin dimer e.g., a C 24 -C 60 hydrogenated linear olefin dimer
  • PAO low viscosity polyalphaolefin
  • a low viscosity PAO may have a viscosity of about 10 centistokes (cSt) or less (or 8 cSt or less, or 6 cSt or less, or 4 cSt or less, or 2 cSt or less) at 100°C as measured by ASTM method D445.
  • cSt centistokes
  • the metathesis reaction of the olefinic feed may be carried out using heterogeneous catalysts. In that case, the metathesis reaction may be carried out in a fixed-bed reactor.
  • Olefin metathesis e.g., dimerization
  • inert atmosphere e.g, Ar or N 2
  • partial vacuum by contacting the olefini c feed with the metal carbene catalyst under conditions effective to form a hydrocarbon substance comprising at least one linear olefin dimer having a structure represented by Formula 1.
  • suitable metal carbene catalysts may include those comprising a group 6 or 8 transition meta1, such as the metal carbene catalysts described below and represented by Formulas 2 to 7.
  • Suitable metal carbene catalysts for forming linear olefin dimers may be transition metal carbene complexes comprising a group 6 or a group 8 transition meta1, such as molybdenum, ruthenium, tungsten or osmium, for example. Molybdenum and ruthenium carbene complexes may be particularly suitable for this purpose.
  • Suitable reaction temperatures during metathesis may range from about room temperature to about 200°C (i.e., about 25°C to about 200°C), or any subrange in between. More desirably, the metal carbene catalyst may be contacted with the olefinic feed at a temperature of about 60°C to about 80°C, for example. In at least one embodiment, the reaction temperature may be about 65°C. Pressure conditions may be chosen to maintain the olefinic feed in a liquid state during the metathesis reaction.
  • Some metal carbene catalysts suitable for forming linear olefin dimers via metathesis according to the disclosure herein may include, for example, those having a structure represented by Formula 2 wherein M is a group 8 transition metal (e.g., Os or Ru); X 1 and X 2 are anionic ligands, wherein X 1 and X 2 may be the same or different; R 3 and R 4 are independently selected from the group consisting of hydrogen, hydrocarby1, substituted hydrocarby1, heteroatom-containing hydrocarby1, substituted heteroatom-containing hydrocarby1, and -(Z) n -Fn where n is zero or 1, Z is a hydrocarbylene, substituted hydrocarbylene and/or heteroatom-containing hydrocarbylene linkage, and Fn is an optional functional group containing a heteroatom; and L 1 and L 2 are independently selected from any Lewis base ligand.
  • M is a group 8 transition metal (e.g., Os or Ru)
  • X 1 and X 2 are anionic ligand
  • R 3 and/or R 4 may be covalently bonded to L 1 or L 2 to form at least one metallocycle ring.
  • metal carbene catalysts are described further in US Patents 7,683,180, 8,846,939, 6,838,489, and 6,613,910, and International Patent Application Publication WO 2000/071554, each of which is incorporated herein by reference in its entirety.
  • Particularly suitable examples include those in which M is Ru, which may be referred to as Grubbs-type catalysts.
  • R 3 and R 4 may be independently selected from hydrogen, C 2 -C 20 alkeny1, C 2 -C 20 alkyny1, C 1 -C 20 alky1, ary1, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbony1, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl or C 1 -C 20 alkylsulfiny1, each optionally substituted with C 1 -C 5 alky1, halogen, Ci -C5 alkoxy or with a phenyl group optionally substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
  • Suitable alkyl groups can include, for example, methy1, ethy1, n-propy1, i-propy1, buty1, penty1, hexy1, or any isomer thereof.
  • Alkenyl groups can include, for example, 1-propeny1, 2-propenyl; 3-propeny1, buteny1, penteny1, hexeny1, or any isomer thereof, 1,3-hexadieny1, 2,4,6-heptatrieny1, or cycloalkenyl.
  • Alkynyl groups can include, for example, ethyny1, 1-propyny1, 3-propyny1, butyny1, pentyny1, hexyny1, or any isomer thereof, 2,7-octadiyny1, or 2,5,8-decatriynyl.
  • Alkynyloxy groups can include, for example, HC ⁇ CCH 2 O, CH 3 C ⁇ CCH 2 O, or CH 3 C ⁇ CCH 2 OCH 2 O.
  • Alkylthio groups can include, for example, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, or any isomer thereof.
  • Alkylsulfonyl groups can include, for example, CH 3 SO 2 , CH 3 CH2SO2, CH3CH2CH2SO2, (CH 3 ) 2 CHS0 2 , butylsulfony1, pentylsulfony1, hexylsulfony1, or any isomers thereof.
  • Alkylsulfinyl groups can include, for example, CH 3 SO, CH 3 CH 2 SO, CH 3 CH 2 CH 2 SO, (CH 3 )2CHSO, butylsulfmy1, pentylsulfmy1, hexylsulfmy1, or any isomers thereof.
  • Carboxylate groups can include, for example, CH 3 CO 2 CH 3 CH 2 CO 2 , C 6 H 5 CO 2 , or (C 6 H 5 )CH 2 CO 2 .
  • Aryl groups can include, for example, pheny1, p-toly1, or p-fluorophenyl.
  • Alkoxide groups can include, for example, methoxide, ethoxide, t-butoxide, or phenoxide.
  • Diketonates can include, for example, acetylacetonate, or 2,4-hexanedionate.
  • Sulfonate groups can include, for example, trifluoromethanesulfonate, tosylate, or mesylate.
  • Phosphine groups can include, for example, trimethylphosphine, triphenylphosphine, or methyldiphenylphosphine.
  • Phosphite groups can include, for example, trimethylphosphite, triphenylphosphite, or methyldiphenylphosphite.
  • Phosphinite groups can include, for example, triphenylphosphinite, or methyldiphenylphosphinite.
