WO2004018389A1 - Procede de production d'alpha-olefines lineaires - Google Patents

Procede de production d'alpha-olefines lineaires Download PDF

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WO2004018389A1
WO2004018389A1 PCT/EP2003/009169 EP0309169W WO2004018389A1 WO 2004018389 A1 WO2004018389 A1 WO 2004018389A1 EP 0309169 W EP0309169 W EP 0309169W WO 2004018389 A1 WO2004018389 A1 WO 2004018389A1
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olefin
olefins
catalyst
isomerization
compound
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German (de)
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Dag Wiebelhaus
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
    • C07C1/327—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being an aluminium atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • the present invention relates to a process for the selective production of C - to C 3 o-oc-olefins by isomerizing transalkylation of C 4 - to C 3 o-olefins with an internal double bond and subsequent release of the desired C 4 - to C 3 ⁇ - ⁇ - Olefins, wherein in the first step a catalyst is used which contains a combination of at least two metals. These metals are selected so that one metal predominantly catalyzes the transalkylation, the other metal predominantly the isomerization.
  • olefins Due to their carbon double bond, via which the introduction of a large number of functional groups is possible, olefins represent the most important class of basic chemicals for the chemical industry.
  • olefins which, as is known to the person skilled in the art, are divided into different classes, for example in short - And long-chain, linear and branched olefins or olefins with internal and terminal double bonds ( ⁇ -olefins), there are different manufacturing processes.
  • a frequently used process for the production of olefins is the cracking of saturated hydrocarbons. However, this is particularly suitable for the production of short-chain olefins in the carbon number range up to a maximum of 4.
  • Linear, higher ⁇ -olefins with 4 to 30 carbon atoms represent a class of olefins which, after further processing, are used for the production of detergents, plasticizers and lubricating oils and for which there is therefore a wide range of applications. There are only a limited number of manufacturing processes for this class of olefins. The dehydration of natural alcohols and the cracking of higher paraffins (wax splitting) are insignificant.
  • ⁇ -olefins The majority of linear ⁇ -olefins are produced by transition metal-catalyzed oligomerization of ethylene according to the Ziegler process or the so-called SHOP process of the Shell, whereby highly linear olefin fractions with an ⁇ -olefin content of> 95% can be obtained.
  • Aluminum alkyls serve as catalysts in the Ziegler process, and phosphine-modified nickel complexes are used as active species in the oligomerization reaction in the SHOP process.
  • the need for olefins with terminal double bonds ( ⁇ -olefins) is significantly greater than for olefins with internal double bonds (internal olefins).
  • 1-hexene and 1-octene are required as comonomers for polyethylene, while 1-decene is used for the production of synthetic lubricants.
  • 1-decene is used for the production of synthetic lubricants.
  • internal olefins are more thermodynamically stable than ⁇ -olefins, the internal olefins are formed in numerous processes for the production of long-chain olefins such as the dehydration of alcohols or alcohol mixtures, the dehydration of linear paraffins, the olefin metathesis or the disproportionation of olefins, which subsequently must be converted into the desired ⁇ -olefins.
  • EP-A 0 525 760 and EP-A 0 505 834 relate to a process for the production of aluminum alkyls and linear ⁇ -olefins from olefins with an internal double bond.
  • An internal olefin having 4 to 30 carbon atoms is isomerized on a homogeneous catalyst, in particular on nickel, and this olefin is reacted with a trialkylaluminum compound.
  • the olefin supplied at least partially displaces the olefin originally bound to the aluminum.
  • the aluminum trialkyl compound formed in which at least one radical is formed from a C 1 -C 3 o ⁇ ⁇ -olefin, is then transferred to a release step which is carried out in the presence of a displacement catalyst.
  • a displacement catalyst which generally corresponds to the catalyst of the previous isomerizing transalkylation, must be deactivated by adding an inhibitor, in particular lead. The deactivated displacement catalyst must be removed at the end of the reaction.
  • Nickel catalyst is always used in the transalkylation.
