CN1399620A - Processes for preventing generation of hydrogen halides in oligomerization product recovery system - Google Patents
Processes for preventing generation of hydrogen halides in oligomerization product recovery system Download PDFInfo
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- CN1399620A CN1399620A CN00816222A CN00816222A CN1399620A CN 1399620 A CN1399620 A CN 1399620A CN 00816222 A CN00816222 A CN 00816222A CN 00816222 A CN00816222 A CN 00816222A CN 1399620 A CN1399620 A CN 1399620A
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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
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- 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
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Abstract
The invention is an oligomerization process. A catalyst, a lower olefin, and a process medium are provided. The lower olefin is reacted in the presence of the catalyst to produce a product stream comprising a higher olefin product and a catalyst residue dispoersed in the process medium. The resulting product stream is treated with a quenching material. The quenching material can be an aliphatic primary amine, an aliphatic secondary amine, an alcohol, or a combination of those materials. Amine quenching materials have been found to generate few or no hydrogen halides when used to quench oligomerization catalysts. Alcohol quenching materials can generate hydrogen halides in use. This problem can be alleviated by treating the product stream with a stabilizing material that forms a stable hydrogen halide salt. Exemplary stabilizing materials include aliphatic amines, aromatic amines, and metal salts of amides, butoxides, or carboxylic acids.
Description
Background of the present invention
The present invention relates generally to the catalytic production of alkene.
The present invention relates more specifically to a kind of from oligomerization reactor, as cancellation catalyzer in the overflow of trimerization reaction device to avoid producing the method for hydrogen halide.
Alkene, the alpha-olefin that especially is also referred to as 1-alkene are widely used as speciality chemical and as monomer or comonomer in the polymerization technology.High alpha-olefin and other alkene can be by with light alkenes, and for example ethene contact catalyst and making wherein produces the tripolymer of monoolefine, dimer or other reaction product of diolefine in addition reaction.This reaction can be called " trimerization reaction " or " oligomerization ".Usually, catalyst system is dispersed in the process solvent, and with reactant, rudimentary 1-alkene and dispensable hydrogen add as other.Reaction product or higher alkene are dissolved in the process solvent when it forms.
Product alkene and spent catalyst system be by removing the process solvent comprise them from reactor, that is, and and reactor overflow and reclaiming.Preferably, before separating any reactive component, in this reaction system, add catalyzer and kill agent.This overflow can be through handling with cancellation or " killing " catalyzer.Overflow is separable to be used for the catalyst system waste treatment, reclaims any remaining rudimentary 1-alkene and process solvent content and reclaims product alkene s.
Can use the aluminum alkyls part of quencher with this catalyst system of cancellation.The cancellation of catalyst system is isomerizated into non-required internal olefin to preventing the 1-olefin product, promptly 2-and more higher alkene be important, otherwise can reduce product purity.The cancellation of catalyst system also can relate to air-and the hazardous material of water-susceptibility aluminum alkyls.
Former patent proposes, and alcohol can be added catalyzer ejecta in the overflow of olefin oligomerization device with cancellation or " killing " catalyzer.U.S. patent No.5,689,028 is open, 2-Ethylhexyl Alcohol added in the reactor overflow of trimerization reaction device as quencher with this catalyst system of cancellation.U.S. patent No.5,859,303 embodiment 1 is open, but adds the alcohol cancellation or kill catalyst system.U.S. patent No.5,750,817 disclose use ethanol comes the reaction of cancellation ethylene trimerization.
U.S. patent No.5,750,816 propose to add alcohol in the overflow of ethylene trimerization reactor, phenol, carboxylic acid, uncle or secondary amine, or ammonia is as " metal solubilizing agent ".This patents state, " percentage ratio of used metal solubilizing agent optional since trace to the normal wide region of solvent, but it is preferably 0.001-50% weight, more preferably 0.01-10% weight is with the densitometer in the solvent ".For example use the 1-hexanol (embodiment 5 and 13) of 0.022% weight, hexyl amine (embodiment 6 and 14), or ammonia (embodiment 7 and 15).This patent proposes prevailingly, this step " from the technology circuit of the inlet that is exported to distillation tower of oligomerization reactor " " keeping the most of catalyst component in the reaction dispersion is dispersion state " ".U.S. patent No.5,750,816,12 hurdles, 20-23 and 49-67 are capable.
Summary of the present invention
The inventor has been found that after oligomerization as quencher can produce hydrogen halide with the alcohol of cancellation halogenation catalyst for trimerization system.For example, especially at water or at the bottom of being present in still in the equipment in the presence of can cause producing hydrogen chloride gas with pure cancellation chlorination catalyst.Hydrogen halide is to the processing unit high corrosion.
Therefore, need provide catalyzer cancellation material and the method that does not produce hydrogen halide.
Need reduce or eliminate equally and when using alcohol, produce hydrogen halide as quencher.
One or more aforementioned requirements or one or more satisfied wholly or in part by invention as herein described in other obvious requirement of this specification sheets.
One aspect of the present invention is a kind of oligomerization process.In this technology, provide catalyst system, light alkene reactant and processing medium.Light alkene reacts in the presence of catalyst system and produces the product logistics.This product logistics comprises higher olefin product and catalyst system resistates, and the both is dispersed in process solvent or the medium.
The products therefrom logistics is with comprising aliphatic primary amine, aliphatic secondary amine, or the cancellation material of its combination is handled.According to circumstances, alcohol or other cancellation material also can combine with selected amine to eliminate compound cancellation material.The amount of effective cancellation catalyzer provides the cancellation material so that lack basically.
Have been found that amine cancellation material produces less or do not have hydrogen halide when being used for the cancellation oligomerisation catalyst.
Another aspect of the present invention is a kind of oligomerization process, and wherein the product logistics is used to the alcohol of the amount of the effective cancellation catalyzer of small part and handled.This product logistics is also handled with a kind of stabilization material that can form the stabilisation of halogenated hydrogen salt.This stabilization material provides with the amount that has at least the minimizing of imitating to produce free hydrogen halide.
Although pure cancellation material has been found to produce hydrogen halide, the stabilization material obviously produces stable material by the interaction with any hydrogen halide and relaxes this problem, and the invention is not restricted to any specific binding mode.
Detailed description of the present invention
Although the present invention describes according to one or more embodiments, be appreciated that to the invention is not restricted to these embodiments.They on the contrary, the present invention includes all optional thing, modification and equivalent, because can be included in the purport and scope of appended claims.Mentioned or narration to the preferred of some embodiment and do not mean that and get rid of not mentioned or be stated as preferred other embodiment.