  • Functional groups herein, may be referred to as “Fn” such as halo, hydroxy1, sulfhydry1, C 1 -C 24 alkoxy, C 2 -C 24 alkenyloxy, C 2 -C 24 alkynyloxy, C 5 -C 24 aryloxy, C 6 -C 24 aralkyloxy, C 6 -C 24 alkaryloxy, acyl (including C 2 -C 24 alkylcarbonyl ( — CO-alkyl) and
  • C 1 -C 24 alkyl preferably C 1 -C 12 alky1, more preferably C 1 -C 6 alkyl
  • C 2 -C 24 alkenyl preferably C 2 -C 12 alkeny1, more preferably C 2 -C 6 alkenyl
  • C 2 -C 24 alkynyl preferably C 2 -C 12 alkyny1, more preferably C 2 -C 6 alkynyl
  • C 5 -C 24 aryl preferably C 5 -C 14 aryl
  • C 6 -C 24 alkaryl preferably C 6 -C 16 alkaryl
  • C 6 -C 24 aralkyl preferably C 6 -C 16 aralkyl
  • R 3 and R 4 may be independently viny1, H, Me, or Ph.
  • X 1 and X 2 may be independently a halide (e.g., C1, Br, F), CF 3 CO 2 , CH 3 CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, CF 3 (CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate.
  • X 1 and X 2 are Cl.
  • L 1 and L 2 may be independently PMe 3 , P(C 6 H 11 ) 3 , PPh 3 , P(p-Tol) 3 , P(o-Tol) 3 , PMePh 2 , PPhMe 2 , P(CF 3 ) 3 , P(p-FC 6 H 4 ) 3 , pyridine, P(p-CF 3 C 6 H 4 ) 3 , (p-F)pyridine, (p-CF 3 )pyridine, P(C 6 H 4 -SO 3 Na) 3 , or P(CH2 Ce H4 -SO3 Na)3, substituted or unsubstituted imidazobdines (e.g., 1,3-bis(2,4,6- trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ybdene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazob
  • a particularly suitable example of a metal carbene catalyst for use in forming the linear olefin dimers disclosed herein may have a structure represented by Formula 3.
  • This metal carbene catalyst may be referred to as Grubbs II catalyst herein.
  • L 3 may be an N-heterocyclic Lewis base ligand selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ybdene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, or 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene.
  • N-heterocyclic Lewis base ligand selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ybdene, 1,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, or 1,3-bis(2,
  • a particularly suitable metal carbene catalyst having a structure represented by Formula 5 may be used for forming the linear olefin dimers disclosed herein.
  • the metal carbene catalyst may be referred to as Hoveyda-Grubbs II catalyst herein.
  • metal carbene catalysts having a structure represented by Formula 6 wherein M is a group 6 transition metal atoms (e.g., Mo), R 9 and R 10 are independently a hydrogen atom or a group selected from a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, L 4 is an oxygen atom, or a nitrogen atom that is unsubstituted, or substituted with a substituent selected from a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms and a substituted or un
  • a particularly suitable example of a metal carbene catalyst useful for forming linear olefin dimers according to the disclosure herein may have a structure represented by Formula 7.
  • the metal carbene catalyst may be referred to as Schrock catalyst herein.
  • metal carbene catalysts that may be suitably used for forming the linear olefin dimers disclosed herein include, for example, those having a structure represented by Formula 8.
  • the metal carbene catalyst may be contacted with the olefmic feed at a metal carbene catalyst concentration of about 10 ppm or less, or about 8 ppm or less, or about 6 ppm or less, or about 4 ppm or less, or about 3 ppm or less, or about 2.8 ppm or less, or about 2.6 ppm or less, or about 2.4 ppm or less, or about 2.2 ppm or less, or about 2 ppm or less, or about 1.8 ppm or less, or about 1.6 ppm or less, or about 1.4 ppm or less, or about 1.2 ppm or less, or about 1 ppm or less, based on the transition metal atom therein.
  • Loading of the metal carbene catalyst in the metathesis reactor may range from about 0.0005 mol% to about 0.02 mol%, or about 0.001 mol% to about 0.01 mol%, or about 0.0025 mol% to 0.008 mol%.
  • linear olefin dimers may be promoted by removing the ethylene produced during the metathesis reaction. Removing the ethylene may drive the reaction equilibrium toward linear olefin dimer products. For instance, during the metathesis reaction, concurrent stripping and removing of ethylene gas may be performed. Ethylene stripping may be conducted using a stream of inert gas, sparging the reaction products with inert gas, or applying a partial vacuum. Conversion of the LAOs to linear olefin dimers may range from about 30% to 100% conversion, or about 40% to 100% conversion, or about 50% to 100% conversion, or about 60% to 100% conversion, or about 70% to 100% conversion.
  • the olefmic feed and the metal carbene catalyst may be contacted in a hydrocarbon solvent inert to undergoing olefin metathesis, such as to maintain a liquid phase during the metathesis reaction (e.g ., when employing higher LAOs, such as C 20+ LAOs or C 24+ LAOs).
  • suitable inert hydrocarbon solvents may include, but are not limited to, aromatic and alkylaromatic solvents (e.g., benzene, naphthalene, toluene, and xylenes), paraffinic solvents, or any combination thereof.
  • Use of an inert hydrocarbon solvent may be beneficial if the olefmic feed or the linear olefin dimer formed therefrom is a solid under the reaction conditions.
  • the spent catalyst i.e., transition metals, ligands
  • a solid adsorbent such as, but not limited to, activated carbon and oxides (e.g., alumina, silica), or through liquid-liquid extraction.
  • the spent catalyst may be further deactivated by using a quenching treatment comprising a vinyl halide or vinyl ether (e.g., ethyl vinyl ether), for example.
  • the spent catalyst can be further removed by filtration using a diatomaceous earth (e.g., Celite®).
  • a diatomaceous earth e.g., Celite®
  • spent (deactivated) metal carbene catalyst if not removed may advantageously be used to promote hydrogenation or partial hydrogenation to form an at least partially paraffinic hydrocarbon substance.
  • the linear olefin dimers may be subjected to a purification process before and/or after hydrogenation. Accordingly, the linear olefin dimer or a linear paraffin formed therefrom can be recovered in pure or near-pure form, such as about >95% purity, or about >97% purity, or about >99% purity, or about >99.5% purity. Conventional distillation or falling-film evaporation may be suitable for this purpose.
  • BHT butylated hydroxytoluene
  • the at least partially paraffinic hydrocarbon substance obtained by hydrogenating or partially hydrogenating the linear olefin dimers obtained from olefin metathesis may afford a desired melting point.