  • the service life is not very long, that is to say the catalyst performance drops significantly as the process is carried out.
  • Nickel also has a high Isomerization activity, as a result of which, in processes such as are described in EP-A 0 505 760 and EP-A 525 834, which in the last stage comprise a displacement reaction in which isomerization of the released olefin should no longer occur - that Ni must necessarily be separated off or at least deactivated in good time before the undesired isomerization can occur to any appreciable extent.
  • the object of the present invention is to provide a catalyst which is active in the isomerizing transalkylation and avoids the disadvantages of pure nickel catalysts which have been mentioned above. In particular, long service lives are to be achieved. Furthermore, deactivation of the catalyst before the displacement reaction should be superfluous.
  • Another object is to provide a corresponding process for the preparation of C 4 - to C 3 o- ⁇ -olefins from C - to C 30 -olefins with internal double bonds, in which an isomerization of the C 4 - to C 30 -olefins is carried out first internal double bonds are carried out on a catalyst and the isomerized C - to C 3 o- ⁇ ⁇ olefins obtained displace the olefins contained in the alkyl radicals from a trialkylaluminum compound present in the reaction mixture, with the formation of trialkylaluminum compounds in which at least one of the alkyl groups bound to the aluminum is one is from the desired C 4 ⁇ to C 30 ⁇ ⁇ -olefin alkyl group, and subsequent release of the desired C 4 - to C 3 o- ⁇ -olefin, optionally using a catalyst which has the advantages mentioned.
  • Step b) reacting the trialkylaluminum compound formed in step a) with a suitable olefin to liberate the desired C 4 -C 3 o- ⁇ ⁇ olefin.
  • Step b) can be carried out in the presence of a catalyst, which may have to be deactivated, or thermally, in the absence of a catalyst.
  • This object is further achieved by a process for the preparation of a trialkylaluminum compound in which at least one alkyl radical is derived from a C 4 -C 3 o- ⁇ -olefin, by reacting an internal C 4 -C 3 o-olefin with a trialkylaluminum compound in the presence an isomerization / transalkylation catalyst containing at least one isomerization-active metal component and at least one displacement-active metal component, with the liberation of an olefin which is derived from the originally bound alkyl radical.
  • ⁇ -olefins are understood to mean olefins with a terminal double bond (terminal double bond).
  • First trialkyl aluminum compound (A) is to be understood as the trialkyl aluminum compound used in step a) of the process according to the invention
  • second trialkyl aluminum compound (B) is to be understood as meaning the trialkyl aluminum compound obtained in step a), in which at least one of the aluminum compounds bound alkyl groups is an alkyl group derived from the desired C 4 to C 3 o- ⁇ -olefin.
  • step a) of the process according to the invention is referred to below as “isomerizing transalkylation", step b) as displacement.
  • “isomerizing transalkylation” means the reaction of an olefin with an internal double bond with a trialkylaluminum compound (A) under isomerizing conditions, that is to say in the presence of an isomerization / transalkylation catalyst. It appears that the olefin with an internal double bond rearranges with double bond isomerization to a mixture of olefins with an internal double bond and ⁇ -olefins (i.e. olefins with a terminal double bond), only the ⁇ -olefins reacting to form a trialkylaluminum compound (B).
  • the internal olefin first attaches to the aluminum ion and then isomerization to the linearly bound alkyl radical occurs. In in each case an olefin is released which corresponds to the alkyl radical which was previously bound to the aluminum.
  • the C 4 to C 3u olefins with internal double bonds used in the reaction in step a) can be present in pure form or in a mixture with C 4 to C 3 o- ⁇ -olefins and / or with paraffins. If the C 4 - to C o-olefins with internal double bonds are used in a mixture with C 4 - to C 3 o- ⁇ -olefins or with paraffins, the mixture preferably contains up to 5% by weight of C - to C o- ⁇ -olefins and / or less than 50% by weight paraffins.
