EP1530554A1 - Procede de production d'hydrocarbures synthetiques - Google Patents

Procede de production d'hydrocarbures synthetiques

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Publication number
EP1530554A1
EP1530554A1 EP03793725A EP03793725A EP1530554A1 EP 1530554 A1 EP1530554 A1 EP 1530554A1 EP 03793725 A EP03793725 A EP 03793725A EP 03793725 A EP03793725 A EP 03793725A EP 1530554 A1 EP1530554 A1 EP 1530554A1
Authority
EP
European Patent Office
Prior art keywords
compound
oligomerization
boron trifluoride
olefins
carbon atoms
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Withdrawn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
EP03793725A
Other languages
German (de)
English (en)
Inventor
Hans-Peter Dr. Rath
Arno Dr. Lange
Helmut Dr. Mach
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.)
LANGE, ARNO, DR.
MACH, HELMUT, DR.
RATH, HANS-PETER, DR.
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1530554A1 publication Critical patent/EP1530554A1/fr
Withdrawn legal-status Critical Current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
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • 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
    • C07C2527/08—Halides
    • C07C2527/12—Fluorides
    • C07C2527/1213—Boron fluoride
    • 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

Definitions

  • the present invention relates to a process for the production of synthetic hydrocarbons, which comprises the oligomerization of 1-olefins having 8 to 30 C atoms.
  • Hydrocarbons based on 1-olefins with 8 to 30 C atoms are used as so-called base oils in partially or fully synthetic motor oils.
  • the central step in the production of these base oils is the oligomerization of 1-olefins with 8 to 30 C atoms.
  • the oligomerization takes place in the presence of boron trifluoride and a protic compound which can form a complex with boron trifluoride and which is usually also referred to as an activator, promoter or cocatalyst.
  • the oligomerization of 1-olefins in the presence of boron trifluoride and a protic activator described in the prior art has a number of disadvantages.
  • the reaction mixture during the oligomerization must be supersaturated with boron trifluoride and high boron trifluoride pressures in the reactor - generally ⁇ 2 bar.
  • the consumption of boron trifluoride is consequently high and cannot be reduced to less than 2% by weight, based on the amount of 1-olefin used, even with complex recycle measures.
  • PA04 is obtained by fractional distillation, initially unreacted l-01efin and dimer being separated off and then PA04, which predominantly consists of trimers and tetramers, being distilled off from products of higher viscosity. This also increases the manufacturing costs for PA04.
  • PA04 obtained as a distillate has only a moderate viscosity index, which is particularly undesirable with regard to the use of PA04 in low-viscosity motor oils.
  • WO 01/21675 describes a process in which an I-01efin is first oligomerized in the presence of transition metal catalysts, the low molecular weight part is separated therefrom and then the low molecular weight part is reacted in the presence of an acidic catalyst, for example a boron trifluoride alcohol complex .
  • an acidic catalyst for example a boron trifluoride alcohol complex
  • the metallocene catalysts used are expensive.
  • this is also a coupled production of PA04 with products of higher viscosity.
  • the present invention is based on the object of providing a process for the production of synthetic hydrocarbons by oligomerization of l-01efins in the presence of boron trifluoride catalysts which requires less boron trifluoride consumption.
  • aprotic organic compounds A2 which is selected from ethers with at least one ether oxygen atom, and
  • Halogenated hydrocarbons in particular chlorinated hydrocarbons with 1 to 6 carbon atoms and 1, 2 or 3 halogen atoms, and in particular 1, 2 or 3 chlorine atoms,
  • molar ratio of boron trifluoride to the total amount of compound AI and A2 is in the range from 0.8: 1 to 4: 1.
  • the present invention relates to a process for the preparation of a synthetic hydrocarbon, comprising the oligomerization of l-01efins having 8 to 30 carbon atoms in the presence of boron trifluoride and at least one protic activator AI, characterized in that the reaction in the presence of at least one further Carries out a compound which is selected from the aprotic organic compounds A2 defined above and the halogenated hydrocarbons, in particular chlorinated hydrocarbons, the molar ratio of boron trifluoride to the total amount of compounds AI and A2 being in the range from 0.8: 1 to 4: 1 , and the absolute pressure of boron trifluoride in the reactor does not exceed 1.3 bar.
  • the process according to the invention is advantageously carried out at BF 3 concentrations which do not exceed the saturation concentration of BF 3 in the reaction mixture at reaction temperature and normal pressure, ie a BF 3 partial pressure of 1013 mbar, or only insignificantly, at least at the beginning of the reaction.