  • the extent of unsaturation may be about 5% or greater, or about 10% or greater, or about 15% or greater, or about 20% or greater, or about 25% or greater, or about 50% or greater, or about 75% or greater, or about 90% or greater, or fully hydrogenated (100% hydrogenation).
  • the resulting linear paraffins, or a mixture of linear olefin dimers and linear paraffins may be further distilled, if desired. Blending of linear olefin dimers and linear paraffins may also occur after distillation as well.
  • Spent metal carbene catalyst may be used to promote hydrogenation in some instances.
  • the hydrogenation reaction may be carried out at high temperatures of about 80°C or more, such as from about 80°C to about 350°C, or about 80°C to about 250°C, or about 100°C to about 200°C, or about 120°C to about 250°C, for example, and/or a pressure of about 2 gauge bar (barg) to about 100 barg, or about 5 barg to about 80 barg, or about 10 barg to about 60 barg, or about 20 barg to about 50 barg.
  • barg 2 gauge bar
  • the hydrogenation reaction may be carried out at temperatures of about 80°C or more, such as from about 80°C to about 250°C, or from about 100°C to about 200°C, such as 150°C, for example, and/or pressure of about 5 barg to about 30 barg, or about 10 barg to about 20 barg, such as about 15 barg, for example.
  • hydrogenation may be carried out at hydrogenation catalyst loading of about 0.01 wt% to about 3 wt%, or about 0.05 wt% to about 2.5 wt%, or about 0.1 wt% to about 2 wt%, or about 0.2 wt% to about 1.5 wt%, or about 0.3 wt% to about 1 wt%.
  • hydrogenation catalyst loading of about 0.01 wt% to about 3 wt%, or about 0.05 wt% to about 2.5 wt%, or about 0.1 wt% to about 2 wt%, or about 0.2 wt% to about 1.5 wt%, or about 0.3 wt% to about 1 wt%.
  • a dedicated hydrogenation catalyst may be used in other instances.
  • Hydrogenation of the linear olefin dimers described above may be carried out in any suitable manner in a slurry or fixed bed continuous reactor system or under batch conditions using a variety of hydrogenation catalysts, such as those comprising a Group 10 transition metal such as Ni, Pt or Pd. Suitable hydrogenation conditions, hydrogenation catalysts, reactors and the like will be familiar to one having ordinary skill in the art.
  • Reactors suitable for hydrogenation of the linear olefin dimers include, but are not limited to a batch reactors, plug-flow reactors, and liquid continuous mode reactors.
  • the hydrogenated reaction product may be recycled with a fresh feed of the linear olefin dimers and flashed to carry sufficient hydrogen dissolved therein to perform the hydrogenation reaction.
  • Such system configurations may simplify the reactor design.
  • a residual metal carbene catalyst serves as a hydrogenation catalyst, addition of a separate hydrogenation catalyst may not be required.
  • partial hydrogenation of the hydrocarbon substance may be realized to retain at least some unsaturation in the at least partially paraffinic hydrocarbon substance, thereby allowing physical properties intermediate between those of the linear olefin dimer and the corresponding linear paraffin.
  • hydrogenation may be carried out at hydrogenation catalyst loading of about 0.01 wt% to about
  • hydrogenation catalyst is a Ni- based catalyst
  • hydrogenation may be carried out at a hydrogenation catalyst loading of about 50 wt% or more, such as 60 wt% or more, such as 70 wt% or more.
  • Continuous hydrogenation processes particularly under plug flow conditions, may be partially applicable for producing at least partially paraffinic hydrocarbon substances retaining at least some unsaturation therein.
  • continuous hydrogenation suitable for retaining at least some unsaturation may comprise a weigh hourly space velocity of about 5 hr -1 to about 7 hr -1 and a temperature of about 120°C or less.
  • Hydrogenation may be carried out at temperature of about 80°C to about 350°C, or about 80°C to about 250°C, or about 100°C to about 300°C, or about 120°C to about 250°C, and/or at a pressure of about 2 gauge bar (barg) to about 100 barg, or about 5 barg to about 80 barg, or about 10 barg to about 60 barg, and/or at an 3 ⁇ 4: linear olefin dimer ratio of about 0.2 or greater, or about 1 or greater, or about 2 or greater, or about 3 or greater, or about 4 or greater, or about 5 or greater.
  • hydrogenation is performed at an H 2 :linear olefin dimer molar ratio of about 2.
  • Other hydrogenation conditions that may be used to promote full or partial hydrogenation of the hydrocarbon substance include, for example, a temperature of about 80°C to about 250°C, or about 100°C to about 150°C, and pressure ranging from about 20 gauge bar (barg) to about 50 barg.
  • Hydrogenation may be carried out at a weight hourly space velocity (WHSV) of 2 h -1 or less, or 1.5 h -1 or less, or 1 h -1 or less, or 0.5 h -1 or less. Alternately, hydrogenation may be carried out at a WHSV of 0.1 h -1 or greater, such as a WHSV of 0.1 h -1 to 15 h -1 , or 0.5 h -1 to 12 h -1 , or 1 h -1 to 10 h -1 . Partial hydrogenation may be realized at a WHSV of about
  • the hydrogenation catalyst may be removed using a filter aid, such as Celite® HyFlo filter aid.
  • the processes of the present disclosure may include blending linear olefin dimers with linear paraffins to afford a desired extent of unsaturation in the at least partially paraffinic hydrocarbon substance.
  • the hydrogenation reaction may be conducted so as to intentionally leave a portion of the linear olefin dimers unhydrogenated.
  • wax compositions comprising at least partially paraffinic hydrocarbon substances may be further modified through blending with other olefinic or paraffinic blend stock(s), or with one or more blending waxes, which may have a different degree of unsaturation. Any of the foregoing may be conducted to target particularly physical properties, such as melting point or kinematic viscosity. [0093] The processes of the present disclosure are discussed further hereinafter with reference to FIGS. 1-4.
  • FIG. 1 is a flow diagram of a process for producing wax compositions comprising partially hydrogenated linear olefin dimers.
