EP0487555A1 - Verfahren zur herstellung von linearen alpha-olefinen aus äthylen - Google Patents

Verfahren zur herstellung von linearen alpha-olefinen aus äthylen

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Publication number
EP0487555A1
EP0487555A1 EP19900911427 EP90911427A EP0487555A1 EP 0487555 A1 EP0487555 A1 EP 0487555A1 EP 19900911427 EP19900911427 EP 19900911427 EP 90911427 A EP90911427 A EP 90911427A EP 0487555 A1 EP0487555 A1 EP 0487555A1
Authority
EP
European Patent Office
Prior art keywords
ethylene
process according
component
carbon atoms
catalyst
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Withdrawn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
EP19900911427
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English (en)
French (fr)
Inventor
Georges Marie Karel Mathys
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
Exxon Chemical Patents Inc
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Filing date
Publication date
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of EP0487555A1 publication Critical patent/EP0487555A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of titanium, zirconium or hafnium

Definitions

  • This invention relates to the oligomerisation of ethylene to produce linear alpha-olefins.
  • Japanese Patent Application No. 60-137683 discloses the production of linear alpha-olefins by polymerising ethylene in the presence of a mixture consisting of a zirconium halide, an alkyl aluminium halide and a compound of sulphur or nitrogen.
  • the present invention provides a process for the oligomerisation of ethylene to produce linear alpha-olefins having a very high degree of linearity.
  • a high degree of linearity is important because ethylene oligomers are used as raw materials for preparing surfactants, e.g. ethoxylated linear alcohols, and linearity is necessary for the surfactants to be biodegradable.
  • surfactants e.g. ethoxylated linear alcohols
  • This process gives a mixture of ethylene oligomers having a high degree of linearity. It is, however, desirable still further to increase the linearity of the oligomeric product, especially in the case of the oligomers containing 12 to 18 carbon atoms. It has now been discovered that the addition of a small amount of oxygen to the ethylene feed usefully increases the linearity of the oligomeric alpha-olefin product.
  • the amount of oxygen present in ethylene ordinarily subjected to oligomerisation is no more than three parts per million by volume.
  • the improved linearity characteristic of the present invention is obtained by using from about 10 to about 50 pp of oxygen by volume based on the ethylene feed.
  • the first component of the catalyst used in the present invention is an adduct of ZrCl a Brj ; , with an ester, ketone, ether, amine, nitrile, anhydride, acid chloride, amide or aldehyde, and these various adduct-forming organic compounds may have up to 30 carbon atoms.
  • the adduct generally includes mole ratios of organic component to zirconium of from about 0.9 to 1 up to about 2 to 1. Equimolar adducts are preferred.
  • the adduct must be soluble and stable in the solvent used as the reaction medium for the oligomerisation process of the invention.
  • Suitable zirconium halides include ZrCl 4 , ZrBr 4 and mixed halides such as ZrClBr 3 , ZrCl 2 Br 2 and ZrCl 3 Br. Adducts of ZrCl 4 are especially preferred.
  • the organic compound used to form the adduct is preferably an ester of the general formula RiCOCD ⁇ wherein R ⁇ and R 2 are each alkyl, aryl, alkaryl, aralkyl of 1 to 30 carbon atoms and R ⁇ may also be hydrogen. ⁇ and 2 taken together may also represent a cycloaliphatic group and the ester may be a lactone such as gammabutyrolactone or phthalide. Especially preferred are alkyl acetate esters wherein the alkyl group has 6 to 16 carbon atoms, e.g.
  • Particularly preferred adducts may be represented by the formula (ZrCl 4 . CH3COOR1 2 where R-i is Cg to C 16 alkyl or a mixture thereof.
  • the isohexyl acetate mixture comprises about, by weight, 36 to 38 per cent n-hexyl acetate, 18 to 20 per cent 2-methyl-1-pentyl acetate.
  • Exxate R 1000 isodecyl acetate mixture is a complex mixture of isomers and gas chromatographic analysis shows about a hundred different isomers being present, none of which are greater than about 10 per cent by weight of the mixture.
  • Exxate 1000 has a boiling point range of about 218°C to 250°C (425 ⁇ F to 482 ⁇ F) (95 per cent distilled).
  • the adducts may be prepared by simple addition of the organic ester to a mixture of ZrCl 4 and the inert organic or alpha-olefin solvent. The ester is added slowly to the stirred mixture at room temperature and complete formation and dissolution of the adduct is observed within a few minutes. The dissolution is exothermic and the mixture can reach a temperature of about 50 * C during the adduct formation.
  • ketones, ethers and aldehydes which may be represented respectively by the formulae R 1 COR 2/ ⁇ O 2 and R ⁇ COH wherein R ⁇ and R2 each represent alkyl, aryl alkaryl or aralkyl and a total number of carbon atoms in R ⁇ and R 2 is not more than about 30.
  • R ⁇ and R2 each represent alkyl, aryl alkaryl or aralkyl and a total number of carbon atoms in R ⁇ and R 2 is not more than about 30.
