EP2866936A1 - Catalyseur de métathèse et son procédé d'utilisation - Google Patents

Catalyseur de métathèse et son procédé d'utilisation

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Publication number
EP2866936A1
EP2866936A1 EP20130810862 EP13810862A EP2866936A1 EP 2866936 A1 EP2866936 A1 EP 2866936A1 EP 20130810862 EP20130810862 EP 20130810862 EP 13810862 A EP13810862 A EP 13810862A EP 2866936 A1 EP2866936 A1 EP 2866936A1
Authority
EP
European Patent Office
Prior art keywords
oil
fatty acid
olefin
group
alpha
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20130810862
Other languages
German (de)
English (en)
Other versions
EP2866936A4 (fr
Inventor
Matthew W. Holtcamp
Catherine A. Faler
Caol P. Huff
Matthew S. Bedoya
John R. Hagadorn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
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Filing date
Publication date
Priority claimed from US13/535,875 external-priority patent/US8809563B2/en
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Publication of EP2866936A1 publication Critical patent/EP2866936A1/fr
Publication of EP2866936A4 publication Critical patent/EP2866936A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring

Definitions

  • This invention relates to olefin metathesis, more particularly, metathesis catalyst compounds and processes for the use thereof.
  • the cross-metathesis of two reactant olefins, where each reactant olefin comprises at least one unsaturation site, to produce new olefins which are different from the reactant olefins is of significant commercial importance.
  • the cross-metathesis reaction is usually catalyzed by one or more catalytic metals, usually one or more transition metals.
  • LAOs linear alpha- olefins
  • LAOs are useful as monomers or comonomers in certain (co)polymers (polyalphaolefins or PAOs) and/or as intermediates in the production of epoxides, amines, oxo alcohols, synthetic lubricants, synthetic fatty acids, and alkylated aromatics.
  • Olefins Conversion TechnologyTM is an example of an ethenolysis reaction converting ethylene and 2-butene into propylene. These processes use heterogeneous catalysts, such as tungsten and rhenium oxides, which have not proven effective for internal olefins containing functional groups such as cis-methyl oleate, a fatty acid methyl ester.
  • 1-decene is a co-product typically produced in the cross-metathesis of ethylene and methyl oleate.
  • Alkyl oleates are fatty acid esters that can be major components in biodiesel produced by the transesterification of alcohol and vegetable oils. Vegetable oils containing at least one site of unsaturation include canola, soybean, palm, peanut, mustard, sunflower, tung, tall, perilla, grapeseed, rapeseed, linseed, safflower, pumpkin corn and many other oils extracted from plant seeds.
  • Alkyl erucates similarly are fatty acid esters that can be major components in biodiesel.
  • Useful biodiesel compositions are those which typically have high concentrations of oleate and erucate esters. These fatty acid esters preferably have one site of unsaturation such that cross-metathesis with ethylene yields 1-decene as a co-product.
  • Biodiesel is a fuel prepared from renewable sources, such as plant oils or animal fats.
  • TAG triacylglycerides
  • FAE fatty acid alkyl esters
  • Biodiesel fuel can be used in diesel engines, either alone or in a blend with petroleum-based diesel, or can be further modified to produce other chemical products.
  • Cross-metathesis catalysts reported thus far for the ethenolysis of methyl oleate are typically ruthenium-based catalysts bearing phosphine or carbene ligands.
  • Dow researchers in 2004 achieved catalysts turnovers of approximately 15,000 using the 1 st generation Grubb's catalyst, bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride, (Organometallics 2004, 23, 2027).
  • researchers at Materia, Inc. have reported turnover numbers up to 35,000 using a ruthenium catalyst containing a cyclic alkyl amino carbene ligand, (WO 2008/010961).
  • the instant invention's metathesis catalyst compounds provide both a mild and commercially economical and an "atom-economical" route to desirable olefins, in particular alpha-olefins, which in turn may be useful in the preparation of PAOs. More particularly, instant invention's metathesis catalyst compounds demonstrate improved activity and selectivity towards ethenolysis products in ethylene cross- metathesis reactions.
  • This invention relates to a metathesis catalyst compound represented by the formula:
  • M is a Group 8 metal; X and X 1 are anionic ligands; L is a neutral two electron donor; L 1 is N or P, preferably N; G* is selected from the group consisting of hydrogen, a Ci to C30 hydrocarbyl, and a Ci to C30 substituted hydrocarbyl; R is a Q to C30 hydrocarbyl or a Ci to C30 substituted hydrocarbyl; R 1 is selected from the group consisting of hydrogen, a Ci to C30 hydrocarbyl, and a to C30 substituted hydrocarbyl; R 2 is hydrogen, a Q to C30 hydrocarbyl or a to C30 substituted hydrocarbyl; and G is independently selected from the group consisting of hydrogen, halogen, to C30 hydrocarbyls, and Q to C30 substituted hydrocarbyls.
  • This invention also relates to a process to produce alpha olefin (preferably 1- decene) comprising contacting the metathesis catalyst described above with an olefin (preferably ethylene), and one or more triacylglycerides such as fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate).
  • an olefin preferably ethylene
  • triacylglycerides such as fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate).
  • this relates to a process to produce alpha olefin (preferably 1-decene) comprising contacting the metathesis catalyst described above with an olefin (preferably ethylene), and one or more triacylglycerides such as fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate) derived from biodiesel.
  • an olefin preferably ethylene
  • triacylglycerides such as fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate) derived from biodiesel.
  • Figure 1 is a representation of the molecular structure of (PPh 3 )Ci2Ru(3- pentafluorophenyl-6,8-diisopropoxyinden-l-ylidene) (J) drawn with 30% thermal ellipsoids.
  • the present invention comprises a novel metathesis catalyst compound useful for the cross-metathesis of olefins, and processes for the use thereof. More particularly, the present invention comprises a novel metathesis catalyst compound which comprises a chelating indenylene group. Even more particularly, the present invention comprises a novel metathesis catalyst compound which demonstrates improved activity and selectivity towards ethenolysis products in ethylene cross-metathesis reactions.
  • This invention also relates to a process comprising contacting a feed oil or derivative thereof (and optional alkene) with an olefin metathesis catalyst under conditions which yield an alpha-olefin.
  • the feed oil is esterified or transesterified with an alcohol prior to contacting with the olefin metathesis catalyst.
  • This invention also relates to a process comprising contacting a triacylglyceride or a derivative thereof with an optional alkene (such as ethylene) and an olefin metathesis catalyst under conditions which yield an alpha-olefin, typically yielding a linear alpha-olefin (such as 1-decene, 1-heptene, and/or 1-butene) and an ester or acid functionalized olefin.
  • an optional alkene such as ethylene
  • an olefin metathesis catalyst under conditions which yield an alpha-olefin, typically yielding a linear alpha-olefin (such as 1-decene, 1-heptene, and/or 1-butene) and an ester or acid functionalized olefin.
  • This invention further relates to a process for producing alpha-olefins (preferably linear alpha-olefins) comprising contacting a triacylglyceride with an alcohol (such as methanol) to produce a fatty acid alkyl ester and thereafter contacting the fatty acid alkyl ester with an olefin metathesis catalyst (and optional alkene, such as ethylene) under conditions which yield an alpha-olefin (preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene) and an ester or acid functionalized olefin.
  • an alcohol such as methanol
  • an olefin metathesis catalyst and optional alkene, such as ethylene
  • This invention further relates to a process for producing alpha-olefins (preferably linear alpha-olefins) comprising contacting a triacylglyceride with water and/or an alkaline reactant (such as sodium hydroxide) to produce a fatty acid and thereafter contacting the fatty acid with an olefin metathesis catalyst (and optional alkene, such as ethylene) under conditions which yield an alpha-olefin (preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene) and an ester or acid functionalized olefin.
  • alpha-olefins preferably linear alpha-olefins
  • This invention further relates to contacting unsaturated fatty acid with an alkene (such as ethylene) in the presence of an olefin metathesis catalyst under conditions which yield an alpha-olefin (preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1 -butene) and an ester or acid functionalized olefin.
  • an alpha-olefin preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1 -butene
  • This invention further relates to contacting an unsaturated fatty acid ester with an alkene (such as ethylene) in the presence of an olefin metathesis catalyst under conditions which yield an alpha-olefin (preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene) and an ester or acid functionalized olefin.
  • an alpha-olefin preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene
  • This invention further relates to contacting an unsaturated fatty acid alkyl ester with an alkene (such as ethylene) in the presence of an olefin metathesis catalyst under conditions which yield an alpha-olefin (preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene) and an ester or acid functionalized olefin.
  • an alpha-olefin preferably a linear alpha-olefin, preferably 1-decene, 1-heptene, and/or 1-butene
  • This invention also relates to a process to produce alpha olefin (preferably linear alpha olefin, preferably 1-decene, 1-heptene, and/or 1-butene) comprising contacting a metathesis catalyst with an alkene (preferably ethylene), and one or more fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate).
  • alpha olefin preferably linear alpha olefin, preferably 1-decene, 1-heptene, and/or 1-butene
  • alkene preferably ethylene
  • fatty acid esters preferably fatty acid methyl esters, preferably methyl oleate
  • this relates to a process to produce alpha olefin (preferably linear alpha olefin, preferably 1-decene, 1-heptene, and/or 1-butene) comprising contacting a metathesis catalyst with an alkene (preferably ethylene), and one or more fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate) derived from biodiesel.