  • concentration of BF 3 in the reaction mixture is preferably not more than 120% of this saturation concentration and is in particular the saturation concentration and particularly preferably less, for. B. at a maximum of 90%, based on the value of the saturation concentration.
  • the saturation concentration can be determined in a simple manner by the person skilled in the art by introducing BF 3 into a specific volume of the reaction mixture until saturation at normal pressure and weighing out the introduced BF 3 .
  • the absolute pressure of boron trifluoride in the reactor is not more than 1.3 bar, preferably not more than 1.2 bar, in particular not more than 1.1 bar. particularly preferably not more than 1.05 bar, especially not more than 1 bar, for example 0.5 to 1.1 bar and especially 0.8 to 1.05 bar.
  • the boron trifluoride pressure in the reactor can be set in a manner known per se, for example by supplying the reactor with boron trifluoride with an appropriate BF 3 partial pressure, for example by mixing a mixture of BF 3 with an inert gas feeds into the reactor and / or adjusts the feed rate of BF 3 in the reactor so that - the saturation concentration is not reached.
  • the boron trifluoride concentration in the reaction mixture is therefore generally less than 3% by weight, preferably less than 2% by weight and is in particular in the range from 0.1 to ⁇ 2% by weight, in particular in the range from 0. 3 to 1.8 wt .-% and especially in the range of 0.5 to 1.5 wt .-%, based on the total weight of the reaction mixture. If a phase separation occurs in the reaction in a first phase with a high boron trifluoride concentration and a second phase with a low boron trifluoride concentration, these tasks relate to the second phase.
  • the total concentration of BF 3 in the reaction mixture can then also be higher. However, it will preferably not exceed a value of 10% by weight and in particular 5% by weight.
  • the molar ratio of boron trifluoride to the total amount of compound AI and optionally A2 is preferably not more than 2.5: 1, in particular not more than 2: 1 and in particular not more than 1.8: 1. This ratio is preferably at least 1: 1 and in particular at least 1.2: 1.
  • protic activators known from the prior art which can form a complex with the boron trifluoride are suitable as compounds AI.
  • compounds AI include, for example, water, aliphatic or aromatic alcohols, e.g. B. alkanols with 1 to 20 carbon atoms, aliphatic polyols such as glycerin, glycol and pentaerythritol, hydrogen fluoride and carboxylic acids, eg. B. aliphatic carboxylic acids such as acetic acid or aromatic carboxylic acids such as benzoic acid.
  • Preferred activators AI are selected from alkanols with 1 to 10 C atoms, in particular with 1 to 6 C atoms and especially with 2 to 4 C atoms and among them preferably primary and secondary alkanols.
  • the process according to the invention is characterized in that the oligomerization is carried out in the presence of a compound A2 and / or in the presence of a halogenated hydrocarbon.
  • Suitable compounds A2 are in principle all aprotic, preferably aliphatic ethers, which contain at least 1, e.g. B. 1, 2, 3, 4 or 5, and preferably exactly 1 ether oxygen atom. Aliphatic means that the ether has no aromatic or cyclic groups. The ethers preferably have no further functional groups. The compounds A2 preferably have at least 5 carbon atoms, for. B. 5 to 30 and in particular 10 to 20 carbon atoms. Preferred compounds A2 are dialkyl ethers with at least 5 carbon atoms, e.g. B. 5 to 30 and in particular 10 to 20 carbon atoms.
  • ether compounds of the general formula are also suitable
  • R and R 'independently of one another are alkyl having 1 to 4 • C atoms
  • n is 1, 2, 3 or 4, in particular 1 or 2
  • Alk is a linear or branched alkylene group having 2, 3 or 4 C atoms stands.
  • Alkyl with 1 to 4 carbon atoms includes, for example, methyl, ethyl, n-propyl, n-butyl, 2-propyl, and the like.
  • Alkylene with 2 to 4 carbon atoms includes, for example, 1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,2-butanediyl and 1,4-butanediyl.
  • Preferred compounds A2 are those whose donor number according to Gutmann (V. Gutmann and E. Wychera, Inorg. Nucl. Chem. Lett., 1966, 2, 257) is in the range from 5 to 25 and in particular in the range from 10 to 20 lies. An overview with numerous details of donor numbers and methods for their determination can be found in Y. Marcus, Chemical Society Reviews 1993, pp. 409-416.
  • Halogenated hydrocarbons are in principle all aliphatic hydrocarbons with 1 to 6 carbon atoms in which 1, 2 or 3 of the hydrogen atoms have been replaced by a halogen atom. Halogen here includes in particular fluorine, chlorine and bromine and especially chlorine. Chlorinated hydrocarbons are, for example, dichloromethane, trichloromethane, dichloroethane, trichloroethane, chloropropane, chlorobutane, chloropentane and the like. The preferred chlorinated hydrocarbon is dichloromethane. Chlorofluorocarbons and chlorobromocarbons are also suitable.
  • the concentration of the chlorinated hydrocarbon in the reaction mixture is preferably 2 to 20% by weight and in particular 5 to 15% by weight.