  • Process 100 may include purification 112 of feed 110 by introducing feed 110 comprising at least one linear alpha olefin into a reactor, optionally in combination with one or more internal olefins and/or one or more branched olefins, and removing one or more contaminants therefrom. Removal of the one or more contaminants may be carried out by contacting olefinic feed 110 with an adsorbent, sparging feed 110 with an inert gas, or any combination thereof.
  • the one or more contaminants may comprise a contaminant selected from the group consisting of oxygenates, stabilizers, moisture, metals, heteroatoms, and any combination thereof.
  • purification 112 may involve contacting feed 110 in the melt phase with an adsorbent, as described in further detail above.
  • Purified olefmic feed passes from purification 112 to metathesis reactor 116, such as a CSTR reactor and/or a stirred-tank reactor equipped with an online catalyst injection mechanism 118, wherein the metal carbene catalyst may be formulated as a solution in paraffinic wax or a paraffinic hydrocarbon, for example.
  • Metathesis in reactor 116 may be carried out under inert atmosphere (e.g., Ar or N 2 ) and/or (partial) vacuum by contacting the purified olefmic feed with the metal carbene catalyst under conditions effective to form at least one linear olefin dimer. The pressure may be adjusted to maintain the reaction mixture in a liquid phase.
  • inert atmosphere e.g., Ar or N 2
  • partial vacuum by contacting the purified olefmic feed with the metal carbene catalyst under conditions effective to form at least one linear olefin dimer. The pressure may be adjusted to maintain the reaction mixture in a liquid phase.
  • the ethylene formed during metathesis, as well as any other gaseous byproducts formed therefrom, may be removed via conduit 120 by purging metathesis reactor 116 with an inert gas (e.g., N 2 ) or partial vacuum.
  • an inert gas e.g., N 2
  • At least one linear olefin dimer may be conveyed to catalyst removal 124, wherein the spent metathesis catalyst (e.g., metals, ligands) can be removed through a column packed with a solid adsorbent such as, but not limited to, activated carbon and oxides (e.g., alumina, silica).
  • the spent catalyst may be removed by filtration using a diatomaceous earth (e.g., Celite®).
  • At least one linear olefin dimer free of spent catalyst can then be transferred from catalyst removal 124 to separator 128, such as a distillation column, wherein the linear olefin dimer can be further purified.
  • separator 128, such as a distillation column wherein the linear olefin dimer can be further purified.
  • unconverted feed 130 may be recovered and recycled, if desired.
  • Distilled linear olefin dimer may be removed for further processing into a linear paraffin, or mixture of linear olefin dimers and linear paraffins in hydrogenation reactor 134.
  • product 138 may be obtained as a fully or partially hydrogenated wax composition.
  • FIG. 2 is a flow diagram of a first variant of a process for producing wax compositions comprising linear paraffins formed from hydrogenated linear olefin dimers.
  • hydrogenation reactor 134 is moved upstream of separator 128, thereby providing substantially linear paraffins for distillation.
  • Product 138 obtained after distillation may comprise substantially linear paraffins.
  • FIG. 3 is a flow diagram of a second variant of a process with no catalyst removal for producing wax compositions comprising linear paraffins formed from hydrogenated linear olefin dimers.
  • Process 300 in FIG. 3 differs from process 200 in FIG. 2 in that catalyst removal 124 is omitted prior to hydrogenation.
  • the spent metal carbene catalyst may serve as the hydrogenation catalyst, if desired.
  • FIG. 4 is a flow diagram of a process for producing wax compositions comprising a blend of linear olefin dimers and linear paraffins formed from hydrogenated linear olefin dimers.
  • linear olefin dimers are produced upstream as in process 100 in FIG. 1.
  • process 400 subjects a first portion of the linear olefin dimers to hydrogenation 134 and combines the resulting linear paraffins with a second portion of the linear olefin dimers that have not undergone hydrogenation 134.
  • Blending may be conducted to afford a desired extent of unsaturation in product 138.
  • Hydrogenation 134 may be full or partial in the configuration of process 400.
  • Wax compositions of the present disclosure may comprise a linear olefin dimer and/or a hydrogenated reaction product of the linear olefin dimer in any combination.
  • the wax compositions may be suitable for use in various products such as, for example, candles, cosmetics, rubber, hot melt adhesives, lubricants, pharmaceutical agents, and other articles in which waxes may be used.
  • high temperature properties of hot melt adhesives may be largely controlled by the melt range and the type of wax being used. Accordingly, the wax compositions of the present disclosure may provide the desirable properties for hot melt adhesive formulations due to their tunable melting point.
  • Candles of various types may also be fabricated using the wax compositions disclosed herein.
  • Hot melt adhesives may comprise additional components for adjusting the performance and processing properties.
  • Suitable hot melt adhesives formed from a wax composition of the present disclosure may further comprise a thermoplastic polymer or copolymer, and a tackifier resin, examples of which will be known to a person having ordinary skill in the art.
  • the hot melt adhesives may further include an antioxidant, filler or UV stabilizer or a pigment and others additives suitable for the formulation of the desired hot melt adhesives.
  • Wax compositions of the present disclosure may be used as an ingredient in a variety of hot melt adhesive formulations, including, for example packaging and hygiene hot melt adhesive formulations, wherein the wax compositions may enhance the hot melt adhesive properties, such as, for example, crystallinity kinetics, flow and substrate wetting of the overall hot melt adhesive formulation.
  • Wax compositions of the present disclosure may also be used as an ingredient in PVC lubrication, including, for example, rigid PVC pipe and profile formulations where the wax compositions can be used as lubricants.
  • Suitable processing aids formed from a wax composition of the present disclosure may further comprise a metal complex that provides heat stability, additional intemal/extemal lubricants, a pigment and optionally a filler, examples of which will be known to a person having ordinary skill in the art.
  • Wax compositions of the present disclosure may also be used as an ingredient in the tire manufacturing, including, for example, synthetic and natural rubber formulations where the wax compositions can be used as an ozone protecting barrier (i.e., anti-ozone waxes).
  • ozone protecting barrier i.e., anti-ozone waxes
  • Candles formed from wax compositions of the present disclosure may comprise a wick, a wax composition of the present disclosure and an optional blending wax.
  • the wax composition and the optional blending wax may be used to define a body of the candle.