  • alpha olefin preferably linear alpha olefin, preferably 1-decene, 1-heptene, and/or 1-butene
  • alkene preferably ethylene
  • one or more fatty acid esters preferably fatty acid methyl esters, preferably methyl oleate
  • the olefin metathesis catalysts described herein may be combined directly with feed oils, triacylglycerides, biodiesel, fatty acids, fatty acid esters and/or fatty acid alkyl esters to produce alpha-olefins, preferably linear alpha olefins, preferably C 4 to C24 alpha-olefins, preferably linear alpha-olefins, such as 1-decene, 1- heptene, and/or 1-butene.
  • a mixture of one or more biodiesels, triacylglycerides, fatty acids, fatty acid esters and/or fatty acid alkyl esters is used to produce alpha-olefins, preferably linear alpha olefins, preferably C 4 to C24 alpha-olefins, preferably C 4 to C24 linear alpha-olefins.
  • alpha-olefins preferably linear alpha olefins, preferably 1-decene, 1-heptene, and/or 1-butene is produced.
  • the metathesis catalysts described herein may be combined directly with feed oils, seed oils, biodiesel, triacylglycerides, fatty acids, fatty acid esters, and/or fatty acid alkyl esters ("feed materials") to produce alpha-olefins, preferably linear alpha olefins, preferably C 4 to C24 alpha-olefins, preferably C 4 to C24 linear alpha- olefins, such as preferably 1-decene, 1-heptene, and/or 1-butene.
  • feed oils preferably linear alpha olefins, preferably C 4 to C24 alpha-olefins, preferably C 4 to C24 linear alpha- olefins, such as preferably 1-decene, 1-heptene, and/or 1-butene.
  • the molar ratio of alkene to unsaturated feed material is greater than about 0.8/1.0, preferably greater than about 0.9/1.0.
  • the molar ratio of alkene to feed material is less than about 3.0/1.0, preferably less than about 2.0/1.0.
  • other molar ratios may also be suitable.
  • ethylene for example, a significantly higher molar ratio can be used, because the self-metathesis of ethylene produces only ethylene again; no undesirable co-product olefins are formed.
  • the molar ratio of ethylene to feed material may range from greater than about 0.8/1 to typically less than about 20/1.
  • the quantity of metathesis catalyst that is employed in the process of this invention is any quantity that provides for an operable metathesis reaction.
  • the ratio of moles of feed material (preferably fatty acid ester and/or fatty acid alkyl ester) to moles of metathesis catalyst is typically greater than about 10: 1, preferably greater than about 100: 1, preferably greater than about 1000: 1, preferably greater than about 10,000: 1, preferably greater than about 25,000: 1, preferably greater than about 50,000: 1, preferably greater than about 100,000: 1.
  • the molar ratio of feed material (preferably fatty acid ester and/or fatty acid alkyl ester) to metathesis catalyst is typically less than about 10,000,000: 1, preferably less than about 1,000,000: 1, and more preferably less than about 500,000: 1.
  • the contacting time of the reagents and catalyst in a batch reactor can be any duration, provided that the desired olefin metathesis products are obtained.
  • the contacting time in a reactor is greater than about 5 minutes, and preferably greater than about 10 minutes.
  • the contacting time in a reactor is less than about 25 hours, preferably less than about 15 hours, and more preferably less than about 10 hours.
  • the reactants for example, metathesis catalyst; feed materials; optional alkene, optional alcohol, optional water, etc.
  • a reaction vessel at a temperature of 20 to 300°C (preferably 20 to 200°C, preferably 30 to 100°C, preferably 40 to 60°C) and an alkene (such as ethylene) at a pressure of 0.1 to 1000 psi (0.7 kPa to 6.9 MPa) (preferably 20 to 400 psi (0.14 MPa to 2.8 MPa), preferably 50 to 250 psi (0.34 MPa to 1.7 MPa)), if the alkene is present, for a residence time of 0.5 seconds to 48 hours (preferably 0.25 to 5 hours, preferably 30 minutes to 2 hours).
  • the olefin pressure is greater than about 5 psig (34.5 kPa), preferably greater than about 10 psig (68.9 kPa), and more preferably greater than about 45 psig (310 kPa).
  • the aforementioned pressure ranges may also be suitably employed as the total pressure of olefin and diluent.
  • the aforementioned pressure ranges may be suitably employed for the inert gas pressure.
  • from about 0.005 nmoles to about 500 nmoles, preferably from about 0.1 to about 250 nmoles, and most preferably from about 1 to about 50 nmoles of the metathesis catalyst are charged to the reactor per 3 mmoles of feed material (such as triacylglycerides, biodiesel, fatty acids, fatty acid esters, and/or fatty acid alkyl esters or mixtures thereof, preferably fatty acid esters) charged.
  • feed material such as triacylglycerides, biodiesel, fatty acids, fatty acid esters, and/or fatty acid alkyl esters or mixtures thereof, preferably fatty acid esters
  • the alkene and an unsaturated fatty acid ester or unsaturated fatty acid are co-metathesized to form first and second product olefins, preferably a reduced chain first product alpha-olefin and a second product reduced chain terminal ester or acid-functionalized alpha-olefin.
  • first and second product olefins preferably a reduced chain first product alpha-olefin and a second product reduced chain terminal ester or acid-functionalized alpha-olefin.
  • the metathesis of methyloleate with ethylene will yield co-metathesis products of 1-decene and methyl-9-decenoate. Both products are alpha-olefins; the decenoate also terminates in an ester moiety at the opposite end of the chain from the carbon-carbon double bond.
  • the conversion of feed material can vary widely depending upon the specific reagent olefins, the specific catalyst, and specific process conditions employed.
  • conversion is defined as the mole percentage of feed material that is converted or reacted to the cross-metathesis alpha-olefin products.
  • the conversion of feed material is greater than about 50 mole percent, preferably greater than about 60 mole percent, and more preferably greater than about 70 mole percent.
  • the yields of first product olefin and ester or acid- functionalized second product olefin can also vary depending upon the specific reagent olefins, catalyst, and process conditions employed.
  • Yield will be defined as the mole percentage of cross-metathesis alpha-olefin product olefin formed relative to the initial moles of feed material (such as fatty acid ester and/or fatty acid alkyl ester) in the feed.
  • the yield of alpha-olefin will be greater than about 35 mole percent, preferably greater than about 50 mole percent.
  • the yield of ester or acid- functionalized alpha-olefin will be greater than about 35 mole percent, preferably greater than about 50 mole percent.
  • the process is typically a solution process, although it may be a bulk or high pressure process. Homogeneous processes are preferred. (A homogeneous process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is defined to be a process where reactant concentration in all feeds to the reactor is 70 volume % or more.) Alternately no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst or other additives, or amounts typically found with the reactants; e.g., propane in propylene).
  • Suitable diluents/solvents for the process include non-coordinating, inert liquids.
  • Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof such as can be found commercially (IsoparTM); perhalogenated hydrocarbons such as perfluorinated C4 0 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobutane, butane,
  • Suitable diluents/solvents also include aromatic hydrocarbons, such as toluene or xylenes, and chlorinated solvents, such as dichloromethane.
  • the feed concentration for the process is 60 volume % solvent or less, preferably 40 volume % or less, preferably 20 volume % or less.
  • the process may be batch, semi-batch, or continuous.
  • continuous means a system that operates without interruption or cessation.
  • a continuous process to produce a metathesis product would be one where the reactants are continually introduced into one or more reactors and cross-metathesis alpha-olefin product is continually withdrawn.
  • Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruder, pipe, or pump).
  • the processes may be conducted in either glass lined, stainless steel, or similar type reaction equipment.
  • Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruder, pipe or pump, continuous flow fixed bed reactors, slurry reactors, fluidized bed reactors, and catalytic distillation reactors).
  • the reaction zone may be fitted with one or more internal and/or external heat exchanger(s) in order to control undue temperature fluctuations, or to prevent "runaway" reaction temperatures.
  • the weight hourly space velocity given in units of grams feed material (preferably fatty acid ester and/or fatty acid alkyl ester) per gram catalyst per hour (h _1 ), will determine the relative quantities of feed material to catalyst employed, as well as the residence time in the reactor of the unsaturated starting compound.
  • the weight hourly space velocity of the unsaturated feed material is typically greater than about 0.04 g feed material (preferably fatty acid ester and/or fatty acid alkyl ester) per g catalyst per hour (h _1 ), and preferably greater than about 0.1 h _1 .
  • the weight hourly space velocity of the feed material is typically less than about 100 h _1 , and preferably less than about 20 h _1 .
  • reactions utilizing the catalytic complexes of the present invention can be run in a biphasic mixture of solvents, in an emulsion or suspension, or in a lipid vesicle or bilayer.
  • the feed material is typically provided as a liquid phase, preferably neat.
  • the feed material is provided in a liquid phase, preferably neat; while the alkene is provided as a gas that is dissolved in the liquid phase.
  • feed material is an unsaturated fatty acid ester or unsaturated fatty acid and is provided in a liquid phase, preferably neat; while the alkene is a gaseous alpha-olefin, such as for example, ethylene, which is dissolved in the liquid phase.
  • the feed material is an unsaturated fatty acid ester or unsaturated fatty acid and is provided as a liquid at the process temperature, and it is generally preferred to be used neat, that is, without a diluent or solvent.
  • a solvent usually increases recycle requirements and increases costs.