The reaction that this paper considered broadly relates to the oligomerization of ethene and other light alkene s formation higher alkene s.In this article, " rudimentary " is relative with " senior "; Light alkene used herein is any 1-alkene that changes into senior 1-alkene, and the carbonatoms of wherein said senior 1-alkene is greater than described light alkene.Be reflected under the existence of one or more catalyzer promoting and carry out under the condition that reaction is carried out.
The present invention with trimerization reaction as an example, but the present invention can consider to be used for other oligomerization." trimerization reaction " used herein is defined as any two kinds, three kinds or multiple alkene minimizing alkene number, that is, and and any combination of the carbon-carbon double bond between two.For example, three alkene keys in the combination of three ethylene unit can reduce two in the 1-hexene, be kept to an alkene key.In another example, four alkene keys in two unitary combinations of 1,3-butadiene can be 1, reduces two in the 5-cyclooctadiene, is kept to two alkene keys.
Term used herein " trimerization reaction " means dimerization reaction and " trimerization reaction altogether " that comprises diolefine, is further discussed below respectively.Below further describe reactant, catalyzer, equipment and the reaction conditions that can be used for technology of the present invention and pass through reaction product and the by product that trimerization reaction forms.
Reactant
The reactant that can be used for the present invention's three polymerizing technologies comprises can autoreaction, that is, trimerization becomes the olefinic compounds of useful products.For example, the autoreaction of ethene can obtain the 1-hexene, and the autoreaction of 1,3-butadiene can obtain 1, the 5-cyclooctadiene.The reactant that can be used for the present invention's three polymerizing technologies comprises also and can react with other olefinic compounds that promptly, trimerization obtains the olefinic compounds of useful products altogether.For example, the common trimerization reaction of ethene and hexene can obtain 1-decene or 1-tetradecylene.The common trimerization reaction of ethene and 1-butylene can obtain the 1-octene.The common trimerization of 1-decene and ethene can obtain 1-tetradecylene or 1-docosene.
Have about 30 carbon atoms of about 2-and have those compounds of at least a olefinic double bond but suitable trimeric olefin(e) compound is a per molecule.The example of alkene includes, but is not limited to following material.
Can use acyclic olefin, for example, ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 1-hexene, 2-hexene, 3-hexene, the 1-heptene, 2-heptene, 3-heptene, four kinds of positive octenes, four kinds of positive nonenes, and any two or more mixture in these materials.
The example of the operable diolefin compound of this paper includes, but is not limited to, 1,3-butadiene, 1,4-pentadiene and 1,5-hexadiene.
If use side chain or cycloolefin, be confined to it is believed that sterically hindered this trimerization reaction process that hinders under the theoretical situation being reluctant as reactant.Therefore, the side chain of alkene or circular part are generally away from carbon-carbon double bond.The invention is not restricted to use by this theory suggestion and be useful alkene.Any alkene that can participate in this reaction all can consider to be used for the present invention.
Catalyst system
A kind of catalyst for trimerization system that the present invention considers is a kind of three compositions system, comprises the chromium source, contains the combination of pyrroles's compound and metal alkylide.According to circumstances, this catalyst system can be carried on the inorganic oxide carrier.These catalyst systems are particularly useful for two polymerizations and the trimerization reaction of alkene, and for example, vinyl polymerization becomes the 1-hexene.For the present invention, more broadly can consider any catalyzer or catalyst system that comprises metal alkylide.Catalyst system generally includes halide source, for example, and muriate, bromide, iodide, or fluorochemical.
The chromium source can be can be one or more organic or inorganic compounds, and wherein the chromium oxidation state is 0-6.In general, the chromium source has structural formula CrXn, and wherein each X can be identical or different, and can be that any organic or inorganic group and n are integer 1-6.But each group of the example of organic group has about 20 carbon atoms of about 1-, and can be for example alkyl, alkoxyl group, ester, ketone, carboxylate salt or amido.Organic group can be straight or branched, ring-type or acyclic, aromatics or aliphatic series, can be by mixed aliphatic series, aromatics, or cycloaliphatic groups forms.The example of inorganic group includes, but is not limited to any negatively charged ion or oxide group, for example, and halogenide, vitriol, or oxide compound.
Preferably, the chromium source is can access to have the compound that contains chromium (II) or chromium (III) that improves oligomeric or the active catalyst system of trimerization reaction
Most preferably, the chromium source is chromium (III) compound because it use easily, be easy to get and the catalyst system activity higher.The example of chromium (III) compound includes, but is not limited to carboxylic acid chromium, chromium naphthenate, hafnium halide halogenide, and pyrroles's chromium and diketone close chromium.The object lesson of chromium (III) compound (following follow-up in some cases with its corresponding abbreviation) includes, but is not limited to 2,2,6,6, and-dipivaloylmethane closes chromium (III)-Cr (TMHD)
32 ethyl hexanoic acid chromium (III)-Cr (EH)
3Three-(2 ethyl hexanoic acid) chromium (III); Chromium naphthenate (III)-Cr (Np)
3Chromium chloride (III); Chromic bromide; Chromium fluoride; Acetyl Acetone closes chromium (III); Chromium acetate (III); Chromium butyrate (III); PIVALIC ACID CRUDE (25) chromium (III); Lauric acid chromium (III); Chromium stearate (III); Pyrroles's chromium (III); Chromium+oxalic acid (III); Or two or more combination.
The object lesson of chromium (II) compound includes, but is not limited to chromous bromide; Chromous Fluoride; Chromous chloride; Two-(2 ethyl hexanoic acid) chromium (II); Chromium acetate (II); Chromium butyrate (II); PIVALIC ACID CRUDE (25) chromium (II); Lauric acid chromium (II); Chromium stearate (II); Chromium+oxalic acid (II); Pyrroles's chromium (II); Or two or more combination.Chromium (II) and chromium (III) compound also can be used in combination.
The compound that contains the pyrroles of this catalyst system can be any, two or more can form those of pyrroles's chromic compound with chromium source reaction.Term used herein " compound that contains the pyrroles " be meant the hydrogen pyrroles (be the pyrroles--C
4H
5N), hydrogen pyrroles's derivative and the pyrrolesization thing that replaces, and metal pyrroles title complex and composition thereof." pyrrolesization thing " is defined as the compound that comprises 5 member heterocyclic ring containing nitrogens.
