Deactivation of Oligomerization Catalyst Systems and Related Ethylene Oligomerization Processes

Abstract

The catalyst system is 18 A method for deactivating a transition metal-based catalyst system containing a cocatalyst comprising an aluminoxane and, optionally, an alkylaluminum, is disclosed, which comprises contacting the cocatalyst with an alcohol-based cocatalyst deactivator in an amount ranging from 0.5 to 1.5 times the moles of OH of the cocatalyst deactivator: (moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum). Related methods for deactivating residual catalyst systems in reactor effluent streams and related ethylene oligomerization processes are also described.

Description

[Technical Field]

[0001] REFERENCE TO RELATED APPLICATIONS This application was filed as a PCT international patent application on November 10, 2023, and claims the benefit of and priority to U.S. patent application Ser. No. 18 / 054,934, filed on November 14, 2022, the disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE DISCLOSURE This disclosure relates generally to methods for deactivating catalyst systems, and more particularly to deactivating catalyst systems containing aluminoxane and alkylaluminum cocatalysts.

[0003] A variety of multicomponent catalyst systems exist that are suitable for the oligomerization of ethylene to produce 1-hexene or 1-octene. Once the oligomeric products are formed in the oligomerization reactor and subsequently discharged, it is often desirable to deactivate the catalyst system to prevent further oligomerization of the ethylene and to prevent isomerization of the 1-hexene or 1-octene product. The present invention is generally directed to these ends.

[0004] This Summary is provided to introduce a selection of concepts in a simplified form that are further described herein. This Summary is not intended to identify necessary or essential features of the claimed subject matter, nor is this Summary intended to be used to limit the scope of the claimed subject matter.

[0005] Described herein are methods for deactivating catalyst systems. In one aspect, a method for deactivating a transition metal-based catalyst system comprising a cocatalyst, for example, an aluminoxane and optionally an alkylaluminum, is provided by deactivating the catalyst system with a C4-C hydroxybenzoate in a range of 0.5 to 1.5 times the moles of OH of the cocatalyst deactivator: (moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum). 18This may include contacting with an alcohol-based cocatalyst deactivator.

[0006] Another method is directed to deactivating a residual transition metal-based catalyst system containing a cocatalyst comprising an aluminoxane and optionally an alkylaluminum in an effluent stream from an oligomerization reactor. The method comprises deactivating an effluent stream comprising unreacted ethylene, oligomer product, a residual transition metal-based catalyst system containing a cocatalyst comprising an aluminoxane and optionally an alkylaluminum, and an organic reaction medium with a C4-C olefin copolymer in a range of 0.5 to 1.5 times the moles of OH of the cocatalyst deactivator: {(moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum)}. 18 This may include contacting with an alcohol-based cocatalyst deactivator.

[0007] Also described herein are oligomerization processes. A representative process includes: A) introducing ethylene, a transition metal-based catalyst system or catalyst system components, an organic reaction medium, and optionally hydrogen into an oligomerization reactor, where the transition metal-based catalyst system or catalyst system components include a cocatalyst comprising an aluminoxane and optionally an alkyl aluminum; B) forming oligomer products in the oligomerization reactor, where the oligomer products include hexene and octene; C) discharging an effluent stream from the oligomerization reactor, where the effluent stream includes unreacted ethylene, oligomer products, residual transition metal-based catalyst system (including aluminoxane and optionally an alkyl aluminum cocatalyst), and the organic reaction medium; and D) reacting a C4-C6 18 The method may include contacting the effluent stream with an alcohol-based co-catalyst deactivator in an amount in the range of 0.5 to 1.5 times the number of OH moles of the co-catalyst deactivator: {(number of aluminum moles of the aluminoxane) + (number of aluminum moles of the alkylaluminum) + (number of aluminum moles of the alkylaluminum)}.

[0008] Both the foregoing general description and the following detailed description provide examples and are explanatory only. Accordingly, the foregoing general description and the following detailed description should not be considered limiting. Furthermore, features or variations may be provided in addition to those described herein. For example, certain aspects may be directed to combinations and subcombinations of various features described in the detailed description. [Brief explanation of the drawings]

[0009] [Figure 1] 1 shows gas chromatograph plots of oligomerization experiments of Examples 1-5.

[0010] definition The following definitions are provided to more clearly define the terms used herein. Unless otherwise stated, the following definitions apply to this disclosure. When a term is used in this disclosure and not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) may be applied, unless the definition applied contradicts any other disclosure or definition applicable herein or would obscure or disable any patent claim to which the definition applies. In the event that any definition or usage provided by any document incorporated by reference herein contradicts a definition or usage provided herein, the definition or usage provided herein shall control.