  • a solvent can be employed with the alkene and/or feed material.
  • a solvent may be desirable, for instance, where liquid feed material and alkene are not entirely miscible, and both then can be solubilized in a suitable solvent.
  • the productivity of the process is at least 200 g of linear alpha-olefin (such as decene-1) per mmol of catalyst per hour, preferably at least 5000 g/mmol/hour, preferably at least 10,000 g/mmol/hr, preferably at least 300,000 g/mmol/hr.
  • productivity is defined to be the amount in grams of linear alpha-olefin produced per mmol of catalyst introduced into the reactor, per hour.
  • selectivity is a measure of conversion of alkene and feed material to the cross-metathesis alpha-olefin product, and is defined by the mole percentage of product olefin formed relative to the initial moles of alkene or feed material.
  • the selectivity of the process is at least 20 wt% linear alpha-olefin, based upon the weight to the material exiting the reactor, preferably at least 25%, preferably at least 30%, preferably at least 35%.
  • catalyst turnover number is a measure of how active the catalyst compound is and is defined as the number of moles of cross- metathesis alpha-olefin product formed per mole of catalyst compound.
  • the (TON), of the process is at least 10,000, preferably at least 50,000, preferably at least 100,000, preferably at least 1,000,000.
  • the alpha olefin yield (when converting unsaturated fatty acids, unsaturated fatty acid esters, unsaturated fatty acid alkyl esters, or mixtures thereof), defined as the mole percentage of cross metathesis alpha olefin product formed per mole of unsaturated fatty acids, unsaturated fatty acid esters, unsaturated fatty acid alkyl esters, or mixtures thereof introduced into the reactor, is 30% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more.
  • the yield for reactions is defined as the moles of alpha olefin formed divided by (the moles of unsaturated R a + moles of unsaturated R b + moles of unsaturated R c ) introduced into the reactor is 30% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more,
  • R a , R b , and R c each, independently, represent a saturated or unsaturated hydrocarbon chain (preferably R a , R b , and R c each, independently, are a C 12 to C 2 g alkyl or alkene, preferably to C 22 alkyl or alkene).
  • the metathesis process of this invention may use an alkene as a reactant.
  • alkene shall mean an organic compound containing at least one carbon-carbon double bond. Alkenes useful herein typically have less than about 10 carbon atoms. The alkene may have one carbon-carbon unsaturated bond, or alternatively, two or more carbon-carbon unsaturated bonds. Since the metathesis reaction can occur at any double bond, alkenes having more than one double bond will produce more metathesis products. Accordingly, in some embodiments, it is preferred to employ an alkene having only one carbon-carbon double bond.
  • the double bond may be, without limitation, a terminal double bond or an internal double bond.
  • the alkene may also be substituted at any position along the carbon chain with one or more substituents, provided that the one or more substituents are essentially inert with respect to the metathesis process.
  • Suitable substituents include, without limitation, alkyl, preferably alkyl; cycloalkyl, preferably cycloalkyl; as well as hydroxy, ether, keto, aldehyde, and halogen functionalities.
  • suitable alkenes include ethylene, propylene, butene, butadiene, pentene, hexene, the various isomers thereof, as well as higher homologues thereof.
  • the alkene is a C2_8 alkene. More preferably the alkene is a C2_6 alkene, even more preferably a C2.4 alkene, and most preferably ethylene.
  • both R* are the same, preferably both R*are hydrogen.
  • Ethylene, propylene, butene, pentene, hexene, and octene are lower olefins useful herein.
  • Triacylglycerides also called triglycerides, are a naturally occurring ester of three fatty acids and glycerol that is the chief constituent of natural fats and oils.
  • the three fatty acids can be all different, all the same, or only two the same, they can be saturated or unsaturated fatty acids, and the saturated fatty acids may have one or multiple unsaturations.
  • Chain lengths of the fatty acids in naturally occurring triacylglycerides can be of varying lengths, but 16, 18, and 20 carbons are the most common. Natural fatty acids found in plants and animals are typically composed only of even numbers of carbon atoms due to the way they are bio-synthesized.
  • Biodiesel is a mono-alkyl ester derived from the processing of vegetable or animal oils and alcohols. The processing is typically carried out by an esterification reaction mechanism, and typically is performed in an excess of alcohol to maximize conversion. Esterification can refer to direct esterification, such as between a free fatty acid and an alcohol, as well as transesterification, such as between an ester and an alcohol.
  • a fatty acid source such as free fatty acids, soaps, esters, glycerides (mono-, di-, tri-), phospholipids, lysophospholipids, or amides and a monohydric alcohol source, such as an alcohol or an ester, can be esterified.
  • a monohydric alcohol source such as an alcohol or an ester
  • various combinations of these reagents can be employed in an esterification reaction.
  • Vegetable and animal oils include triglycerides and neutral fats, such as triacylglyderides, the main energy storage form of fat in animals and plants. These typically have the chemical structure:
  • R a , R b , and R c each, independently, represent a saturated or non-saturated hydrocarbon chain (preferably R a , R b , and R c each, independently, are a C 12 to C 2 g alkyl or alkene, preferably to C 22 alkyl or alkene).
  • R a , R b , and R c each, independently, represent a saturated or non-saturated hydrocarbon chain (preferably R a , R b , and R c each, independently, are a C 12 to C 2 g alkyl or alkene, preferably to C 22 alkyl or alkene).
  • Different vegetable oils have different fatty acid profiles, with the same or different fatty acids occurring on a single glycerol.
  • an oil can have linoleic, oleic, and stearic acids attached to the same glycerol, with each of R a , R b , and R c representing one of these three
  • R a , R b , and R c representing one of these fatty acids.
  • a particularly useful triglyceride consists of three fatty acids (e.g., saturated fatty acids of general structure of CH 3 (CH 2 ) n COOH, wherein n is typically an integer of from 4 to 28 or higher) attached to a glycerol (C3H 5 (OH)3) backbone by ester linkages.
  • fatty acids e.g., saturated fatty acids of general structure of CH 3 (CH 2 ) n COOH, wherein n is typically an integer of from 4 to 28 or higher
  • C3H 5 (OH)3 glycerol
  • esterification process vegetable oils and short chain alcohols are reacted to form mono-alkyl esters of the fatty acid and glycerol (also referred to as glycerin).
  • the alcohol used is methanol (CH3OH)
  • a methyl ester is created with the general form CH3(CH2) n COOCH3 for saturated fatty acids.
  • the length of the carbon backbone chain is from 12 to 24 carbon atoms.
  • the esterification process can be catalyzed or non-catalyzed.
  • Catalyzed processes are categorized into chemical and enzyme based processes.
  • Chemical catalytic methods can employ acid and/or base catalyst mechanisms.
  • the catalysts can be homogeneous and/or heterogeneous catalysts. Homogeneous catalysts are typically liquid phase mixtures, whereas heterogeneous catalysts are solid phase catalysts mixed with the liquid phase reactants, oils and alcohols.
  • the fatty acid rich material useful in the processes described herein can be derived from plant, animal, microbial, or other sources (feed oil).
  • feed oils include vegetable oils such as corn, soy, rapeseed, canola, sunflower, palm, and other oils that are readily available; however, any vegetable oil or animal fat can be employed.
  • Raw or unrefined oil can be used in certain embodiments; however, filtered and refined oils are typically preferred. Use of degummed and filtered feedstock minimizes the potential for emulsification and blockage in the reactors. Feedstock with high water content can be dried before basic catalyst processing.
  • Feedstock with high free fatty acid content can be passed through an esterification process to reduce the free fatty acid content before the process of esterification to convert fatty acid glycerides to monoalkyl esters.
  • the reduction of free fatty acids and the conversion of fatty acid glycerides can also be in the same processing step.
  • Feedstock containing other organic compounds such as hexane, heptane, isohexane, etc.
  • Other materials containing fatty acid glycerides or other fatty acid esters can also be employed, including phospholipids, lysophospholipids, and fatty acid wax esters.
  • the fatty acid rich material useful in the processes described herein typically includes a mixture of fatty acids.
  • the feed oil used as feedstock can also include a mixture of fatty acid glycerides from different sources.
  • the free fatty acid content of useful vegetable oils is preferably about 0.1 wt% or less when employed in a basic homogeneous catalyst esterification reaction. Higher levels can be utilized as well, and levels up to about 3 wt%, or even as high as 15 wt% or more can typically be tolerated.
  • Alcohol also referred to as Alkanols
  • the alcohol used herein can be any monohydric, dihydric, or polyhydric alcohol that is capable of condensing with the feed material (such as the unsaturated fatty acid) to form the corresponding unsaturated ester (such as the fatty acid ester).
  • the alcohol contains at least one carbon atom.
  • the alcohol contains less than about 20 carbon atoms, preferably less than about 12 carbon atoms, and more preferably less than about 8 carbon atoms.
  • the carbon atoms may be arranged in a straight-chain or branched structure, and may be substituted with a variety of substituents, such as those previously disclosed hereinabove in connection with the fatty acid, including the aforementioned alkyl, cycloalkyl, monocyclic aromatic, arylalkyl, alkylaryl, hydroxyl, halogen, ether, ester, aldehyde and keto substituents.
  • the alcohol is a straight-chain or branched alkanol.
  • a preferred alcohol is the trihydric alcohol glycerol, the fatty acid esters of which are known as "glycerides.”
  • Other preferred alcohols include methanol and ethanol.