  • the wick of the candle extends from the wax composition defining the body of the candle.
  • the candles may also include a fragrance or scent.
  • Fragrances and scents may be an artificial fragrance and/or a scent derived from natural sources.
  • the fragrance or scent may be an essential oi1, such as an oil derived from oranges, eucalyptus, peppermint, lavender, or cedarwood, for example, or any combination thereof.
  • the wax composition and the optional blending wax may also be used as additive and/or colorants.
  • Wax compositions of the present disclosure may be used for manufacturing tealights, votives, and wax melts.
  • Pillar candles described herein may be formed into a variety of shapes, including, but not limited to, pillar candles and those situated within a container. Pillar candles are freestanding and, in some embodiments, may be formed using wax compositions formed from higher LAO dimers, such as dimers formed from C 20+ LAOs. Pillar candles may comprise wax compositions of the present disclosure, wherein the wax compositions may have a melting point of about 50°C or greater. Taper candles may also be suitably formed by the disclosure herein.
  • the wick(s) used in the candles may be one or more of hemp-core cotton, zinc-core cotton, coreless cotton, cotton with paper filaments, flat-braided wick, wooden wick, or a wick having a paper core, or any other suitable wick known to one having ordinary skill in the art.
  • the wick may be a high-melting point wick, such as a square braid wick, an ECO wick, a hemp-core wick or a coreless cotton wick.
  • Suitable techniques for forming candles using the wax compositions disclosed herein include, for example, extrusion, compression and slurry processing.
  • Suitable extrusion processes may include, for example, screw, hydraulic ram and rotary drum extrusion, in which the wax compositions are squeezed through a suitably sized orifice and then cut to length.
  • compression processes the wax compositions may be poured into a mold, and the finished candle may be ejected from the mold following solidification.
  • Slurry processes comprise slurrying air or another gas with the wax compositions and forming a candle, thereby utilizing less of the wax compositions than in other types of processes.
  • Dyes or other colorants may be included in the candles in a suitable amount to afford an aesthetically pleasing candle. Suitable amounts of dyes or other colorants will be familiar to one having ordinary skill in the art.
  • Other additives that may be suitably included in the candles disclosed herein include, for example, UV stabilizers, antioxidants, polyethylene waxes, microwaxes, mineral oi1, stearic acid or other fatty acids, and any combination thereof.
  • Embodiments disclosed herein include:
  • A. Processes for making wax compositions comprise: providing a hydrocarbon substance comprising at least one linear olefin dimer, the at least one linear olefin dimer being formed from a first linear alpha olefin having m carbon atoms and a second linear alpha olefin having n carbon atoms in the presence of a metal carbene catalyst, the first linear alpha olefin and the second linear alpha olefin being the same or different, and the linear olefin dimer comprising two carbon atoms less than a sum of m and n; wherein m and n are independently selected integers each ranging from about 12 to about 100; contacting the hydrocarbon substance with a hydrogenation catalyst under hydrogenation reaction conditions; and hydrogenating at least a portion of the at least one linear olefin dimer to form an at least partially paraffinic hydrocarbon substance comprising at least one linear paraffin.
  • the wax compositions comprise: an at least partially paraffinic hydrocarbon substance comprising a hydrogenated or partially hydrogenated reaction product of a hydrocarbon substance comprising at least one linear olefin dimer, the at least one linear olefin dimer being formed from a first linear alpha olefin having m carbon atoms and a second linear alpha olefin having n carbon atoms in the presence of a metal carbene catalyst, the first linear alpha olefin and the second linear alpha olefin being the same or different, and the at least one linear olefin dimer comprising two carbon atoms less than a sum of m and n; wherein m and n are independently selected integers each ranging from about 12 to about 1000; and wherein the at least partially paraffinic hydrocarbon substance has an increased melting point or kinematic viscosity relative to the hydrocarbon substance [0115]
  • Embodiments A and B may have one or more of the following
  • Element 2 wherein the hydrogenation reaction conditions are sufficient to hydrogenate a portion of the least one linear olefin dimer to leave at least some unsaturation in the at least partially paraffinic hydrocarbon substance.
  • Element 3 wherein the at least partially paraffinic hydrocarbon substance has an increased melting point or kinematic viscosity relative to the hydrocarbon substance.
  • Element 4 wherein the hydrocarbon substance has a melting point of at least about 25 °C before hydrogenation, and the at least partially paraffinic hydrocarbon substance has a higher melting point after hydrogenation.
  • Element 5 wherein the hydrocarbon substance has a melting point of at least about 60°C before hydrogenation, and the at least partially paraffinic hydrocarbon substance has a higher melting point after hydrogenation.
  • Element 6 wherein hydrogenating is performed at an 3 ⁇ 4 linear olefin dimer molar ratio of about 0.2 or greater.
  • Element 7 wherein hydrogenating is performed at a temperature of about 80°C to about 250°C.
  • Element 8 wherein hydrogenating is performed at a pressure of about 20 gauge bar (barg) to about 50 barg.
  • Element 9 wherein hydrogenating is performed at a weight hourly space velocity
  • WHSV weight-to-weight ratio
  • Element 10 wherein the hydrogenation catalyst comprises a group 10 transition metal.
  • Element 11 wherein the hydrogenation catalyst comprises spent metal carbene catalyst.
  • Element 12 wherein the at least partially paraffinic hydrocarbon substance has a kinematic viscosity at 100°C of about 3.5 cSt to about 20 cSt.
  • Element 13 wherein the linear olefin dimer has a structure represented by wherein R 1 and R 2 are independently selected alkyl groups having from about 10 to about 98 carbon atoms.
  • Element 14 wherein R 1 and R 2 are independently selected alkyl groups having from about 10 to about 24 carbon atoms or from about 10 to about 28 carbon atoms.
  • Element 15 wherein m and n are independently selected integers each ranging from about 12 to about 30.