[0011] Features of the subject matter may be described herein such that, in certain aspects, combinations of different features may be envisioned. For any and all aspects and / or features disclosed herein, all combinations that do not adversely affect the designs, compositions, processes, and / or methods described herein are contemplated, regardless of whether a specific combination is explicitly recited. Additionally, unless expressly stated otherwise, any aspects and / or features disclosed herein may be combined to describe inventive features consistent with the present disclosure.

[0012] In this disclosure, compositions, processes / methods, and systems are described in terms of "comprising" various materials, steps, and components; however, the compositions, processes / methods, and systems can also "consist essentially of" or "consist of" the various materials, steps, or components unless otherwise specified. The words "a," "an," and "the" are intended to include plural alternatives, e.g., at least one, unless otherwise specified.

[0013] Generally, groups of elements are designated using the numbering system set forth in the version of the Periodic Table of the Elements published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, groups of elements may be designated using the common name assigned to the group, e.g., alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Groups 3-12 elements, and halogens or halides for Group 17 elements.

[0014] For any particular compound or group disclosed herein, any presented name or structure is intended to encompass all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that may result from a particular set of substituents, unless otherwise specified. The name or structure also encompasses all enantiomers, diastereomers, and other optical isomers (if present), as well as mixtures of stereoisomers, whether in enantiomeric or racemic form, as recognized by those of skill in the art, unless otherwise specified. For example, a general reference to hexene (or hexenes) includes all linear or branched, acyclic or cyclic hydrocarbon compounds having six carbon atoms and one carbon-carbon double bond; a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and a general reference to a butyl group includes n-butyl, sec-butyl, isobutyl, and t-butyl groups.

[0015] As used herein, the terms "contact" and "bond," unless otherwise specified, are used to describe compositions, processes / methods, and systems in which materials are contacted or bonded together in any order, in any manner, and for any length of time. For example, substances may be blended, mixed, slurried, dissolved, reacted, treated, impregnated, compounded, or contacted or combined in some other manner or by any suitable method or technique.

[0016] Whenever used in this specification and claims, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of specific groups in the hydrocarbon (e.g., a halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equivalent number of hydrogen atoms in the hydrocarbon).

[0017] The term "olefin," whenever used in this specification and claims, refers to a hydrocarbon having at least one carbon-carbon double bond that is not part of an aromatic ring or aromatic ring system. Unless otherwise specified, the term "olefin" includes aliphatic and aromatic, cyclic and acyclic, and / or straight-chain and branched hydrocarbons having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Olefins having only one, two, three, etc. carbon-carbon double bonds may be identified by using terms such as "mono," "di," "tri," etc. in the name of the olefin. Olefins may be further distinguished by the position of the carbon-carbon double bond(s).

[0018] As used herein, the term "α-olefin" refers to any olefin having a carbon-carbon double bond between the first and second carbon atoms in the longest continuous chain of carbon atoms. Unless otherwise specified, the term "α-olefin" includes linear and branched α-olefins, as well as α-olefins that may have multiple non-aromatic carbon-carbon double bonds. As used herein, the term "standard α-olefin" refers to a straight-chain aliphatic hydrocarbon monoolefin having a carbon-carbon double bond between the first and second carbon atoms. As used herein, the term "linear internal olefin" refers to a straight-chain aliphatic hydrocarbon monoolefin having a double bond that is not between the first and second carbon atoms.

[0019] The term "oligomer" refers to a compound containing 2 to 20 monomer units. The terms "oligomerization product" and "oligomeric product" include all products made by the "oligomerization" process, including "oligomers" and products that are not "oligomeric" (e.g., products containing more than 20 monomer units or solid polymers), but excluding other non-oligomeric components in the oligomerization reactor effluent stream, such as unreacted ethylene, organic reaction medium, and hydrogen, among other components.

[0020] The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like do not relate to the actual product or composition resulting from the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic sites, or the fate of the aluminoxane and / or alkylaluminum and transition metal compound or complex after combining these components. Thus, the terms "catalyst composition," "catalyst mixture," "catalyst system," and the like encompass the initial starting components of the composition, as well as any product(s) that may result from contacting those initial starting components. The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like may be used interchangeably throughout this disclosure.