Broadly, the compound that contains the pyrroles can be pyrroles or any heterolysis (heteroleptic) or isolytic metal complexes or salt that comprises pyrrolesization thing group or part.The compound that contains the pyrroles can initiatively add reaction or on-the-spot the generation.
In general, the compound per molecule that contains the pyrroles has about 20 carbon atoms of about 4-.Example with its hyperergy and the pyrrolesization thing that is mentioned with the activity of other reactant comprises the pyrroles; Pyrroles's lithium; Pyrroles's sodium; Pyrroles's potassium; Pyrroles's caesium; The salt of substituted azole thing; Or its combination.Useful substituted azole thing includes, but is not limited to pyrroles-2-carboxylic acid; The 2-acetyl pyrrole; Pyrrole-2-aldehyde; Tetrahydro indole; 2, the 5-dimethyl pyrrole; 2,4-dimethyl-3-N-ethyl pyrrole N-; 3-ethanoyl-2, the 4-dimethyl pyrrole; 2,4-dimethyl-5-(ethoxy carbonyl)-3-pyrroles-ethyl propionate; 3,5-dimethyl-2-minaline ethyl ester; Or its combination.Comprise chromium if contain pyrroles's compound, the gained chromium cpd can be called pyrroles's chromium.
The compound that contains the pyrroles that most preferably is used for the catalyst for trimerization system can be selected from the hydrogen pyrroles, and 2,5-dimethyl pyrrole or pyrroles's chromium are because they have higher trimerization activity.According to circumstances, for the ease of using, pyrroles's chromium can provide the chromium source and contain pyrroles's compound.When being used for present disclosure, if pyrroles's chromium is used to form catalyst system, the compound that pyrroles's chromium is considered to the chromium source is provided and contains the pyrroles.Although all compounds that contains the pyrroles can produce the catalyst system with high reactivity and productivity, pyrroles or 2, the use of 5-dimethyl pyrrole can produce that to have an enhanced active and to the catalyst system of required product selectivity.
The metal alkylide of this catalyst system can be any heterolysis or isolytic alkyl metal cpd.Can use one or more metal alkylides.Alkyl part on the metal can be an aliphatic series, aromatics, or both (if having more than one part).Preferably, the alkyl part is any saturated or unsaturated aliphatic group.
Metal alkylide can have any carbonatoms.But because commercial availability and be easy to use, metal alkylide comprises usually and is lower than about 70 carbon atoms/each metal alkylide molecule and preferably is lower than about 20 carbon atoms/each molecule.
The example of metal alkylide includes, but is not limited to, alkylaluminium cpd, alkyl boron compound, alkyl magnesium compound, alkyl zinc compound or alkyl lithium compounds.The example of metal alkylide includes, but is not limited to the n-butyllithium; The s-butyllithium; The t-butyllithium; Magnesium ethide; Zinc ethyl; Triethyl aluminum; Trimethyl aluminium; Triisobutyl aluminium; Or its combination.
Preferably, metal alkylide is selected from unhydrolysed, that is, do not contact in advance with water, and alkylaluminium cpd, the derivative of alkylaluminium cpd, the halogenated alkyl aluminum compound, and composition thereof.The mixed alkyl metal can produce improved selectivity of product and improved catalyst system reactivity, activity or productivity.The use of the metal alkylide of hydrolysis can cause lower alkene (being liquid) to be produced and higher polymkeric substance (being solid) is produced.
Most preferably, metal alkylide is unhydrolysed alkylaluminium cpd, is expressed as general formula AlR
3, AlR
2X, AlRX
2, AlR
2OR, AlRXOR, or Al
2R
3X
3, wherein Al is the aluminium atom, and each R is an alkyl group, and O is that Sauerstoffatom and X are halogen atoms.For the catalyst system activity and the selectivity of product of the best, exemplary compounds includes, but is not limited to triethyl aluminum; Tri-propyl aluminum; Tri-butyl aluminum; Diethyl aluminum chloride; The diethyl aluminum bromide; The diethyl aluminum ethylate; Diethyl phenol aluminium; Ethylaluminum dichloride; Ethyl sesquialter aluminum chloride; And composition thereof.For the catalyst system activity and the selectivity of product of the best, most preferred single alkylaluminium cpd is a triethyl aluminum.The optimal catalyst system of the present invention is comprised the Halogen root, as the aluminum alkyls of chlorine root or bromine root.
Be reluctant to be confined to theory, it is believed that chloride compound can improve product purity and selectivity.Can use any chloride compound, for example, DEAC and organic chloride.The example of organic chloride includes, but is not limited to tetracol phenixin, methylene dichloride, chloroform, benzyl chloride, 1-hexachloroethane and composition thereof.
A kind of special composite catalyst that this paper considers is thylhexoic acid chromium (III), 2, and 5-dimethyl pyrrole, the combination of triethyl aluminum and diethyl aluminum chloride.This complex catalyst system can be used for three polyethylene to form the 1-hexene.U.S. patent No.5,198,563 have proposed to be applicable to the application of catalyst for trimerization of the present invention.Whole patent is incorporated it into the present invention with open trimerization reaction catalyzer as a reference at this.
Medium
Usually, the chromium source contains pyrroles's compound and metal alkylide combination in olefinic or aromatics unsaturated hydrocarbons reaction medium.Hydrocarbon can be any aromatics or aliphatic hydrocrbon, is gaseous state, liquid state or solid-state.Preferably,, contain pyrroles's compound in order fully to contact the chromium source, and metal alkylide, this hydrocarbon is liquid.
But this hydrocarbon per molecule has any carbonatoms.Usually, this hydrocarbon comprises and is lower than about 70 carbon atoms/each molecule and preferred, is lower than about 20 carbon atoms/each molecule, gets and uses easily because low-molecular weight compound is commercial.The reaction product that most preferred hydrocarbon compound is to use this catalyst system to form.For example, if the 1-hexene is a reaction product, some 1-hexene product is recyclable as reaction medium.
Consideration includes, but is not limited to as the example of the unsaturated aliphatic hydrocarbon compound of reaction medium, ethene, and the 1-hexene, 1,3-butadiene, and composition thereof.The example that can be used as the unsaturated aromatic hydrocarbon of reaction medium includes, but is not limited to, benzene, and toluene, ethylbenzene, dimethylbenzene, mesitylene, hexamethyl-benzene, and composition thereof.Unsaturated aromatic hydrocarbon is preferably with the stability that improves catalyst system and produce high activity and catalyst system optionally.For the catalyst system activity and the selectivity of product of the best, most preferred unsaturated aromatic hydrocarbon is an ethylbenzene.