  • Element 16 wherein the hydrocarbon substance further comprises: one or more branched olefin dimers; wherein the one or more branched olefin dimers comprise a dimerized reaction product of an internal olefin and the first linear alpha olefin or the second linear alpha olefin, a self-dimerized reaction product of the internal olefin, a dimerized reaction product of a branched olefin and the first linear alpha or the second linear alpha olefin, a self-dimerized reaction product of the branched olefin, a dimerized reaction product of the internal olefin and the branched olefin, or any combination thereof; wherein each of the one or more branched olefin dimers comprises at least two carbon atoms less than a sum of the number of carbon atoms in a first olefin and a second olefin from which the one or
  • Element 18 wherein substantially all of the at least one linear olefin dimer is hydrogenated to form the at least partially paraffinic hydrocarbon substance.
  • Element 19 wherein a portion of the least one linear olefin dimer is hydrogenated to form the at least partially paraffinic hydrocarbon substance.
  • Element 20 wherein the melting point or kinematic viscosity of the at least partially paraffinic hydrocarbon substance is continuously variable between a value of the melting point or kinematic viscosity for the hydrocarbon substance up to a value of the melting point or kinematic viscosity for the at least partially paraffinic hydrocarbon substance obtained after substantially complete hydrogenation.
  • Element 21 wherein the hydrocarbon substance has a melting point of at least about 25°C before hydrogenation, and the at least partially paraffinic hydrocarbon substance has a higher melting point after hydrogenation.
  • Element 22 wherein the hydrocarbon substance has a melting point of at least about 60°C before hydrogenation, and the at least partially paraffinic hydrocarbon substance has a higher melting point after hydrogenation.
  • Element 23 wherein the linear olefin dimer has a structure represented by wherein R 1 and R 2 are independently selected alkyl groups having from about 10 to about 98 carbon atoms.
  • Element 24 wherein R 1 and R 2 are independently selected alkyl groups having from about 10 to about 24 carbon atoms or from about 10 to about 28 carbon atoms.
  • Element 25 wherein m and n are independently selected integers each ranging from about 12 to about 30.
  • Element 26 wherein the hydrocarbon substance further comprises: one or more branched olefin dimers; wherein the one or more branched olefin dimers comprise a dimerized reaction product of an internal olefin and the first linear alpha olefin or the second linear alpha olefin, a self-dimerized reaction product of the internal olefin, a dimerized reaction product of a branched olefin and the first linear alpha or the second linear alpha olefin, a self-dimerized reaction product of the branched olefin, a dimerized reaction product of the internal olefin and the branched olefin, or any combination thereof; wherein each of the one or more branched olefin dimers comprises at least two carbon atoms less than a sum of the number of carbon atoms in a first olefin and a second olefin from which the one or
  • exemplary combinations applicable to A include, but are not limited to: 1 or 2, and 3; 1 or 2, and 4; 1 or 2, and 5; 1 or 2, and 6; 1 or 2, and 6 and 7; 1 or 2, and 7; 1 or 2, and 8; 1 or 2, and 6-8; 1 or 2, and 7 and 8; 1 or 2, and 9; 1 or 2, and 6- 9; 1 or 2, and 11; 1 or 2, and 13; 1 or 2, and 13 and 14; 1 or 2, and 16; 13 and 14; 13 and 15; and 13 and 16.
  • exemplary combinations applicable to B include, but are not limited to: 18 or 19, and 20; 18 or 19, and 21; 18 or 19, and 22; 18 or 19, and 23; 18 or 19, and 23 and 24; 18 or 19, and 26; 21 or 22, and 23; 21 or 22, and 23 and 24; 23 and 25; and 23 and 26.
  • LAO feeds comprising commercial CM, CM, Ci8, or C26+ LAOs or blends of C 12 -C 18 , C 16 -C 18 , or C 20 -C 24 LAOs were reacted using a continuous polymerization unit.
  • CSTR I gallon continuous stirred-tank reactor
  • SS316 low carbon stainless steel I gallon continuous stirred-tank reactor
  • the reactor was thoroughly flushed and cleaned with dewatered toluene and then flushed with purified LAOs.
  • the reactor was subsequently passivated with hot toluene at about 95 °C by circulating the hot toluene through the system for about 4 to 5 hours.
  • the LAO feeds were degassed inline using vacuum to remove any remaining dissolved gasses. Unless indicated below, dimerization was conducted under continuous processing conditions in Examples 1-9. Batch reaction conditions were employed as an alternative where indicated below.
  • LAOs typically contain a mixture of alpha olefins, branched olefins, internal olefins, saturates, and other impurities, some of which may remain in the feed even after purification, which potentially can reduce the activity of the catalyst. Accordingly, prior to the metathesis process, the LAO feeds were purified by passage through a hybrid adsorbent bed of AZ-300 molecular sieves (Honeywell - UOP) for impurity removal (e.g. , sulfur, oxygen, ethylene, peroxides, and other heteroatoms). The AZ-300 was pre-activated with N 2 at 250°C for about 8 hours prior to use.
  • AZ-300 molecular sieves Heneywell - UOP
  • the metal carbene catalyst having a structure represented by Formula 8 is Grubbs CatalystTM 2nd Generation Gr
  • the metal carbene catalysts were used either in solution (previously dissolved in toluene), as a dry powder, or as a slurry mixed with SPECTRASYNTM 4, a polyalphaolefin synthetic basestock (ExxonMobil Chemicals), also referred to as a Group IV base oil according to the API Base Oil Classification system, without any prior activation process.
  • Homogeneous catalyst solutions were prepared in a glove box under N 2 at room temperature by dissolving the metal carbene catalyst (initially in a powder form) in purified, dewatered toluene. The catalyst solutions were protected from moisture and stored at about 4°C in a refrigerator.
  • Catalyst suspensions were also prepared using, for example, the metal carbene catalyst powder dispersed in a low viscosity polyalphaolefm (e.g., viscosity of 2-10 cSt, such as 2, 4 or 6 cSt), or a hydrogenated olefin dimer, such as, for example, a hydrogenated C26 dimer (prepared from a C 14 LAO via a metathesis reaction according to the disclosure herein, followed by hydrogenation).
  • Aromatic solvents such as toluene, may be excluded from the reaction by using a polyalphaolefm catalyst dispersant.
  • the catalyst solution in toluene was delivered sub-surface to the CSTR reactor via a dip tube using a dedicated metering pump.
  • the catalyst solution was stirred continuously in a separate vessel prior to delivery.
  • stirring was conducted at a rate of about 380 rpm.
