WO2001047839A1 - Procedes permettant d'eviter la generation d'halogenures d'hydrogene dans un systeme de recuperation de produits d'oligomerisation - Google Patents

Procedes permettant d'eviter la generation d'halogenures d'hydrogene dans un systeme de recuperation de produits d'oligomerisation Download PDF

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WO2001047839A1
WO2001047839A1 PCT/US2000/035366 US0035366W WO0147839A1 WO 2001047839 A1 WO2001047839 A1 WO 2001047839A1 US 0035366 W US0035366 W US 0035366W WO 0147839 A1 WO0147839 A1 WO 0147839A1
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process according
material comprises
catalyst
quenching
stabilizing material
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PCT/US2000/035366
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English (en)
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Jeffrey W. Freeman
Bruce E. Kreischer
Warren M. Ewert
Ronald D. Knudsen
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Phillips Petroleum Company
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Priority to CA002392233A priority Critical patent/CA2392233C/fr
Priority to EP00989508A priority patent/EP1242341A4/fr
Priority to MXPA02005399A priority patent/MXPA02005399A/es
Priority to AU26006/01A priority patent/AU773364B2/en
Publication of WO2001047839A1 publication Critical patent/WO2001047839A1/fr

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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates generally to the catalytic production of olefins. This invention relates more specifically to a process of quenching the catalyst in the effluent from an oligomerization reactor, such as a trimerization reactor, to avoid the generation of hydrogen halides.
  • Olefins particularly alpha-olefms, also referred to as 1 -olefins, have many uses as specific chemicals and as monomers or co-monomers in poly- merization processes.
  • Higher alpha-olefms and other olefins can be produced by contacting lower olefins, for example ethylene, with a catalyst, producing trimers of mono-olefms, dimers of diolefms, or other reaction products in an addition reaction. This reaction can be referred to as "trimerization” or "oligomerization”.
  • the catalyst system is dispersed in a process solvent, and the reactants, a lower 1 -olefin and optionally hydrogen, are fed in as gases. The reaction product or higher olefins dissolve in the process solvent as they are formed.
  • Product olefins and spent catalyst system are recovered by removing the process solvent containing them, i.e. the reactor effluent, from the reactor.
  • a catalyst kill agent is added to the reaction system prior to separating any of the reaction components.
  • the effluent can be treated to quench or "kill" the catalyst.
  • the effluent can be separated for catalyst system waste disposal, recycle any remaining lower 1 -olefin and process solvent content, and recover product olefins.
  • a quenching agent can be used to quench the aluminum alkyl portion of the catalyst system. Quenching of the catalyst system is important to prevent isomerization of the 1 -olefin product to undesirable internal, i.e. 2- and higher, olefins, which lowers the product purity. Quenching of the catalyst system also can remove hazards associated with the air- and water- sensitive aluminum alkyls.
  • U.S. Patent No. 5,750,816 teaches the addition of alcohols, phenols, carboxylic acids, primary or secondary amines, or ammonia to the effluent of an ethylene trimerization reactor as a "metal solubilizing agent".
  • the percentage of the metal solubilizing agent used may be selected from a wide range from a trace amount to a solvent equivalent, but it is preferably in a range from 0.001 to 50% by weight, more preferably 0.01 to 10% by weight in terms of concentration in the solvent”. For example 0.022% by weight 1-hexanol (Examples 5 and 13), hexylamine (Examples 6 and 14), or ammonia (Examples 7 and 15) is used.
  • alcohols used as quenching agents to quench a halogenated trimerization catalyst system, following an oligomerization reaction, can produce hydrogen halides.
  • quenching a chlorinated catalyst with an alcohol particularly in the presence of water or the kettle bottoms found in a plant (which may contain ferrous chloride), may lead to the production of hydrogen chloride gas.
  • Hydrogen halides can be highly corrosive to process equipment.
  • One aspect of the invention is an oligomerization process.
  • a catalyst system a lower olefin reactant, and a process medium are provided.
  • the lower olefm is reacted in the presence of the catalyst system to produce a product stream.
  • the product stream includes a higher olefin product and catalyst system residue, both dispersed in the process solvent or medium.
  • the resulting product stream is treated with a quenching material comprising an aliphatic primary amine, an aliphatic secondary amine, or a combination of those materials.
  • a quenching material comprising an aliphatic primary amine, an aliphatic secondary amine, or a combination of those materials.
  • an alcohol or other quenching materials also can be combined with the selected amine to form composite quenching materials.
  • the quenching material is provided in an amount at least substantially effective to quench the catalyst.
  • Amine quenching materials have been found to generate few or no hydrogen halides when used to quench oligomerization catalysts.
  • Another aspect of the invention is an oligomerization process in which the product stream is treated with an alcohol in an amount at least partially effective to quench the catalyst.
  • the product stream is also treated with a stabilizing material that forms a stable hydrogen halide salt.
  • the stabilizing material is provided in an amount effective to at least reduce the generation of free hydrogen halides.
  • the stabilizing material alleviates the problem, apparently by interacting with any hydrogen halides to produce a stable material (though the present invention is not limited to any particular mode of action).
  • a lower olefm as used in this disclosure is any 1- olefm that can be converted to a higher 1 -olefm, wherein the higher 1 -olefin has a greater number of carbon atoms than the lower olefm.
  • the reaction is carried out in the presence of one or more catalysts under conditions encouraging the reaction to proceed.
  • the present invention will be exemplified in the context of a trimerization reaction, although it is contemplated that the invention will find use in other oligomerization reactions.