[0021] In the present invention, several types of ranges are disclosed. When any type of range is disclosed or claimed, the intention is to individually disclose or claim each number that could reasonably be included in such range, including the endpoints of the range, and any subranges and combinations of subranges within the range. For example, when a chemical moiety having a specific number of carbon atoms is disclosed or claimed, the intention is to individually disclose or claim all numbers that could be included in such range and consistent with the disclosure herein. For example, as used herein, a cocatalyst deactivator is a C4-C 18 or, in other words, an alcohol having 4 to 18 carbon atoms, refers to an alcohol compound that can have 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as any range between these two numbers (e.g., C6 to C 16 Alcohol or C8-C 12 alcohol), and also the combination of ranges between these two values ​​(e.g., C6-C 10 and C4~C 18 Similarly, all other ranges disclosed herein should be interpreted in the same manner as this example.

[0022] Generally, a number, size, formulation, parameter, range, or other quantity or characteristic is "about" or "approximately," whether or not expressly stated as such. Whether modified by the word "about" or "approximately," the claims include the equivalent of that quantity or characteristic.

[0023] Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, representative methods and materials are described herein.

[0024] All publications and patents mentioned herein are incorporated by reference in their entirety for the purpose of describing and disclosing, for example, the constructs and methodology described in the publications and patents, which may be used in connection with the presently described invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] Herein, a catalyst system for ethylene oligomerization is deactivated using a cocatalyst deactivator with a surprisingly small amount of OH of the cocatalyst deactivator, based on the amount of aluminum in the aluminoxane and alkylaluminum cocatalysts present in the catalyst system.

[0026] Methods for inactivation In one aspect, a method for deactivating a residual transition metal-based catalyst system containing a cocatalyst comprising an aluminoxane and, optionally, an alkylaluminum is disclosed herein. The method comprises deactivating the catalyst system with a C4-C hydroxyaluminum cocatalyst in a range of 0.5 to 1.5 times the moles of OH of the cocatalyst deactivator: (moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum). 18 This may include contacting with an alcohol-based cocatalyst deactivator.

[0027] In another aspect, disclosed herein is a method for deactivating a residual transition metal-based catalyst system containing a cocatalyst comprising an aluminoxane and optionally an alkylaluminum, contained in an effluent stream from an oligomerization reactor. The method comprises deactivating the effluent stream (which includes unreacted ethylene, oligomer product, the residual transition metal-based catalyst system containing aluminoxane and optionally an alkylaluminum cocatalyst, and an organic reaction medium) with a C4-C olefin copolymer in a range of 0.5 to 1.5 times the moles of OH of the cocatalyst deactivator: {(moles of aluminum in aluminoxane) + (moles of aluminum in alkylaluminum) + (moles of aluminum in alkylaluminum)}. 18 This may include contacting with an alcohol-based cocatalyst deactivator.

[0028] In yet another aspect, disclosed herein is an oligomerization process comprising: A) introducing ethylene, a transition metal-based catalyst system or catalyst system components, an organic reaction medium, and optionally hydrogen into an oligomerization reactor, wherein the transition metal-based catalyst system or catalyst system components include a cocatalyst comprising an aluminoxane and optionally an alkyl aluminum; B) forming oligomer products in the oligomerization reactor, wherein the oligomer products include hexene and octene; C) discharging an effluent stream from the oligomerization reactor, wherein the effluent stream includes unreacted ethylene, the oligomer products, residual transition metal-based catalyst system (including aluminoxane and optionally an alkyl aluminum cocatalyst), and the organic reaction medium; and D) reacting a C4-C6 18 The method may include contacting the effluent stream with an alcohol-based co-catalyst deactivator in an amount in the range of 0.5 to 1.5 times the moles of OH of the co-catalyst deactivator: {(moles of aluminum of the aluminoxane) + (moles of aluminum of the alkylaluminum) + (moles of aluminum of the alkylaluminum)}.

[0029] Generally, features of these methods / processes for deactivating catalyst systems (e.g., the relative amounts of cocatalyst, aluminoxane:alkylaluminum (if both are present), cocatalyst deactivator, and catalyst deactivator, among others) are described independently herein; these features may be combined without limitation and in any combination to further describe the disclosed methods / processes. Furthermore, additional steps may be performed before, between, and / or after these method and / or process steps and, unless otherwise stated, may be utilized in any combination, without limitation, to further describe methods of deactivating catalyst systems and processes for ethylene oligomerization. Moreover, beneficially, these methods / processes may be performed continuously.