The trimerization reaction process is generally carried out in the slurry of catalyst component in inert media or thinner.Broadly, common trimerization reaction thinner can be whiteruss, naphthenic hydrocarbon, alkene or aromatic hydrocarbons.The example of reactor dilution agent includes, but is not limited to, Trimethylmethane, hexanaphthene, and methylcyclohexane.Trimethylmethane can be used for strengthening the consistency with known olefin polymerization process.But easier being dispersed in the hexanaphthene of homogeneous phase catalyst for trimerization system.Therefore, the thinner that is preferred for the trimerization reaction process of homogeneous catalysis is a hexanaphthene.
According to another embodiment of the present invention, slurry process can carry out in thinner (medium), and the latter is the product of olefin oligomerization process.Therefore, the selection of reactor dilution agent or medium is based on the selection to the starting olefin reactant.For example, if use oligomerization that ethylene trimerization is become the 1-hexene, the solvent that is used for this oligomerization is the 1-hexene.If ethene and hexene trimerization generate 1-decene, the oligomerization solvent is a 1-decene.If the 1,3-butadiene trimerization becomes 1, the 5-cyclooctadiene, trimerization reaction device solvent is 1, the 5-cyclooctadiene.
Comprise the chromium source, comprise pyrroles's compound, the catalyst system of metal alkylide and reaction medium can comprise other component that has no adverse effect and can strengthen the gained catalyst system, for example, and halogenide.
Equipment
Trimerization reaction can preferably have fluid chuck or interior heat transfer coiled pipe and suitable whipping appts aptly in suitable reactors, for example carries out in the continuous charging autoclave reactor of mechanical stirring or rare gas element (nitrogen usually), washing unit, pipeline and valve.Can use any other suitable reactions equipment.For example, can use to have mechanical stirring, for example stir the loop reactor of pump.
Reaction conditions
Ding Yi trimerization reaction product can use conventional equipment and contact process by disperseing reaction, slurry reaction or gas-phase reaction technology in this manual, is made by catalyst system of the present invention.One or more monomers can be undertaken by any way known in the art with contacting of catalyst system.A kind of technology of routine is to be suspended in catalyst system in the reaction medium and to stir this mixture to keep the dispersion of catalyst system in whole trimerization reaction process.Also can use other known contact process.
Usually, the continuous or one or many adding reactor of catalyst system and reaction medium, and olefin reactant adds as gas under pressure in reaction process continuously or intermittently.Pressure in the reactor keeps with the alkene that the replacement reaction is consumed by add the gaseous olefin reactant under appropriate speed usually.
Hydrogen can add reactor to improve the speed of reacting and to strengthen the active and trimer product selectivity of catalyst system in reaction process.The existence of hydrogen can be advantageously used in by-product polymer is reduced into powdery, non-viscous forms, so for example by filtering and/or evaporation and remove from reactor easily and separate from overflow easily.
The dividing potential drop of existing hydrogen is generally the about 100kg/cm of about 0.1-
2(about 1-1000N/cm
2), the about 80kg/cm of preferably about 0.1-
2(about 1-800N/cm
2).
Used temperature of reaction can be to make any temperature of olefin reactant trimeric.In general, temperature of reaction be about 0 ℃-Yue 250 ℃ preferred, adopt about 60 ℃-Yue 200 ℃ and most preferably from about 80 ℃-Yue 150 ℃ temperature of reaction.If reactant mainly is an ethene, generally can adopt about 0 ℃-Yue 300 ℃ temperature.Preferably, if reactant mainly is an ethene, adopt about 60 ℃-Yue 110 ℃ temperature.If temperature of reaction is too low, polymkeric substance often adheres on the reactor surface.If temperature of reaction is too high, catalyst system and reaction product may be decomposed.
Used total reaction pressure can be to make any pressure of olefin reactant trimeric.In general, reaction pressure is about normal atmosphere (0psig or 0N/cm
2Gauge pressure)-Yue 2500psig (about 1700N/cm
2Gauge pressure).Preferably, adopt about normal atmosphere-Yue 1000psig (690N/cm
2Gauge pressure) and most preferably 300-900psig (the about 620N/cm of about 200-
2Gauge pressure) reaction pressure.If reaction pressure is too low, catalyst system is active can be too low.Peak pressure is generally determined by security consideration with to the demand that wall is not thicker than required container.
The content of reactor can pass through rare gas element (as nitrogen) and clean, by adding reactant in a kind of mode of stirring that causes, and hydrogen, fluid medium, or the catalyzer or the overflow of finding time by machinery or magnetic agitation, or stir with any other suitable manner.
Reaction is usually by stably adding rudimentary 1-olefin reactant, and catalyst system and processing medium are also removed the liquid contents of reactor and carried out continuously.For example, can use a kind of continuously stirring formula jar reactor system, comprise being used for catalyst system, the reinforced system of reactant and medium and the discharging system that is used for overflow.But can use batch technology.
Reactor overflow is by handling to kill the residuum of catalyst system, and separated product makes the component recirculation of Residual reactants, medium and other suitable recirculation, and removes the no longer any component of round-robin.
Trimerization reaction generates heat, so temperature of reaction can be transferred to heat outside the reactor like this by regulating through chuck or heat transfer coiled pipe cooling water circulation usually.Importantly heat can be transferred to outside the reactor effectively, reactor can remain under the desired reaction temperature and heat can be used minimum heat-eliminating medium and removes effectively like this.Another advantage of more effective heat transfer is that trimerization reaction can improve productivity like this to carrying out under the fixed temperature under higher output.
After catalyst system has been used to prepare one or more olefin products, to comprise the alkene trimer product, catalyst system kills agent with the reactor overflow logistics and the catalyzer of some polymkeric substance or higher oligomers by product and contacts with " killing ", this catalyzer of deactivation or cancellation.It is alcohol that the exemplary catalyst that this paper considers is killed agent, uncle or secondary amine, or alkanolamine.
Can use any alcohol that can be dispersed in easily in the reactor overflow logistics to kill agent as catalyzer.For example, lower alcohol such as methyl alcohol, ethanol, propyl alcohol, Virahol waits and can kill catalyst system.But preferably, the boiling point of selected alcohol or molecular weight make this alcohol not form azeotrope with the olefinic monomer product.In general, the easier formation azeotrope of material that has similar boiling point and similar molecular weight.