  • the alcohol employed in the esterification and/or transesterification reactions is preferably a low molecular weight monohydric alcohol such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, or t-butanol.
  • the alcohol is preferably anhydrous; however, a small amount of water in the alcohol may be present (e.g., less than about 2 wt%, preferably less than about 1 wt%, and most preferably less than about 0.5 wt%; however, in certain embodiments higher amounts can be tolerated).
  • Acid esterification reactions are more tolerant of the presence of small amounts of water in the alcohol than are basic transesterification reactions. While specific monohydric alcohols are discussed herein with reference to certain embodiments and examples, the preferred embodiments are not limited to such specific monohydric alcohols. Other suitable monohydric alcohols can also be employed in the preferred embodiments.
  • the conversion of TAGs to fatty acid alkyl esters ("FAAE") through transesterification of the TAG typically involves forming a reactant stream, which includes TAG (e.g., at least about 75 wt%), alkanol (e.g., about 5 wt% to 20 wt%), a transesterification catalyst (e.g., about 0.05 wt% to 1 wt%), and optionally, glycerol (typically up to about 10 wt%).
  • Suitable alkanols may include to alkanols and commonly may include methanol, ethanol, or mixtures thereof.
  • Suitable transesterification catalysts may include alkali metal alkoxides having from 1 to 6 carbon atoms and commonly may include alkali metal methoxide, such as sodium methoxide and/or potassium methoxide.
  • the basic catalyst is desirably selected such that the alkali metal alkoxide may suitably contain an alkoxide group which is the counterpart of the alkanol employed in the reaction stream (e.g., a combination of methanol and an alkali metal methoxide such as sodium methoxide and/or potassium methoxide).
  • the reactant stream may suitably include about 0.05 wt% to 0.3 wt% sodium methoxide, at least about 75 wt% triacylglyceride, about 1 wt% to 7 wt% glycerol, and at least about 10 wt% methanol.
  • the reactant stream may desirably include about 0.05 wt% to 0.25 wt% sodium methoxide, at least about 75 wt% triacylglyceride, about 2 wt% to 5 wt% glycerol, and about 10 wt% to 15 wt% methanol.
  • the rate and extent of reaction for esterification of the fatty acid glycerides or other fatty acid derivates with monohydric alcohol in the presence of a catalyst depends upon factors including, but not limited to, the concentration of the reagents, the concentration and type of catalyst, the temperature and pressure conditions, and time of reaction.
  • the reaction generally proceeds at temperatures above about 50°C, preferably at temperatures above 65°C; however, the catalyst selected or the amount of catalyst employed can affect this temperature to some extent. Higher temperatures generally result in faster reaction rates.
  • very high temperatures such as those in excess of about 300°C, or even those in excess of 250°C, can lead to increased generation of side products, which can be undesirable as their presence can increase downstream purification costs. Higher temperatures can be advantageously employed, however, e.g., in situations where the side products do not present an issue.
  • the reaction temperature can be achieved by preheating one or more of the feed materials or by heating a mixture of the feed materials. Heating can be achieved using apparatus known in the art, e.g., heat exchangers, jacketed vessels, submerged coils, and the like. While specific temperatures and methods of obtaining the specific temperatures are discussed herein with reference to certain embodiments and examples, the preferred embodiments are not limited to such specific temperatures and methods of obtaining the specific temperatures. Other temperatures and methods of obtaining temperatures can also be employed in the preferred embodiments.
  • the amount of alcohol employed in the reaction is preferably in excess of the amount of fatty acid present on a molar basis.
  • the fatty acid can be free or combined, such as to alcohol, glycol or glycerol, with up to three fatty acid moieties being attached to a glycerol. Additional amounts of alcohol above stoichiometric provide the advantage of assisting in driving the equilibrium of the reaction to produce more of the fatty acid ester product. However, greater excesses of alcohol can result in greater processing costs and larger capital investment for the larger volumes of reagents employed in the process, as well as greater energy costs associated with recovering, purifying, and recycling this excess alcohol.
  • lower relative levels of alcohol to fatty acid result in decreased yield and higher relative levels of alcohol levels to fatty acid result in increased capital and operating expense.
  • Some instances of operation at ratios of alcohol to fatty acid over a wider range include when first starting up the process or shutting down the process, when balancing the throughput of the reactor to other processing steps or other processing facilities, such as one that produces alcohol or utilizes a side stream, or when process upsets occur.
  • a molar ratio of 2: 1 methanol to fatty acid is employed and a sodium hydroxide concentration of about 0.5 wt% of the total reaction mixture is employed
  • the ratio of sodium hydroxide to methanol is about 2 wt% entering the reactor and about 4 wt% at the exit because about half of the alcohol is consumed in the esterification reaction.
  • the amount of homogeneous catalyst is preferably from about 0.2 wt% to about 1.0 wt% of the reaction mixture when the catalyst is sodium hydroxide; at typical concentration of 0.5 wt% when a 2: 1 molar ratio of methanol to fatty acid is used; however, in certain embodiments higher or lower amounts can be employed.
  • the amount of catalyst employed can also vary depending upon the nature of the catalyst, feed materials, operating conditions, and other factors. Specifically, the temperature, pressure, free fatty acid content of the feed, and degree of mixing can change the amount of catalyst preferably employed. While specific catalyst amounts are discussed herein with reference to certain embodiments and examples, the preferred embodiments are not limited to such specific catalyst amounts. Other suitable catalyst amounts can also be employed in the preferred embodiments.
  • the esterification reaction can be performed batchwise, such as in a stirred tank, or it can be performed continuously, such as in a continuous stirred tank reactor (CSTR) or a plug flow reactor (PFR).
  • CSTR continuous stirred tank reactor
  • PFR plug flow reactor
  • a series of continuous reactors including CSTRs, PFRs, or combinations thereof
  • batch reactors can be arranged in parallel and/or series.
  • one or more of the feed materials is preferably metered into the process.
  • Various techniques for metering can be employed (e.g., metering pumps, positive displacement pumps, control valves, flow meters, and the like). While specific types of reactors are discussed herein with reference to certain embodiments and examples, the preferred embodiments are not limited to such specific reactors. Other suitable types of reactors can also be employed in the preferred embodiments.
  • Fatty acids are carboxylic acids with a saturated or unsaturated aliphatic tails that are found naturally in many different fats and oils. Any unsaturated fatty acid can be suitably employed in the process of this invention, provided that the unsaturated fatty acid can be metathesized in the manner disclosed herein.
  • An unsaturated fatty acid comprises a long carbon chain containing at least one carbon-carbon double bond and terminating in a carboxylic acid group. Typically, the unsaturated fatty acid will contain greater than about 8 carbon atoms, preferably greater than about 10 carbon atoms, and more preferably greater than about 12 carbon atoms.
  • the unsaturated fatty acid will contain less than about 50 carbon atoms, preferably less than about 35 carbon atoms, and more preferably less than about 25 carbon atoms. At least one carbon-carbon double bond is present along the carbon chain, this double bond usually occurring about the middle of the chain, but not necessarily. The carbon-carbon double bond may also occur at any other internal location along the chain. A terminal carbon-carbon double bond, at the opposite end of the carbon chain relative to the terminal carboxylic acid group, is also suitably employed, although terminal carbon-carbon double bonds occur less commonly in fatty acids. Unsaturated fatty acids containing the terminal carboxylic acid functionality and two or more carbon-carbon double bonds may also be suitably employed in the process of this invention.
  • a fatty acid having more than one double bond may produce a variety of metathesis products.
  • the unsaturated fatty acid may be straight or branched and substituted along the fatty acid chain with one or more substituents, provided that the one or more substituents are substantially inert with respect to the metathesis process.
  • Non-limiting examples of suitable substituents include alkyl moieties, preferably C ⁇ Q alkyl moieties, including, for example, methyl, ethyl, propyl, butyl, and the like; cycloalkyl moieties, preferably C 4 _g cycloalkyl moieties, including for example, cyclopentyl and cyclohexyl; monocyclic aromatic moieties, preferably aromatic moieties, that is, phenyl; arylalkyl moieties, preferably C . ⁇ arylalkyl moieties, including, for example, benzyl; and alkylaryl moieties, preferably C7 6 alkylaryl moieties, including, for example, tolyl, ethylphenyl, xylyl, and the like; as well as hydroxyl, ether, keto, aldehyde, and halide, preferably chloro and bromo, functionalities.
  • alkyl moieties
  • Non-limiting examples of suitable unsaturated fatty acids include 3-hexenoic (hydrosorbic), trans-2-heptenoic, 2-octenoic, 2-nonenoic, cis-and trans-4-decenoic, 9- decenoic (caproleic), 10-undecenoic (undecylenic), trans-3-dodecenoic (linderic), tridecenoic, cis-9-tetradeceonic (myristoleic), pentadecenoic, cis-9-hexadecenoic (cis-9-palmitoelic), trans-9-hexadecenoic (trans-9-palmitoleic), 9-heptadecenoic, cis-6-octadecenoic (petroselinic), trans-6-octadecenoic (petroselaidic), cis-9-octadecenoic (oleic), trans-9- octadecenoic (oleic
  • Fatty acid esters are formed by condensation of a fatty acid and an alcohol.
  • Fatty acid alkyl esters are fatty acids where the hydrogen of the -OH of the acid group is replaced by a hydrocarbyl group, typically a to C30 alkyl group, preferably a Q to C20 alkyl.
