EP0785245A2 - Olefin Oligomerizationsverfahren - Google Patents

Olefin Oligomerizationsverfahren Download PDF

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Publication number
EP0785245A2
EP0785245A2 EP97300152A EP97300152A EP0785245A2 EP 0785245 A2 EP0785245 A2 EP 0785245A2 EP 97300152 A EP97300152 A EP 97300152A EP 97300152 A EP97300152 A EP 97300152A EP 0785245 A2 EP0785245 A2 EP 0785245A2
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EP
European Patent Office
Prior art keywords
promoter
hexanol
alcohol
butanol
monomer
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Application number
EP97300152A
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English (en)
French (fr)
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EP0785245A3 (de
Inventor
Kenneth D. Hope
Ting C. Ho
Russell J. Bak
J. Barry Collins
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Chevron Phillips Chemical Co LP
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Chevron Chemical Co LLC
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Publication date
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Publication of EP0785245A2 publication Critical patent/EP0785245A2/de
Publication of EP0785245A3 publication Critical patent/EP0785245A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes

Definitions

  • the present invention relates to a process of producing a higher degree of olefin oligomerization.
  • Synthetic lubricants produced by the oligomerization of alpha-olefins are well-known.
  • the nature of the alpha-olefin from which these oligomers are produced prescribes the properties of the resultant lubricant.
  • linear olefins of from eight to twelve carbons have proven most effective. Normal alpha-olefins are generally preferred.
  • Oligomerization may be achieved with a wide variety of catalysts.
  • Representative catalyst include such Friedel-Crafts agents as AlCl 3 , AlBr 3 , BF 3 , BCl 3 , GaCl 4 , and the like. Although each such agent facilitates oligomerization, the activity of the catalyst will differ widely.
  • the very active catalyst such as AlCl 3
  • Other Friedel-Craft catalysts, such as SnCl 4 or GaCl 3 may present disposal problems after use.
  • solid catalysts present difficulties with respect to control of the exothermic oligomerization reaction due to the heterogeneous nature of the reaction system.
  • a preferred catalyst has been boron trifluoride (BF 3 ), which forms a liquid complex with the necessary promoters, and thus lends itself to conventional reaction systems.
  • the promoter complexes with the BF 3 and, in so doing, provides an activated system needed for initiation of the oligomerization reaction.
  • the most widely used promoters are the alkanoic and/or inorganic acids which are suitable for selective formation of oligomers ranging from two to four monomeric units.
  • the rate of oligomerization is related to some degree to the BF 3 pressure, since the probability of excess BF 3 in the liquid reactants is directly related to its pressure.
  • the subsequent refining processes can be modified to yield particular product compositions. Where, for example, a lubricant consisting chiefly of higher oligomers is desired, one may remove unreacted monomer and low boiling dimer by distillation at atmospheric pressure. Trimer has also been removed in this manner, but through conditions of high vacuum distillation.
  • the substantially saturated lubricant material is then ready for compounding. Depending upon its composition and properties, it may be used directly in a wide variety of known applications. Alternatively, known lubricant additives may be incorporated. The material may be mixed with other available lubricants, to achieve the characteristics necessary for given conventional utilities.
  • the present invention provides a process for producing a high degree of olefin oligomerization.
  • the oligomer distribution can be affected by the size of the primary alcohol that is used as promoter.
  • a higher degree of oligomerization can be achieved by increasing the carbon to hydroxyl ratio for alcohol promoters.
  • a synthetic lubricant material is produced by oligomerizing a C 8-16 ⁇ -olefin monomer in the presence of a boron trifluoride catalyst and a straight-chain alcohol promoter, wherein substantially all of the alcohol promoter has a carbon number of at least four, and at least 80 wt.% of the alcohol promoter has a carbon number of at least five.
  • the olefinic monomer contains predominately 10 to 12 carbon atoms.
  • substantially all of the alcohol promoter has a carbon number of at least five, and least 80 wt.% of the alcohol promoter has a carbon number of at least six.
  • the alcohol promoter is 1-hexanol.
  • the Figure shows the effect of longer chain alcohols on the oligomer distribution of the product. It shows the data from Examples 6 through 8 and Comparative Example B.
  • the present invention involves the oligomerization of an olefinic monomer by contacting that monomer with boron trifluoride and a straight-chain alcohol promoter.
  • Substantially all of the alcohol promoter has a carbon number of at least four, at least 80 wt.% of the alcohol promoter has a carbon number of at least five.
  • the olefins used in making the oligomer are predominately (at least 50 mole %) C 8 -C 16 straight-chain, mono-olefinically unsaturated hydrocarbons in which the olefinic unsaturation occurs at the 1- or ⁇ -position of the straight carbon chain.
  • Straight-chain ⁇ -olefins are used because they are more reactive and commercially available.
  • Such ⁇ -olefins can be made by the thermal cracking of paraffinic hydrocarbons or by the well known Ziegler ethylene chain growth and displacement on triethyl aluminum. Individual olefins may be used, as well as mixtures of such olefins.
  • olefins examples include 1-octene, 1-decene, 1-dodecene, 1-hexadecene and 1-tetradecene.
  • the preferred normal ⁇ -olefin monomers are those containing about 10 to 12 carbon atoms.
  • the olefin monomers can also contain minor amounts of up to about 50 mole %, and usually less than 25 mole %, of internal olefins and vinylidene olefins.
  • the alcohol promoter can be either a single straight-chain alcohol or a mixture of straight-chain alcohols.
  • Examples of preferable single alcohols are 1-pentanol, 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, and 1-tetradecanol.
  • the alcohol promoter is 1-hexanol.