  • trialkylaluminum compounds are accessible in one embodiment, in which at least one of the alkyl radicals of a C 4 -C 3 o- ⁇ -olefin, preferably a C 4 -C 4 - ⁇ -olefin, in particular a C 6 -C l ⁇ - ⁇ -olefin is derived.
  • C 4 to C 30 ⁇ -olefins preferably C 4 to C 1 ⁇ -olefins, particularly preferably C 6 to Cio- ⁇ -olefins, which are in particular linear
  • the ⁇ -olefins mentioned include both olefins with a certain defined number of carbon atoms and mixtures of olefins with different carbon numbers.
  • Linear ⁇ -olefins for example 1-hexene, 1-octene and 1-decene, are very particularly preferably produced using the process according to the invention.
  • Suitable olefins with an internal double bond are the olefins corresponding to the desired ⁇ -olefins in terms of carbon number. Ice and trans-2-butene, ice and trans-2-hexene, ice and trans-3-hexene, mixtures of hexenes with an internal double bond, 2-, 3- and 4-octene and mixtures of octenes with are particularly suitable internal double bond as well as 2-, 3-, 4- and 5-decene and mixtures of decenes with internal double bond.
  • Processes for the production of olefins with an internal double bond are known to the person skilled in the art. Suitable processes are, for example, the dehydration of alcohols or alcohol mixtures, the dehydration of paraffins and the metathesis or disproportionation of olefins.
  • the olefins with internal double bonds are preferably obtainable by the dehydrogenation of linear paraffins or by olefin metathesis.
  • Processes for the production of olefins with internal double bonds by olefin metathesis are available, for example, in the unpublished patent applications (official file number: DE 101 36 048.7) and (official file number: DE 101 03 309.5), which are integral parts of the present application.
  • Particularly preferred processes for the preparation of the olefins having an internal double bond are processes based on C 4 fractions which are obtained in steam or FCC cracking or in the dehydrogenation of butane.
  • Raffinate II is preferably used as the C 4 fraction, with the C 4 stream being freed from disturbing impurities, in particular oxigenates, by appropriate treatment on adsorber protective beds, preferably high-surface area aluminum oxides and / or molecular sieves.
  • Raffinate ⁇ is obtained from the C 4 fraction, in which butadiene is first extracted and / or subjected to a selective hydrogenation. After separation of isobutene, raffinate II is then obtained. The raffinate II obtained is then converted directly or after further refinement steps, preferably by metathesis to the desired olefins with an internal double bond.
  • First trialkylaluminum compounds (A) which are preferably used in the isomerizing transalkylation are those which have fewer carbon atoms than the olefins used with internal double bonds (if an olefin mixture with internal double bonds is used, the trialkylaluminum compounds preferably have fewer carbon atoms than the average carbon number of the olefin mixture with internal ones Corresponds to double bonds).
  • the olefin liberated from the trialkylaluminum compound (A) preferably has a lower boiling point than the desired ⁇ -olefin or the olefin used as the starting product with an internal double bond.
  • trialkylaluminum compound (A) This facilitates the removal of the olefin released from trialkylaluminum compound (A), which in one embodiment is continuously removed from the reaction mixture. The removal leads to an acceleration of the reaction by shifting the reaction equilibrium.
  • Suitable trialkylaluminum compounds (A) have alkyl groups with 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, such as triethylaluminium, tri-n-propylaluminium, tri-n-butylaluminium, triisobutylaluminum, trineohexylaluminium.
  • Trialkyl aluminum compounds whose alkyl chains are straight-chain are preferably used, particularly preferably those whose alkyl groups do not isomerize after release, such as tri-n-propyl aluminum.
  • the trialkylaluminum compounds (A) have a low hydride content, generally less than 1.0% by weight, preferably less than 0.1% by weight, since the isomerization catalyst can be deactivated rapidly in the presence of aluminum hydrides.
  • Catalysts that can be used in the transalkylation reaction can be both homogeneous and heterogeneous.
  • the isomerization / displacement catalysts contain at least one displacement-active metal or a compound thereof and at least one isomerization-active metal or a compound thereof.