One wherein catalyst system be used for ethylene trimerization is become the illustrative processes of 1-hexene, the monofunctional alcohol with 6 or more carbon atom/per molecules is preferably catalyzer and kills agent.Most preferably, the monofunctional alcohol with 6-12 carbon atom/per molecule is used for best catalyst system cancellation.These alcohol can be removed from 1-hexene olefin product easily.The example of monofunctional alcohol includes, but is not limited to the 1-hexanol; The 2-hexanol; The 3-hexanol; 2-ethyl-1-hexanol; The 3-octanol; The 1-enanthol; The 2-enanthol; The 3-enanthol; The 4-enanthol; 2-methyl-3-enanthol; The 1-octanol; Sec-n-octyl alcohol; The 3-octanol; The 4-octanol; 7-methyl-2-decyl alcohol; 1-decanol; The 2-decyl alcohol; The 3-decyl alcohol; The 4-decyl alcohol; The 5-decyl alcohol; 2-ethyl-1-decanol; And composition thereof.
In addition, can use low molecular weight diols or polyvalent alcohol, for example ethylene glycol kills agent as catalyzer.Two pure and mild polyvalent alcohols have usually than the obvious higher boiling point of the suitable monohydroxy-alcohol of molecular weight, separate from the 1-hexene therefore easilier.
Alcohol is so that the small part amount use of cancellation catalyzer effectively.For example, alcohol, relatively the metal content of the catalyzer of the deactivation of wanting is can about 0.01-about 100, and preferably about 0.01-is about 10, the most preferably from about mol ratio of 0.05-about 2 adding.
If alcohol kills agent as the catalyzer of halogenation catalyst system, can produce hydrogen halide as mentioned above.The practitioner who makes higher alkene selects to avoid or reduce the generation hydrogen halide usually.The hydrogen halide problem can be by forming stable halogenide or this product logistics of stabilization mass treatment of halogenation hydrogen salt solves with a kind of.
The stabilization material that this paper considers can be an aliphatic amine, aromatic amine, the metal-salt of acid amides, the metal-salt of butanolate, the metal-salt of carboxylic acid, or the combination of these materials.More particularly, the stabilization material among the present invention can be selected from ring-type and acyclic, aromatics and aliphatic amine, and nitrile, acid amides, etc.
Consider to comprise ethylamine as the primary amine of stabilization material; Isopropylamine; Cyclo-hexylamine; Benzyl amine; ALPHA-NAPHTHYL AMINE; With other amine.Secondary amine comprises diethylamide; Diisopropylamine; Dibutylamine; Dicyclohexylamine; Dibenzyl amine and two (trimethyl silyl) amine.The stabilization material can be tertiary amine such as tributylamine.
This paper considers to comprise aniline as the ring of stabilization material and aromatic amine and related compound; Pyridine; Lutidine; Morpholine; Imidazoles; Indoline; Indoles; The pyrroles; 2, the 5-dimethyl pyrrole; 3, the 4-dimethyl pyrrole; 3,4-dichloro pyrroles; 2,3,4,5-tetrachloro pyrroles; The 2-acetyl pyrrole; Pyrazoles; Tetramethyleneimine; Pyrrolidone and dipyrryl methane.
The stabilization material that this paper considers can be an alkanolamine.A special benefits of alkanolamine is to have carbinol-functional degree and amine functionality simultaneously with a part, this can be used for deactivation simultaneously or kill catalyst system and stabilization in case generate hydrogen halide.The example of alkanolamine comprises Yi Bingchunan, monoethanolamine, diethanolamine, and trolamine.
The stabilization material that this paper considers also comprises polyamine.The example of polyamine is a quadrol, diethylenetriamine, and Tetramethyl Ethylene Diamine.
Can be in the present invention comprise with the metal-salt of the acid amides of used as stabilizers, for example, dimethyl formamide; The N-methylformamide; Ethanamide; N-methyl hexane acid amides; Succinic diamide; Maleinamide; N-methyl-benzamide; Imidazoles-2-methane amide; Two-2-thiophenine; Beta-lactam; δ-lactan, or ε-lactan and periodictable IA, the salt of IIA or IIIB family metal.The example of these metal amides is lithium acid amides; The sodium buserelin; The calcium diethylamide; The lithium diisopropylamide; Potassium benzyl acid amides; Sodium two (trimethyl silyl) acid amides; The indoles lithium; Pyrroles's sodium; Pyrroles's lithium; Pyrroles's potassium; Tetramethyleneimine potassium; Diethyl pyrroles aluminium; Ethyl two pyrroles's aluminium; Tripyrrole aluminium; 2,5-dimethyl pyrrole sodium; 2,5-dimethyl pyrrole lithium; 2,5-dimethyl pyrrole potassium; 2,5-dimethyl pyrrole potassium; Diethyl aluminum; 2,5-dimethyl pyrrole thing; Aluminium triethyl; Two (2,5-dimethyl pyrrole thing); Three (2, the 5-dimethyl pyrrole) aluminium, and combination.
Can be in the present invention comprise 1,2-hexanaphthene dicarboximide, succinimide, phthalic imidine, maleimide, 2,4,6-piperidines triketone and perhydro azesine-2,10-diketone with the imide of used as stabilizers.
The metal-salt that can be used for the butanolate of this paper is alkali-metal butanolate (further describing).An exemplary butanolate is a potassium tert.-butoxide.
Can be in this article comprise the metal-salt of carboxylic acid, more specifically lithium, sodium, potassium and/or rubidium salt with the metal-salt of the carboxylic acid of used as stabilizers.The example of carboxylic acid comprises acetate, propionic acid, and butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, phenylformic acid, phenylacetic acid, phthalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, vinylformic acid, toxilic acid, fumaric acid, and Whitfield's ointment.The exemplary carboxylic acids that this paper considers is a silver acetate, lithium acetate, sodium acetate, potassium acetate and composition thereof.
Can be in this article comprise tributylphosphine oxide and triethyl phosphine oxide with the exemplary phosphine of used as stabilizers.
The stabilization material should provide with the amount that has at least the minimizing of imitating to produce hydrogen halide.For example, can add about 100 moles of about 0.01-, about 10 moles of preferably about 0.01-, the more preferably halogen in the stabilization material of 0.05-2 mole/every mol catalyst.
The use of alcohol is to cancellation or to kill catalyzer dispensable.Other material, for example uncle or secondary amine can be used to kill catalyzer separately or with one or more pure combinations.In general, aliphatic primary amine, aliphatic secondary amine, or the combination of these materials can be considered to kill agent as catalyzer.More particularly, amine can be no cycloaliphatic amine or cycloaliphatic amine, all within the scope of the present invention.