[0030] In the disclosed methods / processes, the catalyst system may contain a cocatalyst comprising an aluminoxane and, optionally, an alkylaluminum. Thus, in some aspects, the cocatalyst comprises both an aluminoxane and an alkylaluminum, while in other aspects, the cocatalyst comprises an aluminoxane (and no alkylaluminum is present). When both an aluminoxane and an alkylaluminum are present in the catalyst system, the relative amount of aluminoxane to alkylaluminum (aluminoxane:alkylaluminum) in the catalyst system is not particularly limited. Nevertheless, exemplary, non-limiting ranges include, but are not limited to, aluminoxane:alkylaluminum (based on aluminum) molar ratios of 100:1 to 1:100, 20:1 to 1:20, 10:1 to 1:10, 5:1 to 1:5, 10:1 to 1:1, or 8:1 to 2:1. Often, the number of moles of aluminoxane in the catalyst system will be greater than the number of moles of alkylaluminum, although this is not required.

[0031] Any suitable aluminoxane may be utilized in the catalyst system, such as, for example, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and any mixture or combination thereof. In one aspect, the aluminoxane may comprise (or consist essentially of, or consist of) methylaluminoxane (MAO), alternatively modified methylaluminoxane (MMAO), alternatively ethylaluminoxane, alternatively n-propylaluminoxane, alternatively isopropylaluminoxane, alternatively n-butylaluminoxane, alternatively t-butylaluminoxane, alternatively sec-butylaluminoxane, alternatively isobutylaluminoxane, alternatively 1-pentyl-aluminoxane, alternatively 2-pentylaluminoxane, alternatively 3-pentyl-aluminoxane, alternatively isopentylaluminoxane, or alternatively neopentylaluminoxane.

[0032] Similarly, the alkylaluminum utilized in the catalyst system is not particularly limited, and representative alkylaluminum compounds can include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum, and the like, as well as any mixtures or combinations thereof. In one aspect, the alkylaluminum can comprise (or consist essentially of, or consist of) trimethylaluminum (TMA), alternatively triethylaluminum (TEA), alternatively tri-n-propylaluminum (TNPA), alternatively tri-n-butylaluminum (TNBA), alternatively triisobutylaluminum (TIBA), alternatively tri-n-hexylaluminum, or alternatively tri-n-octylaluminum.

[0033] The number of moles of OH in the cocatalyst deactivator in the disclosed method / process falls within the range of 0.5 to 1.5 times {(moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum)}. The number in the range of 0.5 to 1.5 may also be referred to as the effective amount of quenching OH required based on aluminum. In one aspect, the minimum number of moles of OH (or the minimum effective amount of quenching OH) can be at least 0.5, 0.6, 0.7, 0.8, 0.9, 1, or 1.1, and in another aspect, the maximum number of moles of OH (the maximum effective amount of quenching OH) can be 1.5, 1.4, 1.3, or 1.2. In general, the number of moles of OH per mole of aluminum (or the effective amount of quenching OH based on aluminum) can range from any minimum amount to any maximum amount described herein. For example, the number of moles of OH in the promoter deactivator is 0.5 to 1.4 times, 0.5 to 1.3 times, 0.6 to 1.5 times, 0.6 to 1.4 times, 0.6 to 1.3 times, 0.6 to 1.2 times, 0.7 to 1.5 times, 0.7 to 1.4 times, 0.7 to 1.3 times, 0.7 to 1.2 times, 0.8 to 1.4 times, 0.8 to 1.3 times, 0.9 to 1.5 times, 0.9 to 1.4 times, 0.9 to 1.3 times, 1 to 1.5 times, 1 to 1.4 times, 1 to 1.3 times, 1.1 to 1.5 times, 1.1 to 1.4 times, or 1.1 to 1.3 times of {(number of moles of aluminum in the aluminoxane) + (number of moles of aluminum in the alkylaluminum) + (number of moles of aluminum in the alkylaluminum)}. Without wishing to be bound by theory, it is believed that moles of OH greater than 1.5 result in more free alcohol within the oligomerization system, which can adversely affect the fresh catalyst recycled to the reactor, and also lead to material waste and cost inefficiencies. Conversely, moles less than 0.5 are believed to result in uneven and incomplete deactivation, especially when mixing and mass transfer limitations may prevent contact with all cocatalyst species in the effluent stream, and in situations where process conditions such as temperature may fluctuate.

[0034] In the relationship between the moles of OH in the cocatalyst deactivator and the total amount of aluminum, reflected by {(moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum)}, the moles of aluminum in the aluminoxane are counted once, while the moles of aluminum in the alkylaluminum are counted twice. Again, without wishing to be bound by theory, it is believed that about 1 / 2 to 1 OH group per aluminum is required to deactivate an aluminoxane, while about 2 OH groups per aluminum are required to deactivate an alkylaluminum.