  • Reactions were conducted at a temperature of about 60°C to about 75°C at a pressure of about 10-25 psi.
  • the reaction temperature was usually limited to about 60°C to about 65°C to limit double bond migration, which may lead to branching in the olefin dimers in addition to that provided by branched or internal olefins in the olefmic feed.
  • the cellulose fiber FIBRA-CEL® BH-40 was added to the bulk of the fluid to be filtered at a loading of about 0.1 wt% to about 0.5 wt% to promote effective filter cake formation.
  • the hydrogenation may be conducted in a plug-flow reactor using heterogeneous Ni or Pt catalysis, or in a batch autoclave reactor using heterogeneous Pd on carbon catalysis.
  • the temperature and pressure conditions for the plug flow and autoclave reactor reactions were as follows: 20 barg to 50 barg and 120°C to 250°C.
  • Example 1 C 16 LAO Metathesis.
  • the catalyst system was a homogeneous solution of Gr II catalyst (Formula 3) in toluene at a loading of 0.0007 mol% or 0.001 mol%.
  • Commercial C 16 LAO feed containing about 90 wt% C 16 LAO, about 3 wt% IOs, and about 7 wt% BOs, was treated with AZ-300 adsorbent and reacted under the general conditions specified above. The reaction was conducted under continuous process conditions.
  • the resulting dimer was further purified by distillation to >99.5% purity.
  • the purified dimer was then hydrogenated using Ni catalyst and filtered.
  • the unhydrogenated dimer had a melting point of about 38°C, and the hydrogenated dimer had a melting point of about 57°C.
  • Example 2 C 16 LAO Metathesis.
  • the catalyst system was a homogeneous solution of Gr II catalyst (Formula 3) in toluene at a loading of 0.0013 mol%.
  • Commercial C 16 LAO feed containing about 90 wt% C 16 LAO, about 3 wt% IOs, and about 7 wt% BOs, was treated with AZ-300 adsorbent and reacted under the general conditions specified above. The reaction was conducted under continuous process conditions. The resulting dimer was further purified by distillation to >99.5% purity. The purified dimer was then hydrogenated using Ni catalyst and filtered.
  • Example 3 Cis LAO Metathesis.
  • the catalyst system was a homogeneous solution of Gr II catalyst (Formula 3) in toluene at a loading of 0.0006 mol%.
  • Commercial C 18 LAO feed containing about 89 wt% C 18 LAOs, about 3 wt% IOs, and about 7 wt% BOs was treated with AZ-300 adsorbent and reacted under the general conditions described above. The reaction was conducted under continuous process conditions.
  • the resulting dimer was further purified by distillation to >99.5% purity.
  • the purified dimer was then hydrogenated using Ni catalyst and filtered.
  • the unhydrogenated dimer had a melting point of about 42°C, and the hydrogenated dimer had a melting point of about 65°C.
  • Example 4 Metathesis of a Blend Comprising C 16 LAO and C 18 LAO.
  • the catalyst system was a homogeneous solution of Gr II catalyst (Formula 3) in toluene at a loading of 0.006 mol%.
  • a blend of commercial Ci6/Ci8 (1:1 wt./wt.) LAOs containing about 90 wt% C 16 /C 18 LAOs, about 3 wt% IOs, and about 7 wt% BOs was treated with AZ-300 adsorbent and reacted under the general conditions specified above. The reaction was conducted under continuous process conditions.
  • the resulting dimer was further purified by distillation to >99.5% purity.
  • the purified dimer was then hydrogenated using Ni catalyst and filtered.
  • the unhydrogenated dimer had a melting point of about 40°C, and the hydrogenated dimer had a melting point of about 61 °C.
  • Table 1 summarizes the continuous process conditions and results obtained for Examples 1-4. Conversion is determined with respect to the LAO content of the feed. Table 1
  • Example 5 Metathesis of a Blend Comprising C 18 , C 20 , C22, and C 24 LAOs.
  • the catalyst system was a homogeneous solution of Gr II catalyst (Formula 3) in toluene.
  • a total of 105 g of white solid was produced.
  • the catalyst residue was filtered from the reactor effluent using Celite® diatomaceous earth filter aid.
  • the resulting dimer was further purified by distillation to >99.5% purity.
  • the purified dimer was then hydrogenated using Pt on alumina catalyst at 200°C and filtered.
  • the unhydrogenated dimer had a melting point of about 57°C, and the hydrogenated dimer had a melting point of about 75°C.
  • Example 6 Metathesis of a Blend Comprising C 18 , C 20 , C22, and C 24 LAOs.
  • the catalyst system was either a homogeneous solution of Gr II catalyst (Formula 3) in toluene or a powder form of the catalyst.
  • Example 7 C14 LAO Metathesis.
  • the catalyst system was either a homogeneous solution of Gr II catalyst (Formula 3) in toluene or a powder form of the catalyst.
  • Commercial C14 LAO feed containing about 91.5 wt% C14 LAOs, about 1.5 wt% IOs, and about 5.5 wt% BOs was treated with AZ-300 adsorbent and reacted under the general conditions specified above in batch mode. About 250 mL of purified C14 LAO were heated up to 55°C while stirring. The reaction was conducted in two steps. A first portion of solid Gr II (Formula 3) catalyst (about 4.2 mg) was added as a powder to the feed to obtain a catalyst loading of 0.0005 mol%.
  • Example 8 Metathesis of a Blend Comprising C 12 , C14, C 16 , and C 18 LAOs.
  • the catalyst system Gr II catalyst (Formula 3) was added to the feed as a powder.
  • a blend of commercial C 12 /C14/C 16 /C 18 LAOs containing about 36 wt% C 12 LAOs, about 29 wt% C14 LAOs, about 21 wt% C 16 LAOs, and about 14 wt% C 18 LAOs was reacted under the general conditions specified above in batch mode.
  • the feed was treated with AZ-300 adsorbent, and purged with a stream of nitrogen.
  • About 0.5 kg of neat feed (0.65 L) was heated to 55°C while stirring.