  • Substantially all of the alcohol promoter has a carbon number of at least four, and at least 80 wt.% of the alcohol promoter should have a carbon number of at least five. In other words, the promoter should have no ethanol or propanol, and should have no more than 20% butanol.
  • substantially all of the alcohol promoter has a carbon number of at five, and at least 80 wt.% of the alcohol promoter should have a carbon number of at least six.
  • the promoter preferably should have no ethanol, propanol, or butanol and should have no more than 20% pentanol.
  • the alcohol promoter is used in minor but effective amounts.
  • the total amount of alcohol promoter used can be from about 0.001 to 0.04 moles per mole of monomer (0.1 to 4.0 mole percent).
  • the boron trifluoride is used in molar excess to the amount of promoter. This can be accomplished by using a closed reactor and maintaining a positive boron trifluoride pressure over the reaction mixture.
  • the alcohol can be mixed with the olefin feed and the reaction can be carried out in a batch or continuous process at temperatures of about 0° to 200° C and pressures ranging from atmospheric up to, for example, 1,000 psig.
  • the reaction temperature will change the oligomer distribution, with increasing temperatures favoring the production of dimers.
  • Preferred reaction temperatures and pressures are about 20° to 90° C and 5 to 100 psig.
  • the reaction is terminated by venting off excess boron trifluoride gas and purging with nitrogen gas to replace all boron trifluoride gaseous residue.
  • the reaction product, unreacted monomer, and boron trifluoride-promoter complex residue are removed from the reactor for further processing.
  • the reactor product is then washed with an aqueous caustic solution and followed by several water washes to ensure neutralization.
  • the oligomer mixture from the reaction contains monomer, which can be removed by distillation.
  • the monomer has been found to contain appreciable amounts of less reactive, isomerized material. However, this monomer can be recycled because it will react to form oligomers in the presence of fresh ⁇ -olefin monomer. For example, portions of up to about 25 wt. %, and preferably 5 to 15 wt. % recycled monomer, based on total monomer, can be mixed with fresh monomer.
  • the product mixture can be further separated by distillation to provide one or more product fractions having the desired viscosities for use in various lubricant applications such as drilling, hydraulic or metal working fluids, gear oils and crankcase lubricants.
  • the oligomer product can be hydrogenated by conventional methods to increase the oxidation stability of the product.
  • Supported nickel catalysts are useful.
  • nickel on a Kieselguhr support gives good results.
  • Batch or continuous processes can be used.
  • the catalyst can be added to the liquid and stirred under hydrogen pressure or the liquid may be trickled through a fixed bed of the supported catalyst under hydrogen pressure. Hydrogen pressures of about 100 to 1,000 psig at temperatures of about 150° to 300° C are especially useful.
  • the oligomerization reaction was carried out in an autoclave reactor equipped with a packless stirrer; and all wetted surfaces were made of 316 stainless steel.
  • the reactor had an external electrical heater and an internal cooling coil for temperature control.
  • the reactor was equipped with a dip tube, gas inlet and vent valves, and a pressure relief rupture disc. Prior to the monomer charge, the reactor was cleaned, purged with nitrogen and tested for leaks.
  • the continuous monomer feed reactor was equipped with monomer, promoter and gas inlet ports, vent valves, and a pressure relief rupture disc. At the onset of oligomerization reaction, the reactor was cleaned, purged with nitrogen and tested for leaks. A 1-dodecene monomer flow rate of 2000 grams per hour, a reactor temperature of 30°C and a reactor pressure of 60 psig were controlled throughout the reaction period. The reactor had a gas cap and its liquid volume was controlled through a level control device and approximately one half of the reactor volume. A preformed BF 3 :n-butanol complex was added at a concentration of 0.3 mole % based on feed. The reaction product was discharged to a low pressure flash tank to remove the gaseous reactant. The liquid product stream was then subjected to neutralization and washing steps. The product was saved for further treatments such as hydrogenation and fractionation.
  • Table 3 shows the results of mixtures of alcohols as promotors on the calculated 100° C kinematic viscosity of the trimer and higher oligomers.
  • n-hexanol gives a heavier product than n-butanol, which in turn produces a heavier product than n-propanol.
  • this data shows that mixtures produce lower viscosities than that produced by the lighter of the two alcohols.
  • a 25:75 mixture of propanol:hexanol gives a product viscosity of less than that produced by propanol alone. Butanol and hexanol mixtures behave in a similar manner.
  • Comparative Example H n-butanol was substituted as the promoter for the promoter complex employed in Comparative Example B. Furthermore, the feed was 1-decene instead of 1-dodecene, the BF 3 pressure was 80 psig and the mole % promoter was 2.21. The rest of the procedure was carried through in the same manner as Comparative Example B.
  • Example 9 n-hexanol was substituted for the n-butanol promoter used in Comparative Example H.
  • Example 9 1.63 mole % of n-hexanol was used and in Example 10, 2.24 mole % of n-hexanol was used. The rest of the procedure was carried through in the same manner as Comparative Example H.
  • Table 4 BF 3 Consumption
  • Example Type of Promoter Mole % Promoter of Feed Trimer+ Calculated Viscosity cSt BF 3 wt% of Feed H n-butanol 2.21 8.5 1.16 9 n-hexanol 1.63 8.3 0.92 10 n-hexanol 2.24 9.6 1.17
  • Table 4 shows the effect of n-hexanol as compared to n-butanol in producing near equivalent product viscosity with a savings of the amount of BF 3 consumed.
  • Comparative Example H and Example 9 show that if n-hexanol is used instead of n-butanol, a 8.3 cSt product can be produced with about 20% savings in BF 3 . Conversely, a 9.5 cSt can be produced with near equivalent use of BF 3 by using n-hexanol instead of n-butanol at equivalent mole % of the promoter.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP97300152A 1996-01-12 1997-01-13 Olefin Oligomerizationsverfahren Withdrawn EP0785245A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US58598196A 1996-01-12 1996-01-12
US585981 1996-01-12