  • primary, secondary and tertiary amines wherein the hydrocarbyl radicals have up to about 30 carbon atoms such as n-dodecyl amine and tri-n- hexyl amine.
  • adduct forming organic compounds useful in the present invention include nitriles and hydrides, acid chlorides and amides having up to 30 carbon atoms. These may be represented by the formulae RCN, (RCO ⁇ O, RC0C1, RC0NH 2 , RCONHR and RCONR 2 where R represents a hydrocarbyl, alkyl, aryl, alkaryl or aralkyl group of up to 30 carbon atoms. Examples are n-undecane nitrile, n-decyl succinic anhydride and n-decanoyl chloride.
  • the second catalyst component used in the present invention is an aluminium alkyl of the formula R 2 A1X, RA1X 2 , R3AI3X 3 , R 3 AI or a zinc alkyl of the formula R 2 Zn where lf R 2 and R 3 each represent alkyl of 1 to 20 carbon atoms and X is Cl or Br. Diethylaluminium chloride, aluminium ethyl dichloride and mixtures thereof are preferred.
  • the process of the present invention may be conducted under generally known oligomerisation conditions of temperature and pressure, that is at a temperature from about 50 ' to 250* C and under a pressure of 3450 to 34500 kPa (500 to 5,000 psig) , preferably 6900 to 24100 kPa (1,000 to 3,500 psig) .
  • the process is conducted in solution in an inert solvent which must be non-reactive with the catalyst system, and optionally in the presence of a solvent comprising a liquid alpha-olefin, especially a C 6 -C 10 0 alpha-olefin.
  • Suitable solvents include aromatic or aliphatic hydrocarbons and halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene and chloro-toluene.
  • Preferred solvents are toluene, xylenes and alkanes of 3 to 24 carbon atoms, especially heptane. Mixtures of these solvents may also be used.
  • Liquid alpha-olefins may also be used as solvents for the process, and these may include, more particularly, liquid alpha- olefins which have been formed by the oligomerisation process, especially those containing 6 to 30 carbon atoms. Such alpha- olefins may be used in admixture with the aforesaid non-reactive aromatic or aliphatic solvents.
  • a useful solvent mixture comprises a minor proportion of C 4 to C30 alpha-olefins, such as about 10 per cent by weight of Cg and C 10 alpha-olefins and
  • the ethylene used in the present invention preferably contains not more than the following limits of impurities: acetylenic hydrocarbons less than 1 part per million by weight; dienes less than 1 part per million by weight; carbon monoxide less than 5 parts per million by weight; carbon dioxide less than 15 parts per million by weight; oxygen- containing compounds (e.g. methanol, ethanol, acetone or sec- butanol) less than 1 part per million by weight; water less than 5 parts per million by weight; hydrogen less than 1 part per million by weight; oxygen less than 3 parts per million by weight; sulphur less than 5 milligrams per cubic meter; chlorine less than 5 milligrams per cubic meter.
  • acetylenic hydrocarbons less than 1 part per million by weight
  • dienes less than 1 part per million by weight
  • carbon monoxide less than 5 parts per million by weight
  • carbon dioxide less than 15 parts per million by weight
  • oxygen- containing compounds e.g. methanol, ethanol, acetone or sec- but
  • the water content of the ethylene is preferably reduced still further to less than 20 parts per billion before it is subjected to the oligomerisation, e.g. by contacting with 3A molecular sieve.
  • the linearity of the alpha-olefin oligomers is improved by introducing into the reaction mixture from 10 to 50 parts per million by volume, preferably 20 to 40 parts per million by volume, of oxygen.
  • the amount of catalyst used needs to be somewhat increased in order to compensate for the reduction of catalyst activity caused by the oxygen. For example, at about 40 ppm of oxygen by volume the catalyst concentration needs to be doubled to achieve the same degree of conversion as that obtained in the absence of the oxygen.
  • the proportion of catalyst should be increased by about 30 per cent.
  • the ethylene and oxygen feed and the catalyst components may be introduced into the reaction vessel in any order, but preferably the ethylene, which may be pre-dissolved in the solvent, and the oxygen and the solution of zirconium tetra- halide adduct are first mixed and the second component of the catalyst, also in solution, is then added.
  • the temperature and pressure of the oligomerisation may be varied to adjust the molecular weight and yield of the desired product.
  • the molecular weight (Mn) may also be controlled by adjustment of the molar ratio of the second component of the catalyst to the first component (i.e. of the aluminium or zinc to the zirconium) .
  • the preferred reaction temperature for the production of high quality linear alpha-olefin oligomers having from 6 to 20 carbon atoms is about 120" to 250'C.
  • the reaction pressure should be about 6900 kPa (1,000 psig) in a continuous stirred tank reactor. This produces about 20 per cent conversion of ethylene and limits the production of high molecular weight polyethylene to less than about 0.1 weight per cent of the product.
  • conversions of 65 to 80 per cent of ethylene at about 120 * to 250"C can be achieved at pressures of about 20700 kPa (3,000 psig), depending upon the exact configuration of the reactor.