  • Fatty acid alkyl esters are fatty acids where the hydrogen of the -OH of the acid group is replaced by an alkyl group.
  • Fatty acid alkyl esters useful herein are typically represented by the formula: R A -C(0)-0-R* ; where R A is a to C ⁇ QO hydrocarbyl group, preferably a to C22 group, preferably a to C 14 1-alkene group, and R* is an alkyl group, preferably a Cj to C20 alkyl group, preferably methyl, ethyl, butyl, pentyl, and hexyl.
  • R A - CH 2 CH 2 -R A -C(0)-0-R* where each R A is, independently a C ⁇ to C 100 alkyl group, preferably a to C20, preferably a Cg to C 14 alkyl group, preferably a C9 group and R* is an alkyl group, preferably a Q to C20 alkyl group, preferably methyl, ethyl, butyl, pentyl, and hexyl.
  • Particularly preferred fatty acid alkyl esters useful herein are represented by the formula:
  • R* is an alkyl group, preferably a to C20 alkyl group, preferably methyl, ethyl, butyl, pentyl, and hexyl
  • m and n are, independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, preferably 5, 7, 9, or 11, preferably 7.
  • Fatty acid methyl esters are fatty acids where the hydrogen of the -OH of the acid group is replaced by methyl group.
  • Fatty acid methyl esters useful herein are typically represented by the formula: R A -C(0)-0-CH 3; where R A is a to C ⁇ QO hydrocarbyl group, preferably a to C22 group, preferably a to C 14 1-alkene group.
  • Preferred fatty acid methyl esters include methyl palmitoleate, methyl oleate, methyl gadoleate, methyl erucate, methyl linoleate, methyl linolenate, methyl soyate, and mixtures of methyl esters derived from soybean oil, beef tallow, tall oil, animal fats, waste oils/greases, rapeseed oil, algae oil, canola oil, palm oil, Jathropa oil, high-oleic soybean oil (e.g., 75 mole% or more, preferably 85 mole% or more, preferably 90 mole% or more), high- oleic safflower oil (e.g., 75 mole% or more, preferably 85 mole% or more, preferably 90 mole% or more), high-oleic sunflower oil (e.g., 75 mole% or more, preferably 85 mole% or more, preferably 90 mole% or more), and other plant or animal derived sources containing
  • a preferred source of fatty acid methyl esters for use herein includes TAG's and biodiesel sources.
  • biodiesel refers to a transesterified vegetable oil or animal fat based diesel fuel containing long-chain alkyl (typically methyl, propyl, or ethyl) esters.
  • Biodiesel is typically made by chemically reacting lipids (such as vegetable oil) with an alcohol.
  • Biodiesel, TAG's and derivatives thereof may be used in the processes described herein.
  • preferred fatty acid methyl esters useful herein may be obtained by reacting canola oil, corn oil, soybean oil, beef tallow, tall oil, animal fats, waste oils/greases, rapeseed oil, algae oil, canola oil, palm oil, Jathropa oil, high-oleic soybean oil, high-oleic safflower oil, high-oleic sunflower oil, or mixtures of animal and/or vegetable fats and oils with one or more alcohols (as described above), preferably methanol.
  • Vegetable oils useful herein preferably contain at least one site of unsaturation and include, but are not limited to, canola, soybean, palm, peanut, mustard, sunflower, tung, tall, perilla, grapeseed, rapeseed, linseed, safflower, pumpkin, corn, and other oils extracted from plant seeds.
  • feed oil refers to one or more plant, animal or microbial oils, including, but not limited to, canola oil, corn oil, soybean oil, fish oil, beef tallow, tall oil, animal fats, waste oils/greases, rapeseed oil, algae oil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil, grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil, Jathropa oil, high-oleic soybean oil, high-oleic safflower oil, high-oleic sunflower oil, mixtures of animal and/or vegetable fats and oils, castor bean oil, dehydrated castor bean oil, cucumber oil, poppyseed oil, flaxseed oil, lesquerella oil, walnut oil, cottonseed oil, meadowfoam, tuna oil, and sesame oils.
  • canola oil corn oil, soybean oil, fish oil, beef tallow, tall oil, animal fats, waste oils/greases, rapeseed oil
  • a combination of oils is used herein.
  • Preferred combinations include two (three or four) or more of tall oil, palm oil, tallow, waste grease, rapeseed oil, canola oil, soy oil, and algae oil.
  • Alternate useful combinations include two (three or four) or more of soy oil, canola oil, rapeseed oil, algae oil, and tallow.
  • processed oils such as blown oils
  • fatty acids are the source of fatty acids useful herein. While vegetable oils are preferred sources of fatty acids for practicing disclosed embodiments of the present process, fatty acids also are available from animal fats including, without limitation, lard and fish oils, such as sardine oil and herring oil, and the like.
  • a desired fatty acid or fatty acid precursor is produced by a plant or animal found in nature.
  • particular fatty acids or fatty acid precursors are advantageously available from genetically modified organisms, such as genetically modified plants, particularly genetically modified algae. Such genetically modified organisms are designed to produce a desired fatty acid or fatty acid precursor biosynthetically or to produce increased amounts of such compounds.
  • Alkyl oleates and alkyl erucates are fatty acid esters that are often major components in biodiesel produced by the transesterification of alcohol and vegetable oils (preferably the alkyls are a to C30 alkyl group, alternately a to C20 alkyl group).
  • Biodiesel compositions that are particularly useful in this invention are those which have high concentrations of alkyl oleate and alkyl erucate esters. These fatty acid esters preferably have one site of unsaturation such that cross-metathesis with ethylene yields 1-decene as the coproduct.
  • Biodiesel compositions that are particularly useful are those produced from vegetable oils such as canola, rapeseed oil, palm oil, and other high oleate oil, high erucate oils.
  • vegetable oils such as canola, rapeseed oil, palm oil, and other high oleate oil, high erucate oils.
  • Particularly preferred vegetable oils include those having at least 50% (on a molar basis) combined oleic and erucic fatty acid chains of all fatty acid chains, preferably 60%, preferably 70%, preferably 80%, preferably 90%.
  • useful fatty acid ester containing mixtures include those having at least 50% (on a molar basis) alkyl oleate fatty acid esters, preferably 60% of alkyl oleate fatty acid esters, preferably 70% of alkyl oleate fatty acid esters, preferably 80% of alkyl oleate fatty acid esters, preferably 90% of alkyl oleate fatty acid esters.
  • useful fatty acid ester containing mixtures include those having at least 50% (on a molar basis) alkyl erucate fatty acid esters, preferably 60% of alkyl erucate fatty acid esters, preferably 70% of alkyl erucate fatty acid esters, preferably 80% of alkyl erucate fatty acid esters, preferably 90% of alkyl erucate fatty acid esters.
  • useful fatty acid ester containing mixtures include those having at least 50% (on a molar basis) combined oleic and erucic fatty acid esters of all fatty acid ester chains, preferably 60%, preferably 70%, preferably 80%, preferably 90%.
  • the feed material is first isomerized, then combined with a metathesis catalyst as described herein.
  • the processes disclosed herein may comprise providing a feed material (typically a fatty acid or fatty acid derivative), isomerizing a site of unsaturation in the feed material (typically a fatty acid or fatty acid derivative) to produce an isomerized feed material (typically a fatty acid or fatty acid derivative), and then contacting the isomerized material with an alkene in the presence of a metathesis catalyst.
  • the isomerized material can be produced by isomerization with or without subsequent esterification or transesterification. Isomerization can be catalyzed by known biochemical or chemical techniques.
  • an isomerase enzyme such as a linoleate isomerase
  • a linoleate isomerase can be used to isomerize linoleic acid from the cis 9, cis 12 isomer to the cis 9, trans 1 1 isomer.
  • This isomerization process is stereospecific; however, nonstereospecific processes can be used because both cis and trans isomers are suitable for metathesis.
  • an alternative process employs a chemical isomerization catalyst, such as an acidic or basic catalyst, can be used to isomerize an unsaturated feed material (typically a fatty acid or fatty acid derivative) having a site of unsaturation at one location in the molecule into an isomerized, feed material (typically a fatty acid or fatty acid derivative) having a site of unsaturation at a different location in the molecule.
  • a chemical isomerization catalyst such as an acidic or basic catalyst
  • an unsaturated feed material typically a fatty acid or fatty acid derivative
  • Metal or organometallic catalysts also can be used to isomerize an unsaturated feed material (typically a fatty acid or fatty acid derivative).
  • nickel catalysts are known to catalyze positional isomerization of unsaturated sites in fatty acid derivatives.
  • esterification, transesterification, reduction, oxidation and/or other modifications of the starting compound or products can be catalyzed by biochemical or chemical techniques.
  • a fatty acid or fatty acid derivative can be modified by a lipase, esterase, reductase, or other enzyme before or after isomerization.
  • the isomerization described above may be practiced with any triacylglycerides, biodiesel, fatty acids, fatty acid esters, and/or fatty acid alkyl esters described herein, typically before contacting with the metathesis catalyst.