  • Dichloromethane is a particularly preferred chlorinated hydrocarbon.
  • the compounds Al and A2 will generally be in a molar ratio of Al: A2 in the range from 5: 1 to 1:20, preferably 3: 1 to 1:10 and in particular 2 : Insert 1 to 1: 5.
  • the type and amount of compound A2 are preferably chosen such that the average donor number of compounds AI and A2, averaged over the mole fraction of AI and A2, is in the range from 15 to 34 and in particular in the range from 15 to 28.
  • the oligomerization is carried out in the presence of a compound A2, it has proven to be advantageous if the average number of carbon atoms in the compounds AI and A2, averaged over the 'mole fraction of AI and A2, in the range from 4 to 8 and in particular in the Range is 4.5 to 7.
  • the compound Al is then preferably selected from alkanols having 2 to 6 and in particular having 2 to 4 carbon atoms, such as ethanol, n-propanol, isopropanol, n-butanol and 2-butanol. Under these conditions, the mixture to be oligomerized, boron trifluoride and the compound Al, A2 and, if appropriate, the halogenated hydrocarbon generally form a homogeneous phase. In this execution the reaction can be carried out in the presence or absence of a chlorinated hydrocarbon.
  • the type and amount of compound AI and the type and amount of any compound A2 used and the type and amount of any chlorinated hydrocarbon used are selected so that the solubility of free BF 3 and that caused by compounds AI and A2 bound boron trifluoride in the reactor discharge after completion of the oligomerization is less than 1% by weight and in particular less than 0.8% by weight.
  • the solubility of the boron trifluoride in the reactor discharge is preferably at least 0.4% by weight and in particular at least 0.5% by weight.
  • a first phase with a high BF 3 concentration and a second phase, poor in BF 3 but rich in product or starting material are formed.
  • the two phases are in the form of a fine emulsion that is largely stable over a period of 3 minutes.
  • the compound AI is then preferably selected from water, alkanols with 1 to 3 carbon atoms and hydrogen fluoride. If a compound A2 is used, it is preferably selected from dialkyl ethers having 5 to 10 and preferably 5 to 8 carbon atoms.
  • Such low solubility can be achieved, for example, by using ethanol, isopropanol or n-propanol as the compound AI in combination with a chlorinated hydrocarbon and in the absence of a compound A2. What has been said above applies to the type and amount of chlorinated hydrocarbon.
  • solubility can also be achieved by using methanol, water or hydrogen fluoride as the compound A1 and a dialkyl ether having at least 5 and preferably 5 to 8 carbon atoms as the compound A2.
  • the molar ratio of compound AI to compound A2 is then preferably in the range from 1: 2 to 1:20.
  • the boron trifluoride concentration in the reaction mixture is preferably 0.5 to 10% by weight and in particular 0.7 to 5% by weight.
  • boron trifluoride concentrations above 3% by weight do not impair the success of the process according to the invention, because, owing to the phase separation into a first catalyst phase rich in boron trifluoride and a second educt / product phase low in boron trifluoride, the catalyst can be carried out in the simplest manner Are separated from the reaction mixture and returned to the oligomerization reaction.
  • the activity of the boron trifluoride complex in the reaction presumably due to the fine distribution of BF 3 -rich phase to the BF 3 poor phase - - sufficiently high to cause a rapid turnover research.
  • the 1-olefins to be oligomerized preferably comprise at least 50% by weight, in particular at least 80% by weight and particularly preferably at least 90% by weight l-01-fine with a vinyl structure.
  • the starting materials in the process according to the invention are, in particular, 1-olefins having 8 to 14 carbon atoms, in particular with regard to the production of oligomers with a viscosity of about 4 mm 2 / sec to about 5 mm 2 / sec (PA04 and PA05).
  • Preferred among the 1-olefins are those which have a low degree of branching.
  • At least 90% by weight of the l-01efine structural units of the formula (CH 2 ) n used for oligomerization have n in which n is an integer which has a value of at least 5, for example a value of 5 to 20 and in particular of 6 to 12.
  • H 2 C CH- (CH 2 ) q HI
  • H 2 C C (CH 3 ) (CH 2 ) p H II where p + 3 corresponds to the total number of carbon atoms of the olefin.
  • Olefins of the formula II are also referred to as 2-methyl- ⁇ -olefins.
  • olefins of the general formula I are 1-octene,
  • olefins of formula II 2-methyloctene-1, 2-methyldecene-1, 2-methyldodecene-1 and the like.
  • Suitable 1-olefins are in principle also the dimerization products of linear 1-olefins having 4 to 14 carbon atoms, which to a large extent, generally> 95%, from vinylidene olefins of the formula III
  • the value r corresponds to the number of carbon atoms of the linear ⁇ -olefins used for the dimerization.
  • olefins are used for the oligomerization which have 8 to 14 and in particular 10 to 12 C atoms.