  • Trimerization is defined as any combination of any two, three, or more olefins reducing the number of olefin, i.e., carbon-carbon, double bonds by two.
  • the three olefin bonds in the combination of three ethylene units can be reduced by two, to one olefm bond, in 1-hexene.
  • the four olefm bonds in the combination of two 1,3-butadiene units can be reduced by two, to two olefm bonds, in 1,5-cyclooctadiene.
  • trimerization is intended to include dimerization of diolefms, as well as “co-trimerization”, each as further discussed below.
  • reactants, catalysts, equipment, and reaction conditions useful in the present process and the reaction products and by-products formed as a result of the trimerization reaction are further described below.
  • the reactants applicable for use in the trimerization process of this invention include olefmic compounds which can self-react, i.e., trimerize, to give useful products.
  • the self-reaction of ethylene can give 1-hexene
  • the self-reaction of 1,3-butadiene can give 1,5-cyclooctadiene.
  • the reactants applicable for use in the trimerization process of this invention also include olefmic compounds which can react with other olefinic compounds, i.e., co-trimerize, to give useful products.
  • co-trimerization of ethylene plus hexene can give 1-decene or 1-tetradecene.
  • Suitable trimerizable olefin compounds are those compounds having from about 2 to about 30 carbon atoms per molecule and having at least one olefinic double bond. Exemplary olefins include, but are not limited to the following.
  • Acyclic olefins are contemplated such as, for example, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, the four normal octenes, the four normal nonenes, and mixtures of any two or more of those.
  • Exemplary diolefm compounds contemplated here include, but are not limited to, 1,3-butadiene, 1 ,4-pentadiene, and 1,5-hexadiene.
  • branched or cyclic olefins are used as reactants, while not wishing to be bound by theory, it is believed that steric hindrance could hinder the trimerization process. Therefore, the branched or cyclic portion of the olefin generally will be distant from the carbon-carbon double bond.
  • the present invention is not limited to use with the olefins suggested by this theory to be useful. Any olefin that will participate in the reaction is contemplated for use according to the present invention. Catalyst Systems
  • One trimerization catalyst system contemplated in accordance with this invention is a three-part system comprising the combination of a chromium source, a pyrrole-containing compound and a metal alkyl.
  • the catalyst system can be supported on an inorganic oxide support.
  • These catalyst systems are especially useful for the dimerization and trimerization of olefins, such as, for example, ethylene to 1-hexene.
  • any catalyst or catalyst system comprising a metal alkyl is more broadly contemplated.
  • the catalyst system commonly includes a halide source, for example, a chloride, bromide, iodide, or fluoride compound.
  • the chromium source can be one or more organic or inorganic compounds, in which the chromium oxidation state is from 0 to 6.
  • the chromium source will have a formula of CrX_take in which each X can be the same or different, and can be any organic or inorganic radical, and n is an integer from 1 to 6.
  • Exemplary organic radicals can have from about 1 to about 20 carbon atoms per radical, and can be alkyl, alkoxy, ester, ketone, carboxylate or amido radicals, for example.
  • the organic radicals can be straight-chained or branched, cyclic or acyclic, aromatic or aliphatic, can be made of mixed aliphatic, aromatic, or cycloaliphatic groups.
  • Exemplary inorganic radicals include, but are not limited to, any anion or oxidizing radical, for example, halides, sulfates, or oxides.
  • the chromium source is a chromium (II)- or chromium (I ⁇ I)-containing compound that can yield a catalyst system with improved oligomerization or trimerization activity.
  • the chromium source is a chromium (III) compound because of its ease of use, availability, and enhanced catalyst system activity.
  • exemplary chromium (III) compounds include, but are not limited to, chromium carboxylates, chromium naphthenates, chromium halides, chromium pyrrolides, and chromium dionates.
  • chromium (III) compounds include, but are not limited to chromium (III) 2,2,6,6,-tetramethylheptanedionate - Cr(TMHD) 3 ; chromium (III) 2-ethylhexanoate - Cr(EH) 3 ; chromium (III) tris-(2-ethylhexanoate); chromium (III) naphthenate - Cr(Np) 3 ; chromium (III) chloride; chromic bromide; chromic fluoride; chromium (III) acetylacetonate; chromium (III) acetate; chromium (III) butyrate; chromium (III) neopentanoate; chromium (III) laurate; chromium (III) stearate; chromium (III) pyrrolide; chromium
  • chromium (II) compounds include, but are not limited to chromous bromide; chromous fluoride; chromous chloride; chromium (II) bis-(2-ethylhexanoate); chromium (II) acetate; chromium (II) butyrate; chromium (II) neopentanoate; chromium (II) laurate; chromium (II) stearate; chromium (II) oxalate; chromium (II) pyrrolides; or combinations of two or more. Chromium (II) and chromium (III) compounds can also be combined.
  • the pyrrole-containing compound of the catalyst system can be any one, two or more of those that will react with a chromium source to form a chromium pyrrolide complex.
  • pyrrole- containing compound refers to hydrogen pyrrolide (i.e. pyrrole ⁇ C 4 H 5 N), derivatives of hydrogen pyrrolide, and substituted pyrrolides, as well as metal pyrrolide complexes and mixtures thereof.
  • a "pyrrolide” is defined as a compound comprising a 5-membered, nitrogen-containing heterocycle.
  • the pyrrole-containing compound can be pyrrole or any heteroleptic or homoleptic metal complex or salt containing a pyrrolide radical or ligand.
  • the pyrrole-containing compound can be either affirmatively added to the reaction or generated in-situ.
  • the pyrrole-containing compound will have from about 4 to about 20 carbon atoms per molecule.
  • Exemplary pyrrolides mentioned because of their high reactivity and activity with the other reactants, include pyrrole; lithium pyrrolide; sodium pyrrolide; potassium pyrrolide; cesium pyrrolide; the salts of substituted pyrrolides; or combinations thereof.
  • the useful substituted pyrrolides include, but are not limited to pyrrole-2-carboxylic acid; 2-acetylpyrrole; pyrrole-2-carboxaldehyde; tetrahydroindole; 2,5-dimethylpyrrole; 2,4-dimethyl-3- ethylpyrrole; 3-acetyl-2,4-dimethylpyrrole; ethyl-2,4-dimethyl-5-(ethoxycarbonyl)-3- pyrrole-propionate; ethyl-3,5-dimethyl-2-pyrrolecarboxylate; or combinations thereof.