  • Isomerization-active metals are those from the groups mb, IVb, Vb, VIb, VHb and Vm of the Periodic Table of the Elements.
  • Preferred metals are selected from the group Ti, Zr, Hf, Cr, Fe, Co, Ru, Rh and Ir.
  • the metals are selected from Cr, Fe, Ti and Zr or a compound thereof.
  • the isomerization / displacement catalyst is nickel-free.
  • the yields and conversions obtained with nickel-free catalysts are in the range of those achieved with nickel-containing catalysts. However, longer service lives are achieved by using the catalysts according to the invention. It is also generally not necessary to deactivate the catalyst in stage b).
  • Displacement-active metals are those from the groups IDb, IVb, Vb, VIb, Vllb and Vi ⁇ of the Periodic Table of the Elements.
  • Preferred metals are selected from the group consisting of La, Ti, Zr, Hf, Ta, Cr, Mo, Fe, Co, Rh, Ir and Ce. In particular, Co and / or Rh or a compound thereof are used.
  • the above-mentioned metals or compounds thereof can be combined with one another as desired.
  • Preferred combinations include Co / Cr, Rh / Cr, Co / Ti and Co / Zr or compounds thereof. If a compound of the abovementioned metals is used, chlorides, bromides, iodides, carboxylates, for example acetates, 2-ethylhexanoates or naphthenates, acetonates, for example acetylacetonate, alkoxylates, carbonyls, olefin complexes, complexes containing amines, phosphines, for example triphenylphosphine or trimethylphosphine are suitable, for example , and phosphites, for example triphenyl phosphite or trimethyl phosphite.
  • Suitable carriers are known to the person skilled in the art and include inorganic and organic carriers.
  • inorganic carriers include SiO 2 , Al 2 O 3 / SiO 2 mixtures, aluminum phosphates and activated carbons and mixtures of the substances mentioned.
  • organic carriers include organic polymers, preferably polystyrene, which can optionally be modified (Merrifield resin, Wang resin, aminomethyl-substituted polystyrene), tentagel and polyamide resins.
  • homogeneous and heterogeneous catalysts can be used in the process according to the invention.
  • the catalyst compound is generally added as such.
  • heterogeneous catalysts they are preferably fixed on an inert support, in particular in such a way that washing out of the active metal component during the reaction is avoided. This can be achieved, for example, by using the fixed catalysts mentioned above.
  • the ratio of the olefins used with internal double bonds to the trialkylaluminum compound (A) is generally from 1 to 40: 1, preferably from 2 to 15: 1, particularly preferably from 6 to 10: 1.
  • the isomerization / displacement catalyst is generally used in an amount of 0.01 to 5 mol%, based on the trialkylaluminum compound (A) used, preferably 0.02 to 1.0 mol%.
  • the isomerization / displacement catalyst is preferably first mixed with the olefins used with internal double bonds, and this mixture is then added to the trialkylaluminum compound (A) used.
  • the olefin released from the trialkylaluminum compound (A) is removed in gaseous form from the reaction mixture, as a result of which the transalkylation with the ⁇ -olefin formed by isomerization, which displaces one of the original alkyl groups of the trialkylaluminum compound (A), by shifting the Equilibrium is accelerated.
  • the alkyl group displaced from the trialkylaluminum compound (A) in the form of an olefin can be reused in step b) of the process according to the invention as an olefin to release the desired ⁇ -olefin.
  • Unreacted olefins with internal double bonds can be separated from the reaction mixture, for example by distillation or stripping in vacuo, and used again in the isomerizing transalkylation (step a)).
  • the trialkylaluminum compound (A) is generally prepared at temperatures from -20 ° C. to 200 ° C., preferably 30 ° C. to 100 ° C.
  • the reaction pressure is generally 0.1 to 20 bar, preferably 0.5 to 8 bar and the reaction time is generally 0.1 to 2 hours.
  • the trialkylaluminum compound (A) can be prepared batchwise, semi-continuously or continuously.
  • the preparation of (A) can be carried out in the presence of solvents, but this is not necessary.