  • the amount of catalyst used is conveniently expressed as the weight ratio of the ethylene feed to the zirconium in the catalyst.
  • ethylene ethylene ethylene
  • the preferred amount being from 25,000 to 35,000 parts by weight of ethylene per part by weight of zirconium and most preferably about 31,000 parts by weight of ethylene.
  • the amount of water present in the reaction system should be reduced as far as possible since the catalyst is particularly sensitive to water. Small amounts of water tend to increase the production of the undesired high molecular weight polyethylene and reduce conversion to the desired linear alpha-olefins.
  • the relative amounts of the two catalyst components used in the process of the invention can be varied, but a mol ratio of the second component to the first component from about 1 : 1 up to about 50 : 1 is generally used, the preferred ratio being from about 10 : l to about 25 : 1.
  • the mol ratio of the ethylene feed to the oligomerisation product should be maintained at about 0.8 in order to minimize copolymerisation reactions which might interfere with the achievement of the desired high degree of linearity of the product.
  • this ratio is greater than 2.
  • the linear alpha-olefin oligomerisation product may be isolated by conventional procedures, e.g. use of an aqueous caustic catalyst quench followed by water washing and recovery of the final product by distillation.
  • Ethylene was fed continuously at a measured rate to the reactor during the test runs.
  • Reaction solvent was dried over molecular sieves to less than 1 ppmw and then etered continuously into the reactor.
  • Catalyst and co-catalyst solutions were prepared in a dry box using heated and evacuated glassware to ensure minimum water contamination.
  • the zirconium catalyst was diluted in dry solvent (solvent dried to less than 1 ppmw over molecular sieves) to a concentration of about 20 x 10 ⁇ 6 gram moles of zirconium per gram of solution.
  • the solutions were then transferred to the reactor feed tanks and held under a nitrogen blanket.
  • the Zr catalyst solution was fed to the reactor at 10 to 100 cc/hr.
  • the aluminium co-catalyst solutions were prepared from concentrated stock solutions obtained from a commercial supplier. Again, dilution solvent was dried to less than 1 ppmw water content before use.
  • Co- catalyst was generally diluted to about 200 x 10" 6 gram moles of aluminium per gram of solution. The diluted solution was transferred to the reactor at 10 to 100 cc/hr.
  • a test run was started by feeding solvent, ethylene, and co-catalyst to the reactor during a heat-up period lasting up to several hours. Then, the Zr catalyst feed was started. A run balance period for data collection was started after steady state was achieved, generally 1-2 hours after the oligomerization was initiated, as noted by the reaction temperature.
  • the catalyst used was a equimolar complex of
  • oxygen was added to the reaction mixture in a proportion of 37, 21 or 23.5 parts per million by volume based on the ethylene.
  • the reaction conditions were otherwise identical except that the Zr and Al catalyst concentration had to be doubled in the case of 37 ppm by volume of oxygen and had to be increased by 30% in the case of 21 or 23.5 ppm by volume of oxygen at achieve comparable conversion levels.
  • This oxygen was deliberately added to ethylene feed and continuously monitored during the runs.
  • Run no. 26 The data for Run no. 26 are included for comparison. They show that, in the presence of 37 ppmw of oxygen, if too small an amount of the catalyst is used, the percentage conversion becomes very small.
  • the proportion of linear olefins obtained decreases and that of branched olefins obtained increases as the conversion rate of the ethylene increases.
  • the amount of internal linear olefins which can be calculated by subtracting the total amount of alpha and branched isomers of a given carbon number from 100, remains the same with or without oxygen being present.
  • the addition of oxygen to the reaction mixture in accordance with the present invention increases the alpha linearity of the oligomers obtained. This is illustrated in the accompanying -awings.
  • Figures 1 and 2 show the weight percentage of linear alpha-olefins plotted against weight percentage conversion of the ethylene feed and: Figures 3 and 4 show the weight percentage of branched olefins plotted against the weight percentage conversion of the ethylene feed.
  • the solid lines represent the weight percentage of linear ( Figures 1 and 2) or branched ( Figures 3 and 4) olefins to be expected in the absence of oxygen.
  • the plotted points show the results obtained in the presence of oxygen as given above in Tables 3 and 4.
  • Figures 1 and 3 relates to oligomers having 8, 12 or 18 carbon atoms
  • Figures 2 and 4 relates to oligomers having 6,10, 14 and 16 carbon atoms. In each case the increased linearity or reduction in branching achieved by the presence of the oxygen is clearly shown.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
EP19900911427 1989-08-14 1990-08-14 Verfahren zur herstellung von linearen alpha-olefinen aus äthylen Withdrawn EP0487555A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898918497A GB8918497D0 (en) 1989-08-14 1989-08-14 Process for preparing linear alpha-olefins from ethylene
GB8918497 1989-08-14