  • the pyrrole-containing compound contains chromium
  • the resultant chromium compound can be called a chromium pyrrolide.
  • the most preferred pyrrole-containing compounds useful in a trimerization catalyst system can be selected from the group consisting of hydrogen pyrrolide, 2,5-dimethylpyrrole or chromium pyrrolides because of enhanced trimerization activity.
  • a chromium pyrrolide can provide both the chromium source and the pyrrole-containing compound.
  • a chromium pyrrolide is considered to provide both the chromium source and the pyrrole-containing compound.
  • the metal alkyl of the catalyst system can be any heteroleptic or homoleptic metal alkyl compound.
  • One or more metal alkyls can be used.
  • the alkyl ligands on the metal can be aliphatic, aromatic, or both (if more than one ligand is present).
  • the alkyl ligands are any saturated or unsaturated aliphatic radical.
  • the metal alkyl can have any number of carbon atoms. However, due to commercial availability and ease of use, the metal alkyl will usually comprise less than about 70 carbon atoms per metal alkyl molecule and preferably less than about 20 carbon atoms per molecule.
  • Exemplary metal alkyls include, but are not limited to, alkylaluminum compounds, alkylboron compounds, alkylmagnesium compounds, alkylzinc compounds or alkyl lithium compounds.
  • Exemplary metal alkyls include, but are not limited to n-butyl lithium; s-butyllithium; t-butyllithium; diethylmagnesium; diethylzinc; triethylaluminum; trimethylaluminum; triisobutylaluminum; or combinations thereof.
  • the metal alkyl is selected from the group consisting of non-hydrolyzed, i.e., not pre-contacted with water, alkylaluminum compounds, derivatives of alkylaluminum compounds, halogenated alkylaluminum compounds, and mixtures thereof.
  • Mixed metal alkyls can provide improved product selectivity, as well as improved catalyst system reactivity, activity, or productivity.
  • the use of hydrolyzed metal alkyls can result in decreased olefin (i.e. liquid) production and increased polymer (i.e. solid) production.
  • the metal alkyl is a non-hydrolyzed alkylaluminum compound expressed by the general formulas A1R 3 , A1R 2 X, A1RX 2 , AlR 2 OR, A1RXOR, or A1 2 R 3 X 3 , in which Al is an aluminum atom, each R is an alkyl group, O is an oxygen atom, and X is a halogen atom.
  • Exemplary compounds include, but are not limited to triethylaluminum; tripropylaluminum; tributylaluminum; diethylaluminum chloride; diethylaluminum bromide; diethylaluminum ethoxide; diethylaluminum phenoxide; ethylaluminum dichloride; ethylaluminum sesquichloride; and mixtures thereof for best catalyst system activity and product selectivity.
  • the most preferred single alkylaluminum compound is triethylaluminum, for the best catalyst system activity and product selectivity.
  • Catalyst systems most pertinent to the present invention comprise aluminum alkyls containing a halide, such as a chloride or a bromide.
  • a chloride containing-compound can improve product purity and selectivity.
  • Any chloride-containing compound can be used, such as, for example, DEAC and organo chlorides.
  • Exemplary organochlorides include, but are not limited to, carbon tetrachloride, methylene chloride, chloroform, benzylchloride, 1-hexachloroethane and mixtures thereof.
  • One particular composite catalyst contemplated here is the combination of chromium (III) ethylhexanoate, 2,5-dimethylpyrrole, triethylaluminum, and diethylaluminum chloride. This composite catalyst system can be used to trimerize ethylene, forming 1-hexene.
  • U.S. Patent No. 5,198,563 teaches the use of a suitable trimerization catalyst for the present invention. The entire patent is incorporated by reference for its disclosure of trimerization catalysts.
  • the chromium source, the pyrrole-containing compound, and the metal alkyl are combined in an olefinically or aromatically unsaturated hydrocarbon reaction medium.
  • the hydrocarbon can be any aromatic or aliphatic hydrocarbon, in a gaseous, liquid or solid state.
  • the hydrocarbon is in a liquid state.
  • the hydrocarbon can have any number of carbon atoms per molecule. Usually, the hydrocarbon will comprise less than about 70 carbon atoms per molecule, and preferably, less than about 20 carbon atoms per molecule, due to the commercial availability and ease of use of low-molecular-weight compounds.
  • the most preferred hydrocarbon compound is a reaction product formed by use of the catalyst system. For example, if 1-hexene is a reaction product, some of the 1- hexene product can be recycled for use as a reaction medium.
  • Exemplary unsaturated aliphatic hydrocarbon compounds contemplated for use as catalyst reaction media include, but are not limited to, ethylene, 1-hexene, 1,3-butadiene, and mixtures thereof.
  • Exemplary unsaturated aromatic hydrocarbons useful as reaction media include, but are not limited to, benzene, toluene, ethylbenzene, xylene, mesitylene, hexamethylbenzene, and mixtures thereof.
  • Unsaturated aromatic hydrocarbons are preferred to improve the stability of the catalyst system and to produce a highly active and selective catalyst system. The most preferred unsaturated aromatic hydrocarbon is ethylbenzene for best catalyst system activity and product selectivity.
  • the trimerization process generally is carried out in a slurry of the catalyst components in an inert medium or diluent.
  • the common trimerization reaction diluents can be liquid paraffins, cycloparaffins, olefins or aromatic hydrocarbons.
  • Exemplary reactor diluents include, but are not limited to, isobutane, cyclohexane, and mefhylcyclohexane. Isobutane can be used for enhanced compatibility with known olefin polymerization processes.
  • a homogenous trimerization catalyst system is more easily dispersed in cyclohexane. Therefore, a preferred diluent for a homogeneous catalyzed trimerization process is cyclohexane.
  • a slurry process can be carried out in a diluent (medium), which is a product of the olefin oligomerization process.
  • diluent medium
  • the choice of reactor diluent, or medium is based on the selection of the initial olefin reactant. For example, if the oligomerization catalyst is used to trimerize ethylene to 1-hexene, the solvent for the oligomerization reaction would be 1-hexene. If ethylene and he ene were trimerized to produce 1-decene, the oligomerization reaction solvent would be 1- decene. If 1,3-butadiene was trimerized to 1,5-cyclooctadiene, the trimerization reactor solvent would be 1,5-cyclooctadiene.