As for alcohol, amine cancellation material can be separately or with alcohol or other quencher with at least basically effectively the amount of this catalyzer of cancellation provide.
Enough catalyzer are killed agent add in the reactor overflow logistics, deactivation, or " killing " this olefin production catalyst system and reduce or eliminate and produce non-required solid, especially polymkeric substance or catalyst solid with cancellation at least basically.If use catalyzer in shortage to kill agent, any metal in this catalyst system is as chromium or the precipitable overflow processing later with interference of aluminium.In general, the catalyzer that can add the highest about 5 molar equivalents kills the metal in the overflow logistics of agent/every mole.Preferably, the catalyzer add-on of the killing agent add-on of killing agent for about 1-4 molar equivalent and most preferred catalysts is that about 2-3 molar equivalent catalyzer kills the metal in the overflow logistics of agent/every mole.Too many catalyzer kills the corrosion that agent can cause reactor.
Catalyst system by cancellation and processing so that after any halogenide stabilization, can remove olefin product, for example, the 1-hexene.
Can use any removal technology, but distillation is preferred because of using easily.
In simple distillation, ethene is removed from reaction product, then 1-hexene and medium are distilled from the reaction dispersion, simultaneously catalyst component is concentrated and reclaim with the by product polyethylene.Distillation temperature in the still kettle is generally about 190 ℃-Yue 210 ℃.These distillation temperatures it is believed that the aluminum halide that is enough to promote to be present in the spent catalyst decomposes, unless take steps in case produce hydrogen halide according to present disclosure is described.
The concentrated dispersion that comprises by-product polymer and catalyst component can be drained, or can further processing as described below.
The product logistics that the ethylene trimerization reaction process forms comprises one or more following compounds usually: butylene; The 1-hexene; Interior hexene (being 2-hexene or 3-hexene); Octene; Decene; Reaction medium; With " last running ".
Can be by removing the waste stream that required olefinic monomer product forms by its contact alkaline solution being removed metal and further handling.Organic bases this moment is not preferred, can not precipitation of heavy metals because organic bases is too weak, and as chromium.Preferred inorganic aqueous base is sodium hydroxide and potassium hydroxide, because their easy uses can get, cost is low and to the beneficial effect with aftertreatment.
The add-on of inorganic aqueous base can be any amount that is enough to precipitate great majority or all basically chromium.The most important target of this step and removal chromium or other heavy metal be not because any remaining dispersion aluminium can produce identical environmental problem.
Add too much or inorganic aqueous base very little can prevent the precipitation of chromium.In general, every mole of chromium and aluminium should use the inorganic aqueous base of the highest about 4 molar equivalents.Preferably, every mole of chromium and aluminium should use about 3 molar equivalents of about 0.2-and the inorganic aqueous base of 1-2 molar equivalent most preferably from about.The solid sediment that contains chromium can be removed subsequently and suitably handle.
After removal contains the solid sediment of chromium, separate waterbearing stratum or part and organic layer or part.Organic layer can be handled.
Remove resistates
Trimerization reaction technology produces two kinds of resistatess that can be deposited on the reactor internal surface usually.
A kind of resistates that is deposited on the reactor wall that is identified for a long time is to be higher than as the chain length that by product forms to expect the oligopolymer or the polymkeric substance of product.For simplicity, this higher oligomers or polymer residues only are called " polymer residues " at this.For example, under the situation of ethylene reaction, polyethylene or paraffin residues can form and be deposited on the reactor internal surface.This polymer residues has been damaged the heat transfer efficiency of reactor internal surface.
Polymer residues can be by removing from reactor with the solvent wash reactor of this resistates.The trimerization reaction device is usually supplied with the solvent that is useful on by-product polymer-as hexanaphthene or methylcyclohexane-as processing medium.If use polymer solvent as processing medium, can use identical processing medium to come this reactor of routine cleaning.Wash conditions can be harsher than common process condition, removes not removed polymer residues under the common process condition like this.For example, this washing step can be " heat is washed ", by being higher than under the temperature of technological temperature this common process medium of circulation with fusing, quicker dissolving or otherwise move this polymer residues and carry out.
In successive ethylene trimerization reaction process, heat is washed and can followingly be carried out.Reaction can be by stopping to add catalyzer and reactant, injects continuously simultaneously and discharge to be the reactor media of (but being not limited to) hexanaphthene and/or methylcyclohexane and medium temperature raise about 60-70 ℃ and stop.Heat is washed lasting several hrs, or as required to remove all or all basically polymer residues.Have been found that this heat washes the accumulation that can remove polymer residues.
Second resistates is the heat transfer efficiency of obvious damage reactor also, is called relict catalyst in this article.It is not known that the precise chemical structure of this relict catalyst is formed.Combination or some other material of the product that it can be between the throw out of whole catalyzer or one or more catalyst components or settling, the catalyst component, react between catalyzer and the reactor wall, spent catalyst composition, these resistatess.This resistates it is believed that relevant with catalyzer, but the invention is not restricted to this theoretical exactness.
By reference following examples, can further understand how to realize and use the present invention and advantage thereof.
Embodiment
Embodiment 1
In 1 liter of 3 neck flask being furnished with nitrogen wash unit, magnetic stirring apparatus, glass column, Dean-Stark pipe and condenser of inert gas purge, add 250 milliliters of anhydrous dodecanes and 260 milliliters of 2-ethyl-1-hexanols.This system was cleaned once more 20 minutes and was added 50 milliliters selectivity 1-hexene catalyzer (5mgCr/ milliliter).Add entry (2 milliliters) and this system is heated to backflow.In 5 hours, get 9 samples.Acidity is also tested this water with pH paper by extraction from the water of the sample of Dean Stark pipe and is estimated.First sample is slightly acidic, and other all samples is unusual tart.Observe in the end and have water in the sample.
Embodiment 2
Repeat embodiment 1, but, also add 4 milliliters of tri-n-butyl amines except 2 ml waters.None is a tart from 9 samples subsequently of Dean-Stark pipe, has shown the validity that amine is added this technology.In the 9th sample, observe water, as the observations of embodiment 1.All acidity signs have been removed in the existence of amine.