  • the metathesis catalyst compound is represented by the Formula (I):
  • M is a Group 8 metal, preferably Ru or Os, preferably Ru;
  • X and X 1 are, independently, any anionic ligand, preferably a halide (preferably CI), an alkoxide, aryloxide, or an alkyl sulfonate, or X and X 1 may be joined to form a dianionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L is a neutral two electron donor, preferably a phosphine or an N-heterocyclic carbene or a cyclic alkyl amino carbene;
  • L 1 is a heteroatom selected from the group consisting of N or P, preferably N;
  • L and X may be joined to form a multidentate monoanionic group and may form single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R is a Ci to C30 hydrocarbyl or a to C30 substituted hydrocarbyl
  • G* is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a C ⁇ to C30 substituted hydrocarbyl, preferably an alkyl or substituted alkyl or hydrogen, preferably fluorinated alkyls or hydrogen;
  • R 1 is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl, preferably methoxy- substituted phenyl, preferably 3,5- substituted phenyl, preferably 3,5-dimethoxyphenyl;
  • R 2 is hydrogen, a to C30 hydrocarbyl, or a Q to C30 substituted hydrocarbyl, preferably methoxy-substituted phenyl, preferably 3,5-substituted phenyl, preferably 3,5- dimethoxyphenyl; and
  • each G is, independently, selected from the group consisting of hydrogen, halogen, a Q to C30 hydrocarbyl, and a Ci to C30 substituted hydrocarbyl hydrogen, (preferably a Ci to C30 alkyl or a substituted to C30 alkyl, or a C 5 to C30 aryl or a substituted C 5 to C30 aryl).
  • Group 8 metal is an element from Group 8 of the Periodic Table, as referenced by the IUPAC in Nomenclature of Inorganic Chemistry: Recommendations 1990, G.J. Leigh, Editor, Blackwell Scientific Publications, 1990.
  • a substituted hydrocarbyl is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom.
  • a substituted alkyl or aryl group is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom or a linear, branched, or cyclic substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms.
  • alkoxides include those where the alkyl group is a C ⁇ to C ⁇ Q hydrocarbyl.
  • the alkyl group may be straight chain or branched.
  • Preferred alkoxides include a C ⁇ to C ⁇ alkyl group, preferably methyl, ethyl, propyl, butyl, or isopropyl.
  • Preferred alkoxides include those where the alkyl group is a phenol, substituted phenol (where the phenol may be substituted with up to 1, 2, 3, 4, or 5 C ⁇ to C12 hydrocarbyl groups) or a C ⁇ to C ⁇ hydrocarbyl, preferably a C ⁇ to C ⁇ alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.
  • Preferred alkyl sulfonates are represented by the Formula (II):
  • R 2 * is a C j to C30 hydrocarbyl group, fluoro-substituted carbyl group, chloro- substituted carbyl group, aryl group, or substituted aryl group, preferably a to alkyl or aryl group, preferably trifluoromethyl, methyl, phenyl, para-methyl-phenyl.
  • aryloxides include those where the aryl group is a phenol or naphthalene, or substituted phenol or substituted naphthalene, where the phenol or naphthalene may be substituted with one or more substituents.
  • Suitable substituents are independently selected and may comprise halogen, Q to hydrocarbyl groups, substituted Q to hydrocarbyl groups, preferably halogen, trifluoromethyl, amino, alkyl, alkoxy, alkylcarbonyl, cyano, carbamoyl, alkoxycarbamoyl, methylendioxy, carboxyl, alkoxycarbonyl, aminocarbonyl, alkyaminocarbonyl, dialkylaminocarbonyl, hydroxy, nitro, and the like, more preferably phenyl, chlorophenyl, trifluoromethylphenyl, chlorofluorophenyl, aminophenyl, methylcarbonylphenyl, methoxyphenyl, methylendioxyphenyl, 1 -naphthyl and 2-n
  • phosphines may be represented by the formula PR3, wherein R is independently selected from the group comprising hydrogen, Q to (3 ⁇ 4 hydrocarbyl groups, substituted Ci to (3 ⁇ 4 hydrocarbyl groups, and halides.
  • N-heterocyclic carbenes (HCs) are represented by the Formula
  • ring A is a 4-, 5-, 6-, or 7-membered ring
  • Q is a linking group comprising from one to four linked vertex atoms selected from the group comprising C, O, N, B, Al, P, S, and Si with available valences optionally occupied by hydrogen, oxo or R- substituents
  • R is independently selected from the group comprising to hydrocarbyl groups, substituted Q to hydrocarbyl groups, and halides
  • each R 4 is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclodo
  • N-heterocyclic carbenes may be represented by the Formula (IV) and (V):
  • each R 4 is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl, phenol, substituted phenol, or CH 2 C(CH 3 ) 3 ; and
  • each R 5 is independently a hydrogen, a halogen, a Q to (3 ⁇ 4 hydrocarbyl group, or a Q to C ⁇ 2 substituted hydrocarbyl group, preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, or aryl.
  • one of the N groups bound to the carbene in Formulae (IV) or (V) is replaced with another heteroatom, preferably S, O, or P, preferably an S heteroatom.
  • Another useful N-heterocyclic carbenes include the compounds described in
  • CAACs are represented by the Formula (VI):
  • ring A is a 4-, 5-, 6-, or 7-membered ring
  • Q is a linking group comprising from one to four linked vertex atoms selected from the group comprising C, O, N, B, Al, P, S, and Si with available valences optionally occupied by hydrogen, oxo or R- substituents
  • R is independently selected from the group comprising to hydrocarbyl groups, substituted Q to hydrocarbyl groups, and halides
  • each R 4 is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclodo
  • CAACs include:
  • CAACs include the compounds described in U.S. 7,312,331 and Bertrand et al, Angew. Chem. Int. Ed. 2005, 44, 7236-7239.
  • Some preferred metathesis catalyst compounds include:
  • catalyst compounds herein are described with respect to olefin cross- metathesis, one of skill in the art will appreciate that the catalyst compounds of this invention may be suitable for any metathesis reaction, including, but not limited to, ring-closing metathesis, enyne metathesis, acyclic diene metathesis, and so on.
  • the catalyst compound employed in the process of this invention may be bound to or deposited on a solid catalyst support.
  • the solid catalyst support will render the catalyst compound heterogeneous, which will simplify catalyst recovery.
  • the catalyst support may increase catalyst strength and attrition resistance.
  • Suitable catalyst supports include, without limitation, silicas, aluminas, silica- aluminas, aluminosilicates, including zeolites and other crystalline porousaluminosilicates; as well as titanias, zirconia, magnesium oxide, carbon, and cross-linked, reticular polymeric resins, such as functionalized cross-linked polystyrenes, e.g., chloromethyl-functionalized cross-linked polystyrenes.
  • the catalyst compound may be deposited onto the support by any method known to those skilled in the art, including, for example, impregnation, ion-exchange, deposition-precipitation, and vapor deposition.
  • the catalyst compound may be chemically bound to the support via one or more covalent chemical bonds, for example, the catalyst compound may be immobilized by one or more covalent bonds with one or more of substituents of the indenylene ligand.
  • the catalyst compound may be loaded onto the catalyst support in any amount, provided that the metathesis process of this invention proceeds to the desired metathesis products.
  • the catalyst compound is loaded onto the support in an amount that is greater than about 0.01 wt% of the Group 8 metal, and preferably greater than about 0.05 wt% of the Group 8 metal, based on the total weight of the catalyst compound plus support.
  • the catalyst compound is loaded onto the support in an amount that is less than about 20 wt% of the Group 8 metal, and preferably less than about 10 wt% of the Group 8 metal, based on the total weight of the catalyst compound and support.
  • catalyst compounds described herein may be synthesized by any methods known to those skilled in the art.
  • Representative methods of synthesizing the Group 8 catalyst compound of the type described herein include, for example, treating a solution of the ligand complex in a suitable solvent, such as THF, with a reactant complex of a Group 8 metal, such as dichloro- bis-(triphenylphosphine)ruthenium (II) and acetyl chloride.
  • a reactant complex of a Group 8 metal such as dichloro- bis-(triphenylphosphine)ruthenium (II) and acetyl chloride.
  • the mixture may be heated, for example to reflux, for a time period appropriate to yield the desired chelating indenylene catalyst compound.
  • removal of the volatiles affords the Group 8 chelating indenylene catalyst compound, which may optionally be purified by suitable chromatographical methods, as known in the art.
  • a phosphine ligand such as tricyclohexylphosphine may be added thereafter, if desired.
  • the reaction conditions typically include mixing the Group 8 reactant catalyst compound and the preferred phosphine ligand in a suitable solvent, such as benzene, for a time sufficient to effectuate the phosphine ligand exchange, at a suitable temperature typically ambient. Copper (I) chloride is then added in excess and removal of the volatiles from resultant slurry typically affords the Group 8 chelating indenylene catalyst compound comprising the more preferred phosphine ligand.
  • transition metal complexes useful in catalyzing metathesis reactions
  • additional ligands may be added to a reaction solution as separate compounds, or may be complexed to the metal center to form a metal-ligand complex prior to introduction to the reaction.
  • the processes described herein produce an alpha olefin, preferably a linear alpha-olefin, which contains at least one more carbon than the alkene used in the reaction to make the alpha-olefin.
  • the processes described herein produce a blend of an alpha olefin and an ester-functionalized alpha olefin.
  • a mixture of non-ester- containing alpha olefins will be produced due to the presence of mono-, di-, and tri- unsubstituted fatty acid chains.
  • the major alpha olefin products are typically 1-decene, 1- heptene, and 1-butene.
  • the major ester-containing alpha olefin product is typically methyl 9- decenoate.
  • the alpha olefin produced herein is 1-decene.
  • the co-product of 1-decene is an ester.