  • the catalyst system comprising a chromium source, pyrrole- containing compound, metal alkyl, and reaction media can contain additional components that do not adversely affect and can enhance the resultant catalyst system, such as, for example, halides.
  • the trimerization reaction can be conveniently carried out in a suitable reactor, preferably a continuous- feed autoclave reactor with a fluid jacket or internal heat transfer coil and any suitable stirring mechanism, such as, for example, mechanical stirring or an inert gas, typically nitrogen, purge, piping and valves. Any other suitable reaction equipment may also be used.
  • a loop reactor with mechanical stirring such as, for example, a stirring pump, can be used
  • Trimerization reaction products can be prepared from catalyst systems of this invention by dispersion reaction, slurry reaction, or gas phase reaction techniques using conventional equipment and contacting processes. Contacting of the monomer or monomers with a catalyst system can be effected by any manner known in the art. One convenient process is to suspend the catalyst system in the reaction medium and to agitate the mixture to maintain the catalyst system in dispersion throughout the trimerization process. Other known contacting processes also can be employed.
  • the catalyst system and reaction media are introduced to the reactor either continuously or in one or more charges, and the olefin reactant is continuously or intermittently introduced throughout the reaction as a gas under pressure.
  • the pressure in the reactor usually is maintained by adding a gaseous olefm reactant at a suitable rate to replace the olefin consumed by the reaction.
  • Hydrogen gas can be charged to the reactor during the reaction to improve the rate of reaction and enhance the catalyst system activity and trimer product selectivity.
  • the presence of hydrogen can be advantageous for reducing the by-product polymers into a powdery, non-tacky form that is easily removed from the reactor and easily separated from the effluent, as by filtering and/or evaporation.
  • the partial pressure of hydrogen present is usually from about 0.1 to about 100 kg/cm 2 (about 1 to 1000 N/cm 2 ), preferably from about 0.1 to about 80 kg/cm 2 (about 1 to 800 N/cm 2 ).
  • reaction temperature employed can be any temperature that can trimerize the olefin reactants. Generally, reaction temperatures are within a range of from about 0°C to about 250°C Preferably, reaction temperatures within a range of from about 60°C to about 200°C, and most preferably within a range of from about 80°C to about 150°C are employed.
  • a temperature in the range of from about 0°C to about 300°C generally can be used.
  • a temperature in the range of from about 60°C to about 110°C is employed. If the reaction temperature is too low, the polymer tends to stick to the reactor surfaces. If the reaction temperature is too high, the catalyst system and reaction products may decompose.
  • reaction pressures can be any pressure that can trimerize the olefin reactants.
  • reaction pressures are within a range of from about atmospheric pressure (0 psig or 0 N/cm 2 gauge pressure) to about 2500 psig (about 1700 N/cm 2 gauge pressure).
  • reaction pressures within a range of from about atmospheric pressure to about 1000 psig (690 N/cm 2 gauge pressure), and most preferably within a range of 300 to 900 psig (about 200 to about 620 N/cm 2 gauge pressure), are employed.
  • the reaction pressure is too low, the catalyst system activity can be too low.
  • the maximum pressure generally is dictated by safety concerns and the desire for vessels having walls no thicker than necessary.
  • the contents of the reactor can be agitated or stined by an inert gas
  • the reaction usually is run continuously by steadily charging lower 1 -olefin reactant(s), catalyst system, and process medium and removing the liquid contents of the reactor.
  • a continuous stirred tank reactor system can be employed that includes feed systems for catalyst system, reactant and medium and a discharge system for the effluent.
  • a batch process can also be employed, however.
  • the reactor effluent is treated to kill the remainder of the catalyst system, separate products, recycle the residual reactants, medium, and other components suitable for recycling, and dispose of any components that are not recycled.
  • the trimerization reaction is exothermic, so the reaction temperature usually can be regulated by circulating cooling water through a jacket or heat transfer coil, thus transferring heat out of the reactor. It is important to be able to transfer heat efficiently out of the reactor, so the reactor can be effectively maintained at the desired reaction temperature and the heat can be removed using a minimum quantity of the cooling medium. Another advantage of more effective heat transfer is that the trimerization reaction can be run at a higher throughput for a given temperature, which can improve production efficiency.
  • the reactor effluent stream comprising olefin trimer product(s), catalyst system, and some polymer or higher oligomer by-products, is contacted with a catalyst kill agent to "kill", deactivate or quench the catalyst.
  • catalyst kill agents contemplated here are alcohols, primary or secondary amines, or alkanolamines. Any alcohol that can be easily dispersed in the reactor effluent stream can be used as a catalyst kill agent. For example, lower alcohols such as methanol, ethanol, propanol, isopropanol, etc. can kill the catalyst system.
  • an alcohol is selected that has a boiling point, or molecular weight, such that the alcohol will not form an azeotrope with the olefin monomer product.
  • materials with similar boiling points and similar molecular weights are more likely to form azeotropes.
  • a mono functional alcohol with six or more carbon atoms per molecule is preferred as the catalyst kill agent.
  • a monofunctional alcohol having six to twelve carbon atoms per molecule is used for best catalyst system quenching. Such alcohols are easily removable from the 1- hexene olefin product.
  • Exemplary monofunctional alcohols include, but, are not limited to 1-hexanol; 2-hexanol; 3-hexanol; 2-ethyl- 1-hexanol; 3-octanol; 1-heptanol; 2-heptanol; 3-heptanol; 4-heptanol; 2-methyl-3-heptanol; 1-octanol; 2-octanol; 3-octanol; 4-octanol; 7-methyl-2-decanol; 1-decanol; 2-decanol; 3-decanol; 4- decanol; 5-decanol; 2-ethyl- 1-decanol; and mixtures thereof.
  • a low-molecular-weight diol or polyol for example ethylene glycol
  • ethylene glycol can be used as a catalyst kill agent.