  • the 1-olefin to be oligomerized comprises at least 90% by weight and in particular at least 99% by weight of 1-decene.
  • the 1-olefin to be oligomerized comprises at least 90% by weight and in particular at least 99% by weight 1-dodecene.
  • the reaction mixture in addition to the 1-olefin as starting material, boron trifluoride, activator compound Al, optionally compound A2 and optionally chlorinated hydrocarbon, the reaction mixture usually does not comprise any further components, ie. H. the proportion of different components is less than
  • the reaction mixture can also be diluted with an inert solvent.
  • Inert solvents are those which do not form any complexes with the boron trifluoride, for example saturated hydrocarbons such as n-hexane, n-octane, n-decane, cyclohexane, cyclopene tan and the like.
  • the proportion of solvent, based on the total weight of the reaction mixture is then generally 5 to 50% by weight, in particular 5 to 20% by weight.
  • the 1-olefins to be oligomerized are brought into contact with boron trifluoride and at least one protic activator and at least one further compound, selected from the aprotic organic compounds A2 and the chlorinated hydrocarbons, in the desired ratio.
  • the contacting can take place in a manner known per se, the individual measures usually being based on whether the reaction is carried out continuously or batchwise.
  • the olefin to be oligomerized or a part thereof e.g. B. 10 to 50 wt .-%
  • the compound AI and optionally the compound A2 and / or the chlorinated hydrocarbon then initiates the desired amount of boron trifluoride at a temperature below the reaction temperature, generally ensuring good mixing becomes.
  • the mixture is then heated to the desired reaction temperature and the temperatures are maintained until the desired conversion is reached, it being possible to add further 1-olefin before or during the heating or in the course of the reaction.
  • boron trifluoride can be added as gaseous boron trifluoride or in the form of a complex of boron trifluoride and the compound AI and optionally the compound A2, optionally dissolved in the chlorinated hydrocarbon.
  • Part of the boron trifluoride can of course also be added as a complex and another part in gaseous form.
  • part of the boron trifluoride and the compound Al, optionally A2 and / or the chlorinated hydrocarbon are initially introduced into the reactor, then the l-01efin to be oligomerized is added at a temperature below the oligomerization temperature, heated to the oligomerization temperature and then adds further boron trifluoride until the desired molar ratio of boron trifluoride to the total amount of compounds AI and A2 is in the desired range.
  • the boron trifluoride can be introduced in such a way that a complex is produced from boron trifluoride, the compound AI and optionally A2 in a separate reaction vessel and this is then introduced into the reaction vessel.
  • the procedure will generally be such that the 1-olefin to be oligomerized, boron trifluoride, the compound AI and the compound A2 and / or the chlorinated hydrocarbon are fed continuously to the reaction zone in the desired proportions and the oligomerization product is removed continuously. All or some of the boron trifluoride can be metered in as a mixture with the compound AI and / or the compound A2. Frequently, BF 3 and the compound AI and possibly the compound A2 are introduced separately, but preferably in spatial proximity to one another, ideally via multi-component nozzles into the reactor.
  • the reaction temperature required for the oligomerization is usually in the range from -20 ° C to +60 ° C and preferably in the range from +0 to +40 ° C. In principle, higher temperatures can be used, but are generally not necessary and are disadvantageous with regard to a high viscosity index.
  • the reaction takes place at normal pressure or at a slightly elevated pressure, e.g. B. up to 1.5 bar, a BF 3 partial pressure of 1.3 bar, preferably of 1.2 bar, in particular of 1.1 bar and especially of normal pressure (1013 mbar), not being exceeded. Higher pressures, especially higher ones
  • BF 3 pressures of> 1.5 bar or even> 2 bar are not required to achieve sufficient conversions and are disadvantageous with regard to the viscosity index of the products obtained in the oligomerization.
  • the reaction is stopped by deactivating the boron trifluoride in a manner known per se.
  • the deactivation is usually carried out by adding sufficient amounts of a demolition agent.
  • the amount of terminating agent is chosen so that the molar ratio of all compounds which form complexes with boron trifluoride exceeds a value of 1.25: 1, in particular a value of 2: 1 and particularly preferably a value of 3: 1.
  • Suitable demolition agents are in particular water, methanol, ethanol, acetonitrile, sodium fluoride, aqueous ammonia and sodium hydroxide solution. Last but not least, water will be used as a demolition agent for deactivation for cost reasons.
  • phase separation into a complex-rich and a BF 3- poor phase occurs during the reaction, it is advisable to first separate the BF 3 -rich phase, which contains comparatively little reaction product, and to recycle it.