The experimental installation that is used for embodiment 3 and 4
The experimental installation that is used for embodiment 3 and 4 is be furnished with to be used for the 1 liter 3 neck round-bottomed flask of thermopair with glass well, feed hopper and the Dean-Stark pipe of monitoring still temperature.Condenser is placed on the top of Dean-Stark pipe, as the line that is used to measure the thermopair of head temperature and be used for pH paper is fixed on Dean-Stark pipe top.This flask also is furnished with magnetic stirring bar and agitator and heating jacket.Nitrogen stream purges material consistently by this device and the aqueous bubbler of bag.
The general step that is used for embodiment 3 and 4
In model experiment, 200 gram dodecanes are added in the flasks and with this system of nitrogen purge.Subsequently the diethyl aluminum chloride (DEAC) in dodecane (1.9M) is added in the flask by the metal graduated cylinder.Slowly add the 2-ethyl-1-hexanol of aequum subsequently and react.Temperature rises to about 50-70 ℃ and observe gas release.With contents stirred 30 minutes with complete reaction and to this still sampling.This content postheating is to refluxing.Remove the top overhead product as required to obtain required still temperature.Regularly by the Dean-Stark pipe to top overhead product sampling (about 2 milliliters).
Embodiment 3
Following material is added in the said apparatus: slowly add the anhydrous dodecane of 200 grams, the DEAC of 80.8 milliliters of 1.9M solution and 96 milliliters of 2-ethyl-1-hexanols in dodecane.This mixture at 2.75 hours internal heating to 170 ℃-209 ℃ of still temperature.Carry out following observation.Soon, the color of the pH paper at Dean-Stark pipe top and the pH of water bubbler do not change after adding alcohol.By heating, the pH paper in the Dean-Stark pipe becomes red-violet colour (strongly-acid).Obtain representing the wet pH paper of acidity from the sample of Dean-Stark pipe bottom, and be male with the muriate experiment that silver acetate carries out.Obviously there is acidic hydrogen chloric acid.
Embodiment 4
Following material is added in the said apparatus: slowly add the anhydrous dodecane of 200 grams, the DEAC of 81 milliliters of 1.9M solution and 96 milliliters of 2-ethyl-1-hexanols in dodecane.Add this mixture of tri-n-butyl amine (40.25 gram) at 4 hours internal heating to 208 ℃ of still temperature.Carry out following observation.In whole experiment, the color of the pH paper at Dean-Stark pipe top does not change.The pH of water bubbler is a neutral when experiment finishes.Sample from Dean-Stark pipe bottom is a neutral or subalkaline, shows as wet pH paper.Obviously, formed any acid is removed from system by adding amine.
Although described the present invention in detail, should not be construed as and limited to by this, but mean all changes and the modification that is included in its purport and the scope to describe.
Claims (35)
1. oligomerization process comprises:
A) provide at least a catalyst system, at least a light alkene and at least a processing medium;
B) described light alkene is reacted in the presence of described catalyst system, generate the product logistics that comprises higher olefin product and be dispersed in the catalyst system resistates in the described processing medium;
C) with a kind of described product logistics of cancellation mass treatment that comprises the combination of aliphatic primary amine, aliphatic secondary amine, aliphatic tertiary amine or these materials, the amount of effective described catalyst system of cancellation provides described cancellation material so that lack basically.
2. according to the technology of claim 1, wherein said cancellation material comprises no cycloaliphatic amine.
3. according to the technology of claim 1, wherein said cancellation material comprises cyclic aliphatic amine.
4. according to the technology of claim 1, wherein said cancellation material comprises primary amine.
5. according to the technology of claim 1, wherein said cancellation material comprises secondary amine.
6. according to the technology of claim 1, wherein said cancellation material comprises cyclo-hexylamine.
7. according to the technology of claim 1, wherein said cancellation material comprises dibutylamine.
8. according to the technology of claim 1, wherein said cancellation material comprises alkanolamine.
9. according to the technology of claim 1, wherein said cancellation material comprises isopropylamine.
10. according to the technology of claim 1, wherein said cancellation material comprises monoethanolamine.
11. according to the technology of claim 1, wherein said cancellation material comprises diethanolamine.
12. according to the technology of claim 1, wherein said cancellation material can separate from described higher alkene by distillation.
13. according to the technology of claim 1, wherein said cancellation material also comprises alcohol.
14. according to the technology of claim 1, wherein said cancellation material adds with the mol ratio of the about 1-5 of described relatively catalyst metal content.
15. an oligomerization process comprises:
A) provide halogenation catalyst system, light alkene and processing medium;
B) described light alkene is reacted in the presence of described catalyst system, generate the product logistics that comprises higher olefin product and be dispersed in the catalyst system resistates in the described processing medium;
C) with a kind of its amount can be effectively to the alcohol of the described catalyst system of small part cancellation handle described product logistics and
D) with a kind of described product logistics of stabilization mass treatment that can form the stabilisation of halogenated hydrogen salt, described stabilization material provides to reduce the amount that produces hydrogen halide effectively.
16. according to the technology of claim 15, wherein said stabilization material is selected from the metal-salt of aliphatic amine, aromatic amine, acid amides, the metal-salt of butanolate, the metal-salt of carboxylic acid or the combination of these materials.
17. according to the technology of claim 15, wherein said stabilization material comprises no cycloaliphatic amine.
18. according to the technology of claim 15, wherein said stabilization material comprises cyclic aliphatic amine.
19. according to the technology of claim 15, wherein said stabilization material comprises aromatic amine.
20. according to the technology of claim 15, wherein said stabilization material comprises primary amine.
21. according to the technology of claim 15, wherein said stabilization material comprises secondary amine.
22. according to the technology of claim 15, wherein said stabilization material comprises tertiary amine.
23. according to the technology of claim 15, wherein said stabilization material comprises alkanolamine.
24. according to the technology of claim 15, wherein said stabilization material comprises isopropylamine.
25. according to the technology of claim 15, wherein said stabilization material comprises monoethanolamine.
26. according to the technology of claim 15, wherein said stabilization material comprises diethanolamine.
27. according to the technology of claim 15, wherein said stabilization material comprises cyclo-hexylamine.
28. according to the technology of claim 15, wherein said stabilization material comprises dibutylamine.
29. according to the technology of claim 15, wherein said stabilization material comprises tributylamine.
30. according to the technology of claim 15, wherein said stabilization material comprises quadrol.
31. according to the technology of claim 15, wherein said alcohol has at least 6 carbon atoms/each molecule.
32. according to the technology of claim 15, wherein said pure and mild described stabilization material can separate from described higher alkene by distillation.
33. according to the technology of claim 15, wherein said alcohol is 2-Ethylhexyl Alcohol.