  • Diols and polyols commonly have much higher boiling points than monoalcohols of comparable molecular weight, and thus can be separated more easily from 1-hexene.
  • the alcohol is used in an amount at least partially effective to quench the catalyst.
  • alcohol may be added in a molar ratio of from about 0.01 to about 100, preferably from about 0.01 to about 10, most preferably from about 0.05 to about 2, in relation to the metal content of the catalyst to be deactivated.
  • the hydrogen halide problem can be addressed by treating the product stream with a stabilizing material that forms a stable halide or hydrogen halide salt.
  • the stabilizing material contemplated here can be an aliphatic amine, an aromatic amine, a metal salt of an amide, a metal salt of a butoxide, a metal salt of a carboxylic acid, or a combination of these materials. More specifically, the stabilizing material in the present invention can be selected from cyclic and acyclic, aromatic and aliphatic amines, nitriles, amides, etc.
  • the primary amines contemplated as stabilizing materials include ethylamine; isopropylamine; cyclohexylamine; benzylamine; naphthylamine; and others.
  • the secondary amines include diethylamine; diisopropylamine; dibutyl- amine; dicyclohexylamine; dibenzylamine, and bis(trimethylsilyl)amine.
  • the stabilizing material can be a tertiary amine such as tributylamine.
  • the cyclic and aromatic amines and related compounds contemplated here as stabilizing materials include aniline; pyridine; dimethylpyridine; morpholine; imidazole; indoline; indole; pyrrole; 2,5-dimethylpyrrole; 3,4-dimethylpyrrole; 3,4-dichloropyrrole; 2,3,4,5-tetrachloropyrrole; 2-acetylpynole; pyrazole; pyrrolidine; pyrrolidone, and dipyrrylmethane.
  • the stabilizing materials contemplated here can be alkanolamines.
  • alkanolamines One particular advantage of alkanolamines is that the same molecule possesses both alcohol functionality and amine functionality, which may contribute both to deactivating, or killing, the catalyst system and to stabilize against the generation of corrosive hydrogen halides.
  • exemplary alkanolamines include isopropanolamine, monoethanolamine, diethanolamine, and triethanolamine.
  • the stabilizing materials contemplated here also include polyamines.
  • Exemplary polyamines are ethylenediamine, diethylenetriamine, and tetramethylethylenediamine.
  • the metal salts of amides usable in the present invention as stabilizers include salts of, for example, dimethylformamide; N-methylformamide; acetamide; N-methylhexaneamide; succinamide; maleamide; N-methylbenzamide; imidazole-2-carboxamide; di-2-thenolamine; beta-lactam; delta-lactam, or epsilon- lactam with metals of IA, IIA or IIIB Group of the periodic table.
  • metal amides examples include lithium amide; sodium ethylamide; calcium diethylamide; lithium diisopropylamide; potassium benzylamide; sodium bis (trimethylsilyl) amide; lithium indolide; sodium pyrrolide; lithium pyrrolide; potassium pyrrolide; potassium pyrrolidide; diethylaluminum pynolide; ethylaluminum dipyrrolide; aluminum tripynolide; sodium 2,5-dimethylpyrrolide; lithium 2,5-dimethylpynolide; potassium 2,5-dimethylpyrrolide; potassium 2,5-dimethylpyrrolidide; diethylaluminum; 2,5-dimethylpyrrolide; ethylaluminum; di(2,5-dimethylpyrrolide); aluminum tri(2,5-dimethylpyrrolide), and combinations of those.
  • the imides usable in the present invention as stabilizers include 1,2-cyclohexanedicarboxyimide, succinimide, phthalimide, maleimide, 2,4, 6-piperidinetrione, and perhydroazesine-2,10-dione.
  • the metal salts of butoxides usable herein are the butoxide salts of alkali metals (describe further).
  • An exemplary butoxide salt is potassium tert- butoxide.
  • the metal salts of carboxylic acids useful herein as stabilizers include the metal salts, more particularly the lithium, sodium, potassium and/or rubidium salts of, carboxylic acids.
  • carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, benzoic acid, phenylacetic acid, phthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, acrylic acid, maleic acid, fumaric acid, and salicylic acid.
  • An exemplary carboxylic acid salt contemplated here is silver acetate, lithium acetate, sodium acetate, potassium acetate, and mixtures thereof.
  • Exemplary phosphines useful herein as stabilizers include tributyl- phosphine oxide and triethylphosphine.
  • the stabilizing material should be provided in an amount effective to at least reduce the generation of hydrogen halide gas. For example, from about 0.01 to about 100 moles, preferably from about 0.01 to about 10 moles, more preferably from 0.05 to 2 moles of the stabilizing material can be added per mole of halogen in the catalysts.
  • an alcohol is not essential to quench or kill the catalyst.
  • Other materials for example primary or secondary amines, can be used to kill a catalyst, either alone or in combination with one or more alcohols.
  • an aliphatic primary amine, an aliphatic secondary amine, or a combination of those materials is contemplated for use as a catalyst kill agent.
  • the amines may be acyclic aliphatic amines or cyclic aliphatic amines, within the scope of the invention.
  • the amine quenching material can be provided in an amount effective to at least substantially quench the catalyst, either alone or when combined with an alcohol or other quenching agent.
  • Enough of the catalyst kill agent is added to the reactor effluent stream to at least substantially quench, deactivate, or "kill", the olefin production catalyst system and to reduce or eliminate the production of undesirable solids, particularly polymer or catalyst solids. If an insufficient amount of catalyst kill agent is used, any metals in the catalyst system, such as chromium or aluminum, can precipitate and interfere with future effluent processing. Generally, up to about five molar equivalents of catalyst kill agent can be added, per mole of metals in the effluent stream.
  • the amount of catalyst kill agent added is from about one to about four molar equivalents, and most preferably the amount of catalyst kill agent added is from about two to about three molar equivalents of catalyst kill agent per mole of metals in the reactor effluent stream. Too much catalyst kill agent can cause corrosion of the reactor.
  • the olefin products such as, for example, 1-hexene
  • Any removal process can be used, although distillation is preferred for ease of use.
  • ethylene is removed from the reaction product, then 1- hexene and the medium are distilled away from the reaction dispersion while the catalyst components are concentrated and recovered together with the by-product polyethylene.