  • the low-complex phase is then treated with the desired amount of demolition agent.
  • the phase rich in BF 3 is separated off in a manner known per se after phase separation with or without aids, such as coalescing filters or coalescing tubes, in phase separation vessels.
  • the reaction mixture can be washed with water, for example, in order to remove inorganic compounds and, if appropriate, compounds Al.
  • the mixture is then worked up by distillation in order to remove residual amounts of solvent, unreacted 1-01-fine and 1-olefin dimers.
  • the residue then contains the desired olefin oligomer. If the viscosity of the residue is too low, the viscosity can be increased by further distilling off trimer. If it is too high, you can add a little trimer distillate. In any case, the bulk of the product, i.e. H. more than 80% and in particular more than 90%, a bottom product and no distillate.
  • the oligomerization product obtained as a rule still has ethylenically unsaturated double bonds, which have a disruptive effect when used as the base oil of motor oils.
  • the oligomerization product obtained is therefore generally subjected to hydrogenation in order to saturate these double bonds.
  • the hydrogenation is usually carried out as catalytic hydrogenation on a transition metal catalyst according to processes known per se, as are also cited in the prior art mentioned at the beginning.
  • Suitable hydrogenation catalysts generally comprise at least one transition metal of groups VI, VIII or I, e.g. B. platinum, palladium, nickel, copper, chromium or combinations of these metals.
  • the catalytically active species is preferably used as a heterogeneous catalyst, in particular in a supported form.
  • the hydrogen partial pressure required for the hydrogenation is generally in the range from 1 to 600 and preferably 5 to 200 bar.
  • the hydrogenation temperature is frequently in the range from 30 to 300 ° C. and in particular in the range from 100 to 200 ° C.
  • the hydrogenation is generally carried out until the olefinic double bonds are more or less completely saturated.
  • the proportion of non-hydrogenated double bonds can be determined in a simple manner via the iodine number or the bromine number (based on DIN 51774).
  • the hydrogenation products usually have iodine numbers below 1.0 and in particular below 0.2.
  • the inventive measures of adding an aprotic organic compound A2 and / or a chlorinated hydrocarbon to the reaction mixture make it possible to significantly reduce the consumption of boron trifluoride in the oligomerization in comparison with the methods of the prior art.
  • the BF 3 consumption is generally less than 2% by weight and in particular less than 1.5% by weight, based on the l-olefins to be oligomerized.
  • the sales of 1-olefins achieved are clearly above the sales achieved without the addition of compound A2 and / or chlorinated hydrocarbon.
  • the method according to the invention also enables the targeted production of low-viscosity products with viscosities of approximately 4 to 5 mm / sec, that is to say of PA04 and PA05, without the formation of by-products of higher viscosity classes. This is particularly surprising since a targeted production of PA05 has not been described so far. Unlike in the prior art, it is not necessary to obtain these components by distillation from the oligomerization mixture. Surprisingly, the viscosity indices of the oligomers obtained according to the invention are also significantly larger than the viscosity indices of products which are obtained by distillation from oligomerization products.
  • the oligomers obtainable by the process according to the invention are therefore new and also a subject of the invention. They generally have viscosities (determined in accordance with DIN 51562-1 to 4 using an Ubbelohde viscometer at 100 ° C.) in the range from 3.5 mm 2 / sec to 8 mm 2 / sec with a viscosity index (determined according to ISO 2909 from the viscosities at 40 ° C and 100 ° C) from> 128 to 140 as a rule (with a viscosity of about 4 mm 2 / sec) and> 135 to 150 (with a viscosity of 5 mm / sec to 8 mm 2 / sec).
  • the following examples serve to illustrate the invention.
  • the viscosities of the oligomerization products were determined in accordance with DIN 51562-1 to 4 using an Ubbelohde viscometer at the temperature specified in each case.
  • the viscosity given is the kinematic viscosity.
  • the viscosity index was determined in the usual way from the values of the viscosity at 40 ° C and 100 ° C (according to ISO 2909).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'hydrocarbures synthétiques au cours duquel des 1-oléfines comportant 8 à 30 atomes de carbone sont soumises à une oligomérisation.
EP03793725A 2002-08-12 2003-08-11 Procede de production d'hydrocarbures synthetiques Withdrawn EP1530554A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10236927 2002-08-12
DE10236927A DE10236927A1 (de) 2002-08-12 2002-08-12 Verfahren zur Herstellung von synthetischen Kohlenwasserstoffen
PCT/EP2003/008903 WO2004022511A1 (fr) 2002-08-12 2003-08-11 Procede de production d'hydrocarbures synthetiques