34. according to the technology of claim 15, wherein said alcohol adds with the mol ratio of the about 0.01-100 of described relatively catalyst metal content.
35. according to the technology of claim 15, wherein said stabilization material adds with the mol ratio of the about 0.01-100 of described relatively catalyst metal content.
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| US47368899A | 1999-12-29 | 1999-12-29 | |
| US09/473,688 | 1999-12-29 |
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| CN00816222A Pending CN1399620A (en) | 1999-12-29 | 2000-12-27 | Processes for preventing generation of hydrogen halides in oligomerization product recovery system |
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| EP (1) | EP1242341A4 (en) |
| CN (1) | CN1399620A (en) |
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| CN108025996A (en) * | 2015-09-16 | 2018-05-11 | 沙特基础工业全球技术有限公司 | Method for the inactivation of olefin oligomerization catalyst |
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| TW200502038A (en) * | 2003-03-14 | 2005-01-16 | Chevron Phillips Chemical Co | Process to decrease or eliminate corrosion from the decomposition of halide containing olefin catalysts |
| US20050187418A1 (en) | 2004-02-19 | 2005-08-25 | Small Brooke L. | Olefin oligomerization |
| US20050187098A1 (en) | 2004-02-20 | 2005-08-25 | Knudsen Ronald D. | Methods of preparation of an olefin oligomerization catalyst |
| US20070043181A1 (en) | 2005-08-19 | 2007-02-22 | Knudsen Ronald D | Methods of preparation of an olefin oligomerization catalyst |
| US7384886B2 (en) | 2004-02-20 | 2008-06-10 | 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 |
| US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
| MY156865A (en) | 2008-01-30 | 2016-04-15 | Linde Ag | Method for preparing linear alpha-olefins |
| KR101642164B1 (en) | 2008-10-31 | 2016-07-22 | 셰브론 필립스 케미컬 컴퍼니 엘피 | Compositions and catalyst systems of metal precursors and olefinic diluents |
| EP2287142B1 (en) * | 2009-07-24 | 2013-11-06 | Linde AG | Method for preparing linear alpha-olefins |
| RU2471762C1 (en) | 2011-06-22 | 2013-01-10 | Открытое акционерное общество "СИБУР Холдинг" (ОАО "СИБУР Холдинг") | Method of extracting products of oligomerisation of olefins and decomposition of oligomerisation catalyst residues |
| US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
| DK3237364T3 (en) | 2014-12-23 | 2019-05-13 | Sibur Holding Public Joint Stock Co | PROCEDURE FOR PRECIPIATING POLYMS AND DEACTIVATED ORGANOMETAL CATALYST IN AN OLEFIN OLIGOMERIZATION REACTION |
| WO2017010998A1 (en) | 2015-07-14 | 2017-01-19 | Chevron Phillips Chemical Company Lp | Olefin compositions |
| US9505011B1 (en) | 2015-12-28 | 2016-11-29 | Chevron Phillips Chemical Company Lp | Mixed decyl mercaptans compositions and use thereof as mining chemical collectors |
| US9512071B1 (en) | 2015-12-28 | 2016-12-06 | Chevron Phillips Chemical Company Lp | Mixed decyl mercaptans compositions and methods of making same |
| US10011564B2 (en) | 2015-12-28 | 2018-07-03 | Chevron Phillips Chemical Company Lp | Mixed decyl mercaptans compositions and methods of making same |
| US9512248B1 (en) | 2015-12-28 | 2016-12-06 | Chevron Phillips Chemical Company Lp | Mixed decyl mercaptans compositions and use thereof as chain transfer agents |
| US10294200B2 (en) | 2015-12-28 | 2019-05-21 | Chevron Phillips Chemical Company, Lp | Mixed branched eicosyl polysulfide 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 |
| US11472756B2 (en) * | 2016-12-19 | 2022-10-18 | Sabic Global Technologies B.V. | Method of separating linear alpha olefins |
| FR3103485B1 (en) * | 2019-11-26 | 2023-03-24 | Ifp Energies Now | Process for separating an effluent from an oligomerization step |
| FR3103486A1 (en) * | 2019-11-26 | 2021-05-28 | IFP Energies Nouvelles | PROCESS FOR NEUTRALIZING A CATALYTIC COMPOSITION CONTAINED IN AN EFFLUENT FROM AN OLIGOMERIZATION STAGE |
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| US4486615A (en) * | 1960-09-14 | 1984-12-04 | Exxon Research & Engineering Co. | Preparation of linear olefin products |
| FR2581381B1 (en) * | 1985-05-02 | 1987-07-10 | Inst Francais Du Petrole | PROCESS FOR PRODUCING IMPROVED PURITY BUTENE-1 FROM THE CRUDE ETHYLENE DIMENSION PRODUCT |
| DE3675385D1 (en) * | 1986-04-17 | 1990-12-06 | Idemitsu Petrochemical Co | METHOD FOR PRODUCING LINEAR ALPHA OLEFINS. |
| SU1662996A1 (en) * | 1987-07-13 | 1991-07-15 | Отделение Института химической физики АН СССР | Method of producing butene-1 |
| FR2715154B1 (en) * | 1994-01-14 | 1996-04-05 | Inst Francais Du Petrole | Process for the production of light alpha olefins of improved purity by oligomerization of ethylene. |
| CA2134503C (en) * | 1994-02-18 | 2001-04-10 | Mark E. Lashier | Olefin production |
| FR2759922B1 (en) * | 1997-02-25 | 1999-05-07 | Inst Francais Du Petrole | IMPROVED CATALYTIC COMPOSITION FOR THE CONVERSION OF ETHYLENE TO LIGHT ALPHA OLEFINS |
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| CN108025996A (en) * | 2015-09-16 | 2018-05-11 | 沙特基础工业全球技术有限公司 | Method for the inactivation of olefin oligomerization catalyst |
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| WO2001047839A1 (en) | 2001-07-05 |
| AU773364B2 (en) | 2004-05-20 |
| AU2600601A (en) | 2001-07-09 |
| EP1242341A4 (en) | 2004-11-03 |
| CA2392233C (en) | 2006-10-24 |
| CA2392233A1 (en) | 2001-07-05 |
| EP1242341A1 (en) | 2002-09-25 |
| RU2249585C2 (en) | 2005-04-10 |
| ZA200203457B (en) | 2003-10-29 |
| MXPA02005399A (en) | 2002-12-05 |
| GC0000217A (en) | 2006-03-29 |
| RU2002120493A (en) | 2004-01-10 |
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