  • Typical distillation temperatures in the distillation kettles are about 190°C to about 210°C. These distillation temperatures are believed to be sufficient to promote the decomposition of aluminum halides present in the spent catalyst to produce hydrogen halides, unless steps are taken as described in this disclosure to prevent hydrogen halide generation.
  • the concentrated dispersion containing by-product polymer and catalyst components may be discarded, or can be further treated as described below.
  • the product stream produced by the ethylene trimerization process commonly contains one of more of the following compounds butene; 1 -hexene; internal hexenes (i.e. 2-hexene or 3-hexene); octenes; decenes; reaction medium; and "heavies".
  • the waste product steam formed by removing the desired olefin monomer products can be further processed by contacting it with an aqueous base to remove metals.
  • Organic bases are not preferred at this point because organic bases can be too weak to precipitate heavy metals, such as chromium.
  • the preferred aqueous inorganic bases are sodium hydroxide and potassium hydroxide, due to their ease of use, availability, low cost, and beneficial effects on future processing.
  • the amount of aqueous inorganic base added can be any amount sufficient to precipitate most or substantially all of the chromium. The most important goal of this step is to remove chromium or other heavy metals, as any remaining dispersed aluminum does not raise the same environmental issues.
  • aqueous inorganic base can prevent precipitation of the chromium.
  • about up to about 4 molar equivalents of aqueous inorganic base should be used per mole of chromium and aluminum.
  • from about 0.2 to about 3 molar equivalents, and most preferably from about 1 to 2 molar equivalents of the aqueous inorganic base should be used per mole of chromium and aluminum.
  • the chromium-containing solid precipitate then can be removed and disposed of properly. Following removal of the chromium containing solid precipitate, the aqueous and organic layers, or portions, are separated. The organic layer can be disposed of.
  • trimerization process commonly produces two residues that can build up on the internal surfaces of the reactor.
  • This higher oligomer or polymer residue is referred to here, for the sake of simplicity, as just "polymer residue".
  • polymer residue For example, in the case of an ethylene reaction, polyethylene or paraffin wax residue can be formed and build up on the internal surfaces of the reactor. This polymer residue detracts from the heat transfer efficiency of the internal surfaces of the reactor. Polymer residue may be removed from the reactor by washing the reactor with a solvent for the residue.
  • the trimerization reactor commonly is supplied with a solvent for by-product polymers - such as cyclohexane or methylcyclohexane - as the process medium.
  • a solvent for by-product polymers - such as cyclohexane or methylcyclohexane -
  • the same process medium can be used to periodically flush out the reactor.
  • the washing conditions can be more stringent than the usual process conditions, to remove the polymer residue that is not removed under the usual process conditions.
  • the washing step can be a "hot wash", carried out by circulating the usual process medium at a higher temperature than the process temperature to melt, more quickly dissolve, or otherwise dislodge the polymer residue.
  • the hot wash can be carried out as follows.
  • the reaction can be halted by stopping the feed of catalyst and reactants while continuing to inject and drain the reactor medium, which can be, but is not limited to, cyclohexane and/or methylcyclohexane and increasing the medium temperature by about 60°C to 70°C.
  • the hot wash is continued for several hours, or as long as necessary to remove all or substantially all of the polymer residue. This hot wash has been found to remove the buildup of the polymer residue.
  • a second residue which also detracts substantially from the heat transfer efficiency of the reactor, is referred to here as catalyst residue. The exact chemical constitution of this catalyst residue is not known.
  • Example 1 To an inert gas purged one liter, three-necked flask equipped with nitrogen purge, magnetic stirrer, glass column, Dean-Stark tube and condenser was added 250 mL dry dodecane and 260 mL of 2-ethyl- 1-hexanol. The system was purged again for 20 minutes and 50 mL of selective 1-hexene catalyst (5 mg Cr/mL) was added. Water (2 mL) was added and the system was heated to reflux. Nine samples were taken over 5 hours. Acidity was assessed by water extraction of the samples taken from the Dean Stark tube and testing the water with pH paper. The first sample was mildly acidic and all of the other samples were very acidic. Water was observed to be present in the last sample.
  • Example 2 Example 1 was repeated but in addition to the 2 mL of water, 4 mL of tri-n-butylamine also was added. None of the subsequent nine samples from the Dean-Stark tube were acidic demonstrating the effectiveness of adding an amine to the process. Water was observed in the ninth sample, as was observed in Example 1. The presence of the amine removed all indications of acidity.
  • Experimental Apparatus for Examples 3 and 4 The apparatus used for Examples 3 and 4 was a one liter, three- necked round bottom flask equipped with a glass well for a thermocouple to monitor the kettle temperature, an addition funnel and a Dean-Stark tube.
  • a condenser was placed at the top of the Dean-Stark tube as was a thermocouple to measure overhead temperature and a wire that held a piece of pH paper at the top of the Dean-Stark tube.
  • the flask also was equipped with a magnetic stirring bar and a stirrer and a heating mantle. A nitrogen stream constantly swept material through the apparatus and a bubbler containing water.
  • Example 4 The following materials were added to the apparatus described above: 200 g of dry dodecane, 81 mL of a 1.9M solution of DEAC in dodecane and 96 mL of 2-ethyl- 1-hexanol was slowly added. Tri-n-butylamine (40.25 g) was added. This mixture was heated to a kettle temperature of 208°C over 4 hours. The following observations were made. There was no change in color of the pH paper in the top of the Dean Stark tube throughout the experiment. The pH of the water bubbler was neutral at the end of the experiment. Samples from the bottom of the Dean Stark tube were neutral or slightly basic as indicated by moist pH paper. It was clear that any acid formed was removed from the system by the addition of the amine.