  • Suitable solvents are inert aliphatic and aromatic hydrocarbons which have a boiling point suitable for the reaction conditions (reaction temperature).
  • Suitable solvents are, for example, isoheptane, heptane, octane, isooctane, dodecane and isododecane.
  • the use of the isomerization / displacement catalysts according to the invention enables, due to the longer service life compared to the catalysts previously used for example, to extend the intervals between the necessary shutdown of the reactors or require small amounts of active substance.
  • step b) the release (displacement) of the desired C 4 - to C 3 o- ⁇ -olefin from the second trialkylaluminum compound (B) formed.
  • the release takes place thermally, in the absence of a catalyst, or in the presence of a displacement-active catalyst, generally the optionally deactivated isomerization / displacement catalyst from step a).
  • the trialuminium alkyl compound (B) is reacted with an olefin in a molar ratio of generally 1: 1 to 1:20, preferably 1: 2 to 1:10.
  • Suitable olefins are ⁇ -olefins with generally 2 to 18 carbon atoms or mixtures thereof.
  • the ⁇ -olefin which was released in step a) from the trialkylaluminum compound (A) is preferably used.
  • the trialkylaluminum compound (A) used in step a) is thus reformed in step b) and can in turn be used in step a) of the process according to the invention.
  • the thermal displacement is generally carried out at temperatures of 150 to 400 ° C, preferably 200 to 360 ° C, particularly preferably 260 to 340 ° C.
  • the pressure is generally from 4 to 150 bar, preferably 20 to 120 bar, particularly preferably 70 to 100 bar.
  • the release step is carried out with a residence time of generally 0.01 to 5 s, preferably 0.1 to 2 s, particularly preferably 0.1 to 0.5 s.
  • reaction mixture is immediately cooled to temperatures which are generally 20 to 200 ° C., preferably 50 to 150 ° C., below the reaction temperature.
  • the reaction b) can take place thermally, in the absence of catalysts, the isomerization / transalkylation catalyst being separated off beforehand. It is also possible to carry out the release of the desired C - to C 30 - ⁇ -olefins from the trialkylaluminum compounds (B) with the aid of a displacement catalyst.
  • the catalyst used as the isomerization / displacement catalyst can continue to be used as the catalyst. If necessary, this can be deactivated to carry out the release step in order to avoid back-isomerization of the desired C - to C 3 ⁇ - ⁇ -olefins to the corresponding olefins with internal double bonds.
  • Suitable catalysts which have a low isomerization activity are those based on Co, Cr, Mo, Fe, Rh and / or Ir or compounds thereof. When using heterogeneous catalysts, low isomerization is generally achieved through a short contact time. If the release step is carried out in the presence of a catalyst, the release generally takes place at temperatures of 10 to 80 ° C. Olefins suitable for the catalytic release stage correspond to the olefins suitable for thermal release and have already been mentioned above.
  • the olefins used in the release stage are generally used in a stoichiometric excess in relation to the alkyl groups to be released as desired C 4 to C 3 o- ⁇ -olefins in the trialkylaluminum compound (B).
  • An at least 200 mol% excess is preferably used, particularly preferably an at least 500 mol% excess. This shifts the equilibrium of the release stage to the substitution side with the olefins used in the release stage, the desired C 4 - to C 3u - ⁇ -olefins being released.
  • the isomerization activity is lower than with pure nickel catalysts. It is therefore often not necessary to deactivate or separate the catalyst before the release in step b).
  • the desired C 4 - to C 3 o- ⁇ -olefin is then isolated from the reaction mixture obtained by processes known to those skilled in the art.
  • the trialkylaluminum compound obtained in step b), preferably the trialkylaluminum compound (A), which are obtained in step b) when the olefins released in step a) are used, can be recycled in step a) of the process according to the invention.
  • the displacement b) can be carried out continuously, semi-continuously or discontinuously.