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EP0785245A2 true EP0785245A2 (de) 1997-07-23
EP0785245A3 EP0785245A3 (de) 1998-05-06

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JP (1) JPH09194864A (de)
CA (1) CA2194616A1 (de)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3780128A (en) 1971-11-03 1973-12-18 Ethyl Corp Synthetic lubricants by oligomerization and hydrogenation
US4045508A (en) 1975-11-20 1977-08-30 Gulf Research & Development Company Method of making alpha-olefin oligomers
US4587368A (en) 1983-12-27 1986-05-06 Burmah-Castrol, Inc. Process for producing lubricant material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4045507A (en) * 1975-11-20 1977-08-30 Gulf Research & Development Company Method of oligomerizing 1-olefins
EP0323759A3 (de) * 1988-01-06 1990-03-07 Mobil Oil Corporation Olefinpolymerisationsverfahren mit Kontrolle der Viskosität und des Fliesspunktes des Produkts
DE69509082T2 (de) * 1995-06-12 1999-11-25 Amoco Corp Verfahren zur Herstellung von Oligomeren von Mono-Olefinen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3780128A (en) 1971-11-03 1973-12-18 Ethyl Corp Synthetic lubricants by oligomerization and hydrogenation
US4045508A (en) 1975-11-20 1977-08-30 Gulf Research & Development Company Method of making alpha-olefin oligomers
US4587368A (en) 1983-12-27 1986-05-06 Burmah-Castrol, Inc. Process for producing lubricant material

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EP0785245A3 (de) 1998-05-06
CA2194616A1 (en) 1997-07-13
JPH09194864A (ja) 1997-07-29

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