Publications (1)

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EP1530554A1 true EP1530554A1 (fr) 2005-05-18

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US (1) US20060025643A1 (fr)
EP (1) EP1530554A1 (fr)
AU (1) AU2003263208A1 (fr)
DE (1) DE10236927A1 (fr)
WO (1) WO2004022511A1 (fr)

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Publication number Priority date Publication date Assignee Title
NZ588129A (en) * 2006-02-03 2012-06-29 Grt Inc Continuous process for converting natural gas to liquid hydrocarbons
US20110137091A1 (en) * 2009-12-07 2011-06-09 Norman Yang Manufacture of Oligomers from Nonene
US10647626B2 (en) * 2016-07-12 2020-05-12 Chevron Phillips Chemical Company Lp Decene oligomers

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL135909C (fr) * 1961-07-11
US3382291A (en) * 1965-04-23 1968-05-07 Mobil Oil Corp Polymerization of olefins with bf3
US3780128A (en) * 1971-11-03 1973-12-18 Ethyl Corp Synthetic lubricants by oligomerization and hydrogenation
US3763244A (en) * 1971-11-03 1973-10-02 Ethyl Corp Process for producing a c6-c16 normal alpha-olefin oligomer having a pour point below about- f.
US3997621A (en) * 1974-02-04 1976-12-14 Mobil Oil Corporation Controlled oligomerization of olefins
US4045508A (en) * 1975-11-20 1977-08-30 Gulf Research & Development Company Method of making alpha-olefin oligomers
US4045507A (en) * 1975-11-20 1977-08-30 Gulf Research & Development Company Method of oligomerizing 1-olefins
US5284988A (en) * 1991-10-07 1994-02-08 Ethyl Corporation Preparation of synthetic oils from vinylidene olefins and alpha-olefins
US5498815A (en) * 1991-12-13 1996-03-12 Albemarle Corporation Preparation of synthetic oils from vinylidene olefins and alpha-olefins
US5396013A (en) * 1993-07-12 1995-03-07 Albemarle Corporation Olefin oligomerization process
US5744676A (en) * 1996-02-26 1998-04-28 Theriot; Kevin J. Olefin oligomerization process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004022511A1 *

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AU2003263208A1 (en) 2004-03-29
US20060025643A1 (en) 2006-02-02
WO2004022511A1 (fr) 2004-03-18

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