  • the present application also relates to a process for the preparation of trialkylaluminum compounds (B) containing at least one alkyl group derived from a C - to C 3 o- ⁇ -olefin Reaction of a C -C 3 o-olefin with an internal double bond or a mixture of C - to C 30 -olefins with internal double bonds with a trialkylaluminum compound (A) in the presence of an isomerization / displacement catalyst.
  • Trialkylaluminum compounds (B) can be obtained by displacement, the desired ⁇ -olefins.
  • Another object of the present application is the use of an isomerization / displacement catalyst according to the invention, which contains at least one displacement-active metal or a compound thereof and at least one isomerization-active metal or a compound thereof, in the isomerizing transalkylation of olefins and the production of ⁇ -olefins from internal olefins comprising such a tansalkylation ring.
  • the olefins mentioned are preferably C 4 -C 30 olefins, more preferably C -C 14 olefins, in particular C O -C 10 O olefins.
  • Preferred isomerization / displacement catalysts are mentioned above.
  • Tripropylaluminum is mixed with 10 equivalents of 3-hexene and heated to reflux (normal pressure, approx. 70 ° C). Then the homogeneous catalyst in the form of Acetylacetonate of the respective metal was quickly added dropwise in toluene. After 2 hours a sample is taken and hydrolyzed in aqueous HCl. The yield of the reaction is determined by gas chromatography.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de production d' alpha -oléfines C4-C30 à partir d'oléfines C4-C30 à liaisons doubles internes, qui consiste (a) à mettre en réaction une oléfine C4-C30 interne avec un composé trialkylaluminium en présence d'un catalyseur d'isomérisation / transalkylation exempt de nickel contenant au moins un constituant métallique à action d'isomérisation et au moins un constituant métallique à action de déplacement, ce qui permet la libération d'une oléfine dérivée du reste alkyle initialement lié et la formation d'un composé trialkylaluminium dans lequel au moins un reste alkyle est dérivé d'une alpha -oléfine C4-C30, et (b) à mettre en réaction le composé trialkylaluminium formé à l'étape (a), ce qui permet la libération de l' alpha -oléfine C4-C30 souhaitée.
PCT/EP2003/009169 2002-08-20 2003-08-19 Procede de production d'alpha-olefines lineaires Ceased WO2004018389A1 (fr)

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Application Number Priority Date Filing Date Title
AU2003266995A AU2003266995A1 (en) 2002-08-20 2003-08-19 Method for the production of linear alpha-olefins

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DE2002138026 DE10238026A1 (de) 2002-08-20 2002-08-20 Verfahren zur Herstellung von linearen alpha-Olefinen
DE10238026.0 2002-08-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2186786A2 (fr) 2010-01-27 2010-05-19 Shell Internationale Research Maatschappij B.V. Procédé pour la séparation des oléfines des paraffines

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0382072A1 (fr) * 1989-02-06 1990-08-16 Ethyl Corporation Réaction de déplacement catalysée au nickel
EP0525760A1 (fr) * 1991-08-02 1993-02-03 Albemarle Corporation Procédé en continu pour préparer d'alkyles d'aluminium et d'1-oléfines linéaires à partir d'oléfines internes
US5597937A (en) * 1995-05-11 1997-01-28 Albemarle Corporation Conversion of deep internal olefins into primary alkylaluminum compounds by isomerization-displacement

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0382072A1 (fr) * 1989-02-06 1990-08-16 Ethyl Corporation Réaction de déplacement catalysée au nickel
EP0525760A1 (fr) * 1991-08-02 1993-02-03 Albemarle Corporation Procédé en continu pour préparer d'alkyles d'aluminium et d'1-oléfines linéaires à partir d'oléfines internes
US5597937A (en) * 1995-05-11 1997-01-28 Albemarle Corporation Conversion of deep internal olefins into primary alkylaluminum compounds by isomerization-displacement

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2186786A2 (fr) 2010-01-27 2010-05-19 Shell Internationale Research Maatschappij B.V. Procédé pour la séparation des oléfines des paraffines

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AU2003266995A1 (en) 2004-03-11

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