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

Abstract

La présente invention concerne un procédé d'oligomérisation. Un catalyseur, une oléfine inférieure et un milieu de traitement sont décrits. L'oléfine inférieure réagit en présence du catalyseur pour produire une vapeur de produit comprenant un produit oléfine supérieure et un reste de catalyseur dispersé dans le milieu de traitement. La vapeur de produit résultante est traitée avec un matériau d'extinction. Ce matériau d'extinction peut être une amine primaire aliphatique, une amine secondaire aliphatique, un alcool ou une combinaison de ces derniers. On a remarqué que les matériaux d'extinction amine génèrent peu ou aucun halogénure d'hydrogène lorsqu'ils sont utilisés pour épuiser des catalyseurs d'oligomérisation. Les matériaux d'extinction alcool peuvent générer des halogénures d'hydrogène en utilisation. Ce problème peut être atténué, il faut alors traiter la vapeur de produit avec une matière de stabilisation qui forme un sel halogénure d'hydrogène stable. Des exemples de matières de stabilisation peuvent comprendre les amines aliphatiques, les amines aromatiques et les sels métalliques d'amides, de butoxydes ou d'acides carboxyliques.
PCT/US2000/035366 1999-12-29 2000-12-27 Procedes permettant d'eviter la generation d'halogenures d'hydrogene dans un systeme de recuperation de produits d'oligomerisation WO2001047839A1 (fr)

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CA002392233A CA2392233C (fr) 1999-12-29 2000-12-27 Procedes permettant d'eviter la generation d'halogenures d'hydrogene dans un systeme de recuperation de produits d'oligomerisation
EP00989508A EP1242341A4 (fr) 1999-12-29 2000-12-27 Procedes permettant d'eviter la generation d'halogenures d'hydrogene dans un systeme de recuperation de produits d'oligomerisation
MXPA02005399A MXPA02005399A (es) 1999-12-29 2000-12-27 Proceso para impedir la generacion de haluros de hidrogeno en un sistema de recuperacion de producto de oligomerizacion.
AU26006/01A AU773364B2 (en) 1999-12-29 2000-12-27 Processes for preventing generation of hydrogen halides in an oligomerization product recovery system

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US09/473,688 1999-12-29

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Cited By (21)

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Publication number Priority date Publication date Assignee Title
WO2004082827A1 (fr) * 2003-03-14 2004-09-30 Chevron Phillips Chemical Company Procede permettant de diminuer ou d'eliminer la corrosion de la decomposition de catalyseurs olefiniques contenant des halogenures
US7820581B2 (en) 2004-02-20 2010-10-26 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US7902415B2 (en) 2007-12-21 2011-03-08 Chevron Phillips Chemical Company Lp Processes for dimerizing or isomerizing olefins
US7910670B2 (en) 2005-08-19 2011-03-22 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US7994376B2 (en) 2004-02-19 2011-08-09 Chevron Phillips Chemical Company Lp Olefin oligomerization
US8049052B2 (en) 2008-10-31 2011-11-01 Chevron Phillips Chemical Company Lp System and method of deactivating and quenching an oligomerization catalyst
US8329608B2 (en) 2004-02-20 2012-12-11 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US8809613B2 (en) 2009-07-24 2014-08-19 Saudi Basic Industries Corporation Method for preparing linear alpha-olefins
US9505011B1 (en) 2015-12-28 2016-11-29 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as mining chemical collectors
US9512248B1 (en) 2015-12-28 2016-12-06 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as chain transfer agents
US9512071B1 (en) 2015-12-28 2016-12-06 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
WO2017011127A1 (fr) * 2015-07-14 2017-01-19 Chevron Phillips Chemical Company Lp Compositions d'oléfine
US9550841B2 (en) 2004-02-20 2017-01-24 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US9586872B2 (en) 2011-12-30 2017-03-07 Chevron Phillips Chemical Company Lp Olefin oligomerization methods
US9593055B2 (en) 2008-01-30 2017-03-14 Saudi Basic Industries Corporation Method for preparing linear alpha-olefins
US10011564B2 (en) 2015-12-28 2018-07-03 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US10040758B2 (en) 2015-12-28 2018-08-07 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US10294200B2 (en) 2015-12-28 2019-05-21 Chevron Phillips Chemical Company, Lp Mixed branched eicosyl polysulfide compositions and methods of making same
FR3103486A1 (fr) * 2019-11-26 2021-05-28 IFP Energies Nouvelles Procede de neutralisation d’une composition catalytique contenu dans un effluent issu d’une etape d’oligomerisation
FR3103485A1 (fr) * 2019-11-26 2021-05-28 IFP Energies Nouvelles Procédé de séparation d’un effluent issu d’une étape d’oligomérisation
RU2826641C1 (ru) * 2019-11-26 2024-09-16 Ифп Энержи Нувелль Способ разделения потока, выходящего с этапа олигомеризации

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2471762C1 (ru) 2011-06-22 2013-01-10 Открытое акционерное общество "СИБУР Холдинг" (ОАО "СИБУР Холдинг") Способ выделения продуктов олигомеризации олефинов и разложения остатков катализатора олигомеризации
DK3237364T3 (da) 2014-12-23 2019-05-13 Sibur Holding Public Joint Stock Co Fremgangsmåde til at præcipitere polymer og deaktiveret organometallisk katalysator i en olefin oligomeriseringsreaktion
WO2017046701A1 (fr) * 2015-09-16 2017-03-23 Sabic Global Technologies B.V. Procédé permettant la dégénérescence d'un catalyseur d'oligomérisation d'oléfine
US11472756B2 (en) * 2016-12-19 2022-10-18 Sabic Global Technologies B.V. Method of separating linear alpha olefins