  • the major alpha olefin produced herein is 1-decene.
  • the coproduct of 1-decene is an ester.
  • ethylene and methyl oleate are combined with the metathesis catalysts described herein (such as triphenylphosphinedichlorideruthenium(3-(3,5- dimethoxyphenyl)-6,8-dimethoxyinden-l-ylidene);
  • triphenylphosphinedichlorideruthenium (3-pentafluorophenyl-6,8-diisopropoxyinden- 1 - ylidene); and/or tricyclohexylphosphinedichlorideruthenium (3-pentafluorophenyl-6,8- diisopropoxyinden-l-ylidene)) to produce 1-decene and methyl 9-decenoate.
  • Separation of the 1 -olefin (such as the 1-decene) from the ester may be by means typically known in the art such as distillation or filtration.
  • the linear alpha-olefin cross-metathesis product (such as 1-decene or a mixture of Cg, Cio , Ci2 linear alpha olefins) is then separated from any esters present and preferably used to make poly-alpha-olefins (PAOs).
  • PAOs may be produced by the polymerization of olefin feed in the presence of a catalyst such as AICI3, BF3, or BF3 complexes. Processes for the production of PAOs are disclosed, for example, in the following patents: U.S.
  • PAOs are also discussed in Will, J.G. Lubrication Fundamentals, Marcel Dekker: New York, 1980. Certain high viscosity index PAO's may also be conveniently made by the polymerization of an alpha-olefin in the presence of a polymerization catalyst such as Friedel-Crafts catalysts.
  • These include, for example, aluminum trichloride, boron trifluoride, aluminum trichloride or boron trifluoride promoted with water, with alcohols such as ethanol, propanol, or butanol, with carboxylic acids, or with esters such as ethyl acetate or ethyl propionate or ether such as diethyl ether, diisopropyl ether, etc., see for example, the methods disclosed by U.S.
  • Patents 4, 149, 178; 3,382,29; 3,742,082; 3,769,363 (Brennan); 3,876,720; 4,239,930; 4,367,352; 4,413, 156; 4,434,408; 4,910,355; 4,956, 122; 5,068,487; 4,827,073; 4,827,064; 4,967,032; 4,926,004; and 4,914,254.
  • PAO's can also be made using various metallocene catalyst systems. Examples include U.S.
  • PAOs are often used as additives and base stocks for lubricants, among other things. Additional information on the use of PAO's in the formulations of full synthetic, semi-synthetic or part synthetic lubricant or functional fluids can be found in "Synthetic Lubricants and High-Performance Functional Fluids", 2nd Ed. L. Rudnick, etc. Marcel Dekker, Inc., N.Y. (1999). Additional information on additives used in product formulation can be found in "Lubricants and Lubrications, Ed. By T. Mang and W. Dresel, by Wiley- VCH GmbH, Weinheim 2001.
  • this invention relates to:
  • M is a Group 8 metal; X and X 1 are anionic ligands; L is a neutral two electron donor; L 1 is N or P, preferably N; R is a Ci to C30 hydrocarbyl or a Ci to C30 substituted hydrocarbyl; G* is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl; R 1 is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a to C30 substituted hydrocarbyl; R 2 is hydrogen, a Q to C30 hydrocarbyl or a Q to C30 substituted hydrocarbyl, preferably methoxy-substituted phenyl, preferably 3,5-substituted phenyl, preferably 3,5-dimethoxyphenyl; and G is independently selected from the group consisting of hydrogen, halogen, Q to C30 hydrocarbyls and to C30 substituted hydrocarbyls.
  • each G is independently, a Q to C30 substituted or unsubstituted alkyl, or a substituted or unsubstituted C 4 to C30 aryl.
  • a process to produce alpha-olefin comprising contacting a feed material (such as a feed oil) with the catalyst compound of any of paragraphs 1 to 10.
  • the feed material is selected from the group consisting of canola oil, corn oil, soybean oil, rapeseed oil, algae oil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil, grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil, Jathropa oil, high-oleic soybean oil, high-oleic safflower oil, high-oleic sunflower oil, mixtures of animal and vegetable fats and oils, castor bean oil, dehydrated castor bean oil, cucumber oil, poppyseed oil, flaxseed oil, lesquerella oil, walnut oil, cottonseed oil, meadowfoam, tuna oil, sesame oils, and mixtures thereof.
  • a process to produce alpha-olefin comprising contacting a triacylglyceride with an alkene and the catalyst compound of any of paragraphs 1 to 10, preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
  • a process to produce alpha-olefin comprising contacting an unsaturated fatty acid with an alkene and the catalyst compound of any of paragraphs 1 to 10, preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
  • a process to produce alpha-olefin comprising contacting a triacylglyceride with the catalyst compound of any of paragraphs 1 to 10, preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
  • a process to produce alpha-olefin comprising contacting an unsaturated fatty acid ester and/or unsaturated fatty acid alkyl ester with an alkene and the catalyst compound of any of paragraphs 1 to 10, preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
  • the alpha olefin is a linear alpha- olefin having 4 to 24 carbon atoms.
  • a process to produce C 4 to C24 linear alpha-olefin comprising contacting a feed material with an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene and mixtures thereof and a metathesis catalyst compound of any of paragraphs 1 to 10, wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acid ester derived from seed oil.
  • an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene and mixtures thereof and a metathesis catalyst compound of any of paragraphs 1 to 10, wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acid ester derived from seed oil.
  • This invention also relates to:
  • M is a Group 8 metal
  • X and X 1 are anionic ligands
  • L is a neutral two electron donor
  • L 1 is or P
  • R is a Ci to C30 hydrocarbyl or a Ci to C30 substituted hydrocarbyl
  • G* is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a
  • R 1 is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a C30 substituted hydrocarbyl;
  • R 2 is hydrogen, a Ci to C30 hydrocarbyl or a Q to C30 substituted hydrocarbyl; and G is independently selected from the group consisting of hydrogen, halogen, C to C30 hydrocarbyls and to C30 substituted hydrocarbyls.
  • each G is independently, a to C30 substituted or unsubstituted alkyl, or a substituted or unsubstituted C 4 to C30 aryl.
  • a process to produce alpha-olefin comprising contacting a feed material with a metathesis catalyst compound represented by the formula:
  • M is a Group 8 metal
  • X and X 1 are anionic ligands
  • L is a neutral two electron donor; L 1 is or P;
  • R is a Ci to C30 hydrocarbyl or a to C30 substituted hydrocarbyl
  • G* is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a to C30 substituted hydrocarbyl;
  • R 1 is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl;
  • R 2 is hydrogen, a to C30 hydrocarbyl or a Q to C30 substituted hydrocarbyl
  • G is independently selected from the group consisting of hydrogen, halogen, to C30 hydrocarbyls and to C30 substituted hydrocarbyls.
  • the feed material is a seed oil and is selected from the group consisting of canola oil, corn oil, soybean oil, rapeseed oil, algae oil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil, grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil, Jathropa oil, high-oleic soybean oil, high-oleic safflower oil, high- oleic sunflower oil, mixtures of animal and vegetable fats and oils, castor bean oil, dehydrated castor bean oil, cucumber oil, poppyseed oil, flaxseed oil, lesquerella oil, walnut oil, cottonseed oil, meadowfoam, tuna oil, sesame oils, and mixtures thereof.
  • canola oil corn oil, soybean oil, rapeseed oil, algae oil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil, grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil, Jathro
  • a process to produce alpha-olefin comprising contacting a triacylglyceride with an alkene and a metathesis catalyst compound represented by the formula:
  • M is a Group 8 metal
  • X and X 1 are anionic ligands; L is a neutral two electron donor;
  • L 1 is or P
  • R is a Ci to C30 hydrocarbyl or a to C30 substituted hydrocarbyl
  • G* is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Ci to C30 substituted hydrocarbyl;
  • R 1 is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl;
  • R 2 is hydrogen, a to C30 hydrocarbyl or a Q to C30 substituted hydrocarbyl
  • G is independently selected from the group consisting of hydrogen, halogen, to C30 hydrocarbyls and Ci to C30 substituted hydrocarbyls;
  • the alpha olefin produced has at least one more carbon atom than the alkene.
  • a process to produce alpha-olefin comprising contacting an unsaturated fatty acid with an alkene and the catalyst compound of paragraph 1A.
  • a process to produce alpha-olefin comprising contacting a triacylglyceride with the catalyst compound of paragraph 1A.
  • a process to produce alpha-olefin comprising contacting an unsaturated fatty acid ester and/or unsaturated fatty acid alkyl ester with an alkene and the catalyst compound of paragraph 1A.
  • alpha olefin is a linear alpha-olefin having 4 to 24 carbon atoms.
  • a process to produce alpha-olefin comprising contacting a feed material with an alkene and a metathesis catalyst compound represented by the formula:
  • M is a Group 8 metal
  • X and X 1 are anionic ligands
  • L is a neutral two electron donor
  • L 1 is or P
  • R is a Ci to C30 hydrocarbyl or a to C30 substituted hydrocarbyl
  • G* is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a to C30 substituted hydrocarbyl;
  • R 1 is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl;
  • R 2 is hydrogen, a to C30 hydrocarbyl or a Q to C30 substituted hydrocarbyl
  • G is independently selected from the group consisting of hydrogen, halogen, to C30 hydrocarbyls and to C30 substituted hydrocarbyls;
  • the alpha olefin produced has at least one more carbon atom than the alkene, wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acid ester derived from biodiesel.