Publications (1)

Publication Number Publication Date
EP0487555A1 true EP0487555A1 (de) 1992-06-03

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Country Status (5)

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EP (1) EP0487555A1 (de)
JP (1) JPH05504942A (de)
CA (1) CA2064832A1 (de)
GB (1) GB8918497D0 (de)
WO (1) WO1991002707A1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2693455B1 (fr) * 1992-07-09 1994-09-30 Inst Francais Du Petrole Procédé de fabrication d'oléfines alpha légères par oligomérisation de l'éthylène.
US8426535B2 (en) * 2001-08-06 2013-04-23 Ineos Europe Limited Chain growth reaction process
US7087686B2 (en) * 2001-08-06 2006-08-08 Bp Chemicals Limited Chain growth reaction process
JP5166662B2 (ja) * 2001-09-27 2013-03-21 出光興産株式会社 α−オレフィン低重合体の製造方法
DE602005024134D1 (de) 2005-08-31 2010-11-25 Saudi Basic Ind Corp Prozess zur Darstellung linearer Alpha-Olefine und ein Katalysator hierfür
US10513473B2 (en) 2015-09-18 2019-12-24 Chevron Phillips Chemical Company Lp Ethylene oligomerization/trimerization/tetramerization reactor
US10519077B2 (en) 2015-09-18 2019-12-31 Chevron Phillips Chemical Company Lp Ethylene oligomerization/trimerization/tetramerization reactor
US11667590B2 (en) 2021-05-26 2023-06-06 Chevron Phillips Chemical Company, Lp Ethylene oligomerization processes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4855525A (en) * 1987-06-19 1989-08-08 Exxon Chemical Patents Inc. Process for preparing linear alpha-olefins using zirconium adducts as catalysts

Non-Patent Citations (1)

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Title
See references of WO9102707A1 *

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Publication number Publication date
WO1991002707A1 (en) 1991-03-07
GB8918497D0 (en) 1989-09-20
JPH05504942A (ja) 1993-07-29
CA2064832A1 (en) 1991-02-15

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