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0200654A1 (fr) * 1985-05-02 1986-11-05 Institut Français du Pétrole Procédé de production de butène-1 de pureté améliorée à partir du produit brut de dimersion de l'éthylène
US5030790A (en) * 1987-07-13 1991-07-09 Sergienko Galina S Process for producing butene-1
US5689028A (en) * 1994-02-18 1997-11-18 Phillips Petroleum Company Process to regulate olefin production by catalyst system inhibition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486615A (en) * 1960-09-14 1984-12-04 Exxon Research & Engineering Co. Preparation of linear olefin products
DE3675385D1 (de) * 1986-04-17 1990-12-06 Idemitsu Petrochemical Co Verfahren zur herstellung von linearen alpha-olefinen.
FR2715154B1 (fr) * 1994-01-14 1996-04-05 Inst Francais Du Petrole Procédé de production d'oléfines alpha légères de pureté améliorée par oligomérisation, de l'éthylène.
FR2759922B1 (fr) * 1997-02-25 1999-05-07 Inst Francais Du Petrole Composition catalytique amelioree pour la conversion de l'ethylene en olefines alpha legeres

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0200654A1 (fr) * 1985-05-02 1986-11-05 Institut Français du Pétrole Procédé de production de butène-1 de pureté améliorée à partir du produit brut de dimersion de l'éthylène
US5030790A (en) * 1987-07-13 1991-07-09 Sergienko Galina S Process for producing butene-1
US5689028A (en) * 1994-02-18 1997-11-18 Phillips Petroleum Company Process to regulate olefin production by catalyst system inhibition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1242341A4 *

Cited By (33)

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WO2004082827A1 (fr) * 2003-03-14 2004-09-30 Chevron Phillips Chemical Company Procede permettant de diminuer ou d'eliminer la corrosion de la decomposition de catalyseurs olefiniques contenant des halogenures
US7994376B2 (en) 2004-02-19 2011-08-09 Chevron Phillips Chemical Company Lp Olefin oligomerization
US8993822B2 (en) 2004-02-20 2015-03-31 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US7820581B2 (en) 2004-02-20 2010-10-26 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US8329608B2 (en) 2004-02-20 2012-12-11 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US9550841B2 (en) 2004-02-20 2017-01-24 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US7910670B2 (en) 2005-08-19 2011-03-22 Chevron Phillips Chemical Company Lp Methods of preparation of an olefin oligomerization catalyst
US7902415B2 (en) 2007-12-21 2011-03-08 Chevron Phillips Chemical Company Lp Processes for dimerizing or isomerizing olefins
US9593055B2 (en) 2008-01-30 2017-03-14 Saudi Basic Industries Corporation Method for preparing linear alpha-olefins
US8049052B2 (en) 2008-10-31 2011-11-01 Chevron Phillips Chemical Company Lp System and method of deactivating and quenching an oligomerization catalyst
US8809613B2 (en) 2009-07-24 2014-08-19 Saudi Basic Industries Corporation Method for preparing linear alpha-olefins
US9586872B2 (en) 2011-12-30 2017-03-07 Chevron Phillips Chemical Company Lp Olefin oligomerization methods
EP4039668A1 (fr) * 2015-07-14 2022-08-10 Chevron Phillips Chemical Company LP Compositions d'oléfine
US10435336B2 (en) 2015-07-14 2019-10-08 Chevron Phillips Chemical Company Lp Olefin compositions
WO2017011127A1 (fr) * 2015-07-14 2017-01-19 Chevron Phillips Chemical Company Lp Compositions d'oléfine
WO2017010998A1 (fr) * 2015-07-14 2017-01-19 Chevron Phillips Chemical Company Lp Compositions d'oléfines
US10000590B2 (en) 2015-12-28 2018-06-19 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as chain transfer agents
US9512071B1 (en) 2015-12-28 2016-12-06 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US9738601B2 (en) 2015-12-28 2017-08-22 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US9879102B2 (en) 2015-12-28 2018-01-30 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as chain transfer agents
US9938237B2 (en) 2015-12-28 2018-04-10 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US9505011B1 (en) 2015-12-28 2016-11-29 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as mining chemical collectors
US10011564B2 (en) 2015-12-28 2018-07-03 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US10040758B2 (en) 2015-12-28 2018-08-07 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and methods of making same
US10294200B2 (en) 2015-12-28 2019-05-21 Chevron Phillips Chemical Company, Lp Mixed branched eicosyl polysulfide compositions and methods of making same
US9631039B1 (en) 2015-12-28 2017-04-25 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as chain transfer agents
US9512248B1 (en) 2015-12-28 2016-12-06 Chevron Phillips Chemical Company Lp Mixed decyl mercaptans compositions and use thereof as chain transfer agents
FR3103485A1 (fr) * 2019-11-26 2021-05-28 IFP Energies Nouvelles Procédé de séparation d’un effluent issu d’une étape d’oligomérisation
WO2021104925A1 (fr) * 2019-11-26 2021-06-03 IFP Energies Nouvelles Procede de neutralisation d'une composition catalytique contenu dans un effluent issu d'une etape d'oligomerisation
WO2021104924A1 (fr) * 2019-11-26 2021-06-03 IFP Energies Nouvelles Procede de separation d'un effluent issu d'une etape d'oligomerisation
CN114728865A (zh) * 2019-11-26 2022-07-08 Ifp 新能源公司 分离获自低聚步骤的流出物的方法
FR3103486A1 (fr) * 2019-11-26 2021-05-28 IFP Energies Nouvelles Procede de neutralisation d’une composition catalytique contenu dans un effluent issu d’une etape d’oligomerisation
RU2826641C1 (ru) * 2019-11-26 2024-09-16 Ифп Энержи Нувелль Способ разделения потока, выходящего с этапа олигомеризации

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AU2600601A (en) 2001-07-09
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CA2392233C (fr) 2006-10-24
CA2392233A1 (fr) 2001-07-05
EP1242341A1 (fr) 2002-09-25
CN1399620A (zh) 2003-02-26
RU2249585C2 (ru) 2005-04-10
ZA200203457B (en) 2003-10-29
MXPA02005399A (es) 2002-12-05
GC0000217A (en) 2006-03-29
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