  • R a , R b , and R c each, independently, represent a saturated or unsaturated hydrocarbon chain.
  • a process to produce C 4 to C 24 linear alpha-olefin comprising contacting a feed material with an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene, and mixtures thereof and a metathesis catalyst compound represented by the formula:
  • M is a Group 8 metal
  • X and X 1 are anionic ligands
  • L is a neutral two electron donor
  • R is a Ci to C30 hydrocarbyl or a to C30 substituted hydrocarbyl
  • G* is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a to C30 substituted hydrocarbyl;
  • R 1 is selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl;
  • R 2 is hydrogen, a to C30 hydrocarbyl or a Q to C30 substituted hydrocarbyl
  • G is independently selected from the group consisting of hydrogen, halogen, to C30 hydrocarbyls and to C30 substituted hydrocarbyls;
  • the alpha olefin produced has at least one more carbon atom than the alkene, wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acid ester derived from seed oil.
  • Et is ethyl
  • Me is methyl
  • Ph is phenyl
  • Cy is cyclohexyl
  • THF is tetrahydrofuran
  • AcCl is acetyl chloride
  • DMF is dimethylformamide
  • TLC thin layer chromatography.
  • a sample of the metathesis product will be taken and analyzed by GC.
  • An internal standard usually tetradecane, is used to derive the amount of metathesis product that is obtained.
  • the amount of metathesis product is calculated from the area under the desired peak on the GC trace, relative to the internal standard.
  • Yield is reported as a percentage and defined as 100 x [micromoles of metathesis products obtained by GC]/[micromoles of feed material weighed into reactor].
  • Selectivity is reported as a percentage and is defined as 100 x [area under the peak of desired metathesis products]/[sum of peak areas of cross-metathesis and the homometathesis products].
  • Catalyst turnovers for production of the metathesis products is defined as the [micromoles of metathesis product]/[micromoles of catalyst].
  • the metathesis of methyl oleate with ethylene will yield co-metathesis products of 1-decene and methyl-9-decenoate.
  • the methyl oleate may homometathesize to produce small amounts of 9-octadecene, a less desirable product, and l, 18-dimethyl-9-octadecenedioate, a second less desirable product. Yield is defined as 100 x [micromoles of etheno lysis products obtained from the GC]/[micromoles of methyl oleate weighed into reactor].
  • 1-decene selectivity is shown as a percentage and is defined as 100 x [GC peak area of 1-decene & methyl-9-decenoate]/[sum of GC peak areas of 1-decene, methyl-9-decenoate, and the homometathesis products, 9- octadecene, and l, 18-dimethyl-9-octadecenedioate].
  • Catalyst turnovers for production of the 1-decene is defined as the [micromoles of 1-decene obtained from the GC]/[micromoles of catalyst].
  • Acetyl chloride (5 - 10 ⁇ ) was added to a solution of (PPh3) 3 RuCl 2 (336 mg, 0.35 mmol) and 1, 1 di(3,5-dimethoxy)phenyl 2-propyn-l-ol (compound C, 172 mg, 0.525 mmol) in 6 mL THF.
  • the propynol was added as a 0.2 M solution in THF.
  • the solution was allowed to reflux for 18 hours, after which the reaction flask was placed under high vacuum to remove the solvent.
  • Isopropanol (12 mL) was added to the reaction flask and the purple material was removed from the walls by intense stirring overnight.
  • X-ray quality crystals of these ruthenium complexes may be grown by dissolving the crude material in a minimal amount of a solvent such as dichloromethane and then adding an excess of another solvent of differing polarity, for example, isopropanol or hexanes. This solution is then allowed to evaporate at ambient temperature, usually under a nitrogen atmosphere, to yield crystals of the desired ruthenium complex. The crystals are usually removed from the solvent by using a glass frit. Any solid isolated from the filtrate usually contains impure crystals.
  • a solvent such as dichloromethane
  • another solvent of differing polarity for example, isopropanol or hexanes
  • X-ray quality crystals of compound J were grown by dissolving the crude material in a minimal amount of dichloromethane and adding a tenfold excess of isopropanol. This solution was allowed to partially evaporate overnight at ambient temperature under a 2 atmosphere to yield X-ray quality crystals.
  • triphenylphosphineruthenium(3-(3,5-dimethoxyphenyl)-5,7- dimethoxy-indenylidene) (compound D, 5.0 mg, 6.57 ⁇ ) was combined with 100 mL dichloromethane to make a stock solution.
  • Some of this ruthenium catalyst compound stock solution (3.8 mL, 250 nmol) was added to a 20 mL scintillation vial along with 1 equivalent of tricyclohexylphosphine (250 nmol, added as a solution in dichloromethane).
  • Tetradecane (0.152 g) was then added as a standard for gas chromatography analysis.
  • the contents of the vial were transferred to a 100 mL Fisher-Porter vessel equipped with a stirring bar which was then sealed and charged with ethylene (150 psi).
  • the bottle was then placed in an oil bath heated to 40°C for 2 hours.
  • the bottle was depressurized, opened and a few drops ( ⁇ 0.1 mL) of ethyl vinyl ether were added prior to analysis.
  • 1-decene and methyl-9-decenoate yields corresponded to 1800 turnovers of decene per equivalent of ruthenium.
  • Example 5 Ethylenolysis of Methyl Oleate using Compound K, (PCyg ' CbRuP- pentafluorophenyl-6,8-diisopropoxyinden-l-ylidene)
  • the vessel was then filled with ethylene to 150 psig and placed in an oil bath heated to 40°C for 3 hours. The vessel was then depressurized and 5 drops ethyl vinyl ether added to stop the reaction. A sample was analyzed by gas chromatography. The cross-metathesis reaction yielded 18.5% 1-decene and methyl-9- decenoate with 99% selectivity 1-decene and methyl-9-decenoate yields corresponded to 4300 turnovers of decene per equivalent of ruthenium.

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Abstract

La présente invention concerne un composé catalyseur destiné à la métathèse d'oléfines, répondant à la formule : (I) dans laquelle M est un métal du Groupe 8 ; X et X1 sont des ligands anioniques ; L est un donneur neutre de paire d'électrons ; L1 représente N ou P, de préférence N ; R représente un groupe hydrocarbyle en C1 à C30 ou un groupe hydrocarbyle en C1 à C30 substitué ; G* est choisi dans le groupe constitué par un atome d'hydrogène, un groupe hydrocarbyle en C1 à C30 et un groupe hydrocarbyle en C1 à C30 substitué ; R1 est choisi dans le groupe constitué par un atome d'hydrogène, un groupe hydrocarbyle en C1 à C30 et un groupe hydrocarbyle en C1 à C30 substitué ; R2représente un atome d'hydrogène, un groupe hydrocarbyle en C1 à C30 ou un groupe hydrocarbyle en C1 à C30 substitué ; et G est indépendamment choisi dans le groupe constitué par un atome d'hydrogène, un atome d'halogène, un groupe hydrocarbyle en C1 à C30 et un groupe hydrocarbyle en C1 à C30 substitué. La présente invention concerne également un procédé de fabrication d'alpha-oléfines, consistant à mettre en contact une oléfine, telle que l'éthylène, avec une huile d'alimentation contenant un triacylglycéride (typiquement un ester d'acide gras (tel que l'oléate de méthyle)) et avec le composé catalyseur décrit ci-dessus. L'ester d'acide gras peut être un ester méthylique d'acide gras dérivé d'un biodiesel.
EP13810862.6A 2012-06-28 2013-06-12 Catalyseur de métathèse et son procédé d'utilisation Withdrawn EP2866936A4 (fr)

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US13/535,875 US8809563B2 (en) 2009-11-09 2012-06-28 Metathesis catalyst and process for use thereof
PCT/US2013/045390 WO2014004089A1 (fr) 2012-06-28 2013-06-12 Catalyseur de métathèse et son procédé d'utilisation

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EP3219778A1 (fr) * 2016-03-15 2017-09-20 Umicore AG & Co. KG Biocarburant et procédé de préparation par isomérisation de métathèse
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PL379879A1 (pl) * 2006-06-07 2007-12-10 Umicore Ag & Co.Kg. Kompleksy rutenu i osmu, sposób ich wytwarzania oraz ich zastosowanie jako (pre)katalizatorów reakcji metatezy
DE602007002199D1 (de) * 2006-06-30 2009-10-08 Hoffmann La Roche Neue rutheniumkomplexe als katalysatoren für metathesereaktionen
CN102123979A (zh) * 2006-10-13 2011-07-13 埃莱文斯可更新科学公司 通过烯烃复分解由内烯烃合成末端烯烃的方法
US8237003B2 (en) * 2009-11-09 2012-08-07 Exxonmobil Chemical Patents Inc. Metathesis catalyst and process for use thereof
US8592618B2 (en) * 2010-01-08 2013-11-26 Zannan Scitech Co., Ltd. Highly active metathesis catalysts selective for ROMP and RCM reactions
CN102781583B (zh) * 2010-02-12 2015-07-22 埃克森美孚化学专利公司 复分解催化剂和其应用方法
US20130204026A1 (en) * 2010-03-24 2013-08-08 Materia, Inc. Method for in-situ formation of metathesis catalysts
CN102503988A (zh) * 2011-09-23 2012-06-20 内蒙古大学 新型钌卡宾络合物的制备方法及其在烯烃复分解反应中的用途

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