  • Solid Gr II catalyst (Formula 3) (23 mg) was added to provide a catalyst loading of 0.0011 mol%, and nitrogen was bubbled through the reaction mixture for 3 hours. An additional portion of the catalyst was then added (23 mg) to provide a final catalyst loading of 0.0022 mol%, and the mixture was stirred for an additional 12 hours at 55°C. The reaction mixture was filtered through a short plug of silica to provide 366 g of a colorless liquid, which then crystallized at room temperature. 1 H NMR showed that the LAO conversion was about 100%. The unhydrogenated dimer had a melting point of about 28°C, and the hydrogenated dimer had a melting point of about 50°C.
  • Example 9 C 24 + LAO Metathesis.
  • the catalyst system was a dry powder of Grubbs CatalystTM 2nd Generation Gr II DIPP (Formula 8). A C 24+ cut was obtained from LAOs produced via ethylene polymerization.
  • the feed was treated with AZ-300 adsorbent, purged with a stream of nitrogen, and was reacted under the general conditions specified above in batch mode.
  • the feed (10 g) was suspended in 200 mL of toluene and the resulting mixture was passed through a fine (N4) filter to give a clear, colorless solution. The solution was then sparged with nitrogen, and stored overnight over a bed of AZ-300 molecular sieves.
  • the catalyst (0.5 mg) was added to the solution at 55°C to provide catalyst concentration of 0.0023 mol%. After stirring for 2 days at 55°C, the solvent was evaporated and a white solid product was dried in vacuum to obtain 7.5 g of dimerized product.
  • the dimerized product was sparingly soluble in benzene and toluene.
  • the unhydrogenated dimer had a melting point of about 80°C, and the hydrogenated dimer had a melting point of about 88°C.
  • Example 10 Melting Point Variation of Various Linear Olefin Dimers Before and After Hydrogenation.
  • Various LAO feeds comprising blends of C 12 -C14 LAOs, C 12 -C 18 LAOs, C14-C 18 LAOs, C14-C 24 LAOs, or C 20 -C 24 LAOs were dimerized into C22-C26 linear olefin dimers, C22-C34 linear olefin dimers, C26-C34 linear olefin dimers, C 26 -C 46 linear olefin dimers, or C38-C46 linear olefin dimers, respectively, under the general conditions specified above and subsequently hydrogenated at 250°C and 300 atm for 1-2 hours.
  • FIG. 5 is a graph depicting the melting points of various linear olefin dimers and the corresponding linear paraffins obtained following hydrogenation.
  • a blend of commercial C14-C 24 LAOs was reacted under the general conditions specified above in batch mode.
  • the feed contained 33 wt% C14 LAOs, 24 wt% C 16 LAOs, 18 wt% C 18 LAOs, 12 wt% C 20 LAOs, 9 wt% C22 LAOs, and 4 wt% C 24 LAOs.
  • the feed was treated with AZ-300 adsorbent and purged with a stream of nitrogen. Neat feed (150 mL) was heated to 55°C while stirring.
  • FIG. 6 is a graph depicting the melting point of C 26 -C 46 linear olefin dimers having variable extents of hydrogenation.
  • FIG. 7 is a graph depicting the kinematic viscosity (measured at 100°C, KvlOO) of C 26 -C 46 linear olefin dimers having variable extents of hydrogenation. As shown, both the melting points and kinematic viscosity values increased as the extent of hydrogenation increased (i.e., increased saturation). Thus, partial hydrogenation of the linear olefin dimers formed via metathesis of LAOs may afford wax compositions having tunable physical properties.
  • Example 12 Hydrogenation of C 26 -C 46 Linear Olefin Dimers Mediated by Spent Ru Metathesis Catalyst.
  • C 24 -C 46 linear olefin dimers were prepared as in Example 11, but the spent Gr II Ru metathesis catalyst was not removed.
  • Hydrogenation of the C 26 -C 46 linear olefin dimers was conducted in the presence the Ru spent metathesis catalyst in a 75 cm 3 batch reactor. The batch reactor was pressure tested with N 2 and then pressurized and flushed with H 2 several times. Hydrogenation of the linear olefin dimers was then conducted with stirring for 24 hours at 200°C and a 3 ⁇ 4 pressure of 40 barg. Heating was discontinued, and the batch reactor was depressurized. GC analysis with a flame ionization detector showed that the LAO conversion was about 95%. Cracked products were not observed.
  • Example 13 Melting Point Variation of Various Linear Olefin Dimers Before and After Hydrogenation Under Batch Conditions.
  • Various LAO feeds comprising blends of C 14 -C 18 LAOs, C 18 -C 24 LAOs (Examples 5-6), or C 24+ LAOs (Example 10) were dimerized into C 26 -C 34 linear olefin dimers, C 38 -C 46 linear olefin dimers, or C 46+ linear olefin dimers, respectively, under the general conditions specified above.
  • the metathesis reactions were carried out in batch mode.
  • compositions described herein may be free of any component, or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein.
  • compositions, element or group of elements are preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

Selon l'invention, des compositions de cire peuvent être obtenues par la soumission d'une une ou de plusieurs alpha-oléfines linéaires à une métathèse d'oléfines et à une hydrogénation. Des procédés de production de compositions de cire peuvent comprendre la fourniture d'une substance hydrocarbonée comprenant au moins un dimère d'oléfines linéaires formé à partir d'une première alpha-oléfine linéaire comprenant m atomes de carbone et d'une deuxième alpha-oléfine linéaire comprenant n atomes de carbone en présence d'un catalyseur de type carbène métallique, la première et la deuxième alpha-oléfine linéaire étant identiques ou différentes et le dimère d'oléfines linéaires comprenant deux atomes de carbone de moins que la somme de m et de n ; la mise en contact de la substance hydrocarbonée avec un catalyseur d'hydrogénation dans des conditions de réaction d'hydrogénation ; et l'hydrogénation d'au moins une partie dudit au moins un dimère d'oléfines linéaires pour former une substance hydrocarbonée au moins partiellement paraffinique comprenant au moins une paraffine linéaire. Les variables m et n varient indépendamment d'environ 12 à environ 100.
PCT/US2021/020532 2020-03-10 2021-03-02 Compositions de cire comprenant des dimères d'oléfines linéaires hydrogénées ou partiellement hydrogénées et procédés de production correspondants WO2021183330A1 (fr)

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