[0035] The methods and processes disclosed herein can be utilized with any suitable transition metal-based catalyst system containing an aluminoxane and, optionally, a cocatalyst comprising an alkyl aluminum. The metal in the catalyst system can be chromium, iron, cobalt, vanadium, titanium, zirconium, hafnium, or the like, or any combination thereof. In one aspect, the transition metal-based catalyst system can include chromium, alternatively iron, alternatively cobalt, alternatively vanadium, alternatively titanium, alternatively zirconium, or alternatively hafnium.

[0036] As noted above, although not limited to use with any particular catalyst system, the methods and processes disclosed herein are particularly suitable for use with transition metal-based catalyst systems or catalyst system components comprising (i) a heteroatom-ligand transition metal compound complex and a cocatalyst, or (ii) a heteroatom ligand, a transition metal compound, and a cocatalyst. Accordingly, these methods and processes can be used with transition metal-based catalyst systems or catalyst system components comprising (i) a heteroatom-ligand chromium compound complex and a cocatalyst, or (ii) a heteroatom ligand, a chromium compound, and a cocatalyst. Other catalyst systems with which the disclosed methods and processes are particularly suitable for use include those described in U.S. Patent Nos. 10,493,422, 10,464,862, 10,435,336, and 11,267,909.

[0037] In the methods / processes disclosed herein, the catalyst system is 18 For example, in one aspect, the cocatalyst deactivator is a C6-C 16 In another aspect, the cocatalyst deactivator may comprise a C-C alcohol. 12 The term alcohol is generally used as a general term for mono-ols, diols, and polyols, and thus the cocatalyst deactivator can include a mono-alcohol compound, a diol compound, a polyol compound, or any combination thereof.

[0038] Consistent with certain aspects of the present invention, the cocatalyst deactivator may include butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, and the like, and any mixture or combination thereof. Specific examples of cocatalyst deactivators that can be utilized to deactivate the catalyst system include, for example, 1-butanol, 2-butanol, isobutanol, sec-butanol, t-butanol, 1-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-ethyl-1-hexanol, 2-methyl-3-heptanol, 1-nonanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 1-undecanol, 2-undecanol, 7-methyl-2-decanol, 1-dodecanol, 2-dodecanol, 2-ethyl-1-decanol, and the like, as well as any mixtures or combinations thereof. In certain aspects disclosed herein, the cocatalyst deactivator can include 2-ethyl-hexanol.

[0039] The suitability of a particular cocatalyst deactivator with a particular catalyst system can depend on many factors, one of which is the prevailing temperature at which the catalyst system and the cocatalyst deactivator are contacted. Accordingly, the particular boiling point of the cocatalyst deactivator can be important. Thus, the cocatalyst deactivator can have a minimum boiling point (at 1 atmosphere) of 130°C, 140°C, 150°C, 160°C, or 170°C, and, additionally or alternatively, a maximum boiling point (at 1 atmosphere) of 300°C, 280°C, 250°C, or 220°C. Generally, the boiling point of the deactivator can range from any minimum temperature disclosed herein to any maximum temperature disclosed herein. Thus, suitable non-limiting ranges may include the following: 130° C. to 300° C., 130° C. to 220° C., 140° C. to 280° C., 150° C. to 250° C., 160° C. to 280° C., 160° C. to 250° C., 170° C. to 300° C., or 170° C. to 220° C. For example, in an oligomerization process, it may be beneficial for the cocatalyst deactivator to be with the heavier products, which may facilitate separation of the cocatalyst deactivator from the 1-hexene and / or 1-octene; therefore, a cocatalyst deactivator having a boiling point of at least 130° C., more often at least 150° C. or at least 170° C., may be advantageous.

[0040] Another factor related to the suitability of a cocatalyst deactivator is that the deactivated catalyst system component (e.g., alkoxide) formed by contacting the catalyst system with the cocatalyst deactivator beneficially dissolves in the effluent stream (e.g., comprising an organic reaction medium or a hydrocarbon) at a minimum temperature of 130° C., 140° C., 150° C., 160° C., or 170° C., and also or alternatively at a maximum temperature of 300° C., 280° C., 250° C., or 220° C. In general, the deactivated catalyst system component may be soluble in the effluent stream (e.g., comprising a hydrocarbon) at any minimum temperature disclosed herein to any maximum temperature disclosed herein. Thus, suitable non-limiting ranges may include the following: 130° C. to 300° C., 130° C. to 220° C., 140° C. to 280° C., 150° C. to 250° C., 160° C. to 280° C., 160° C. to 250° C., 170° C. to 300° C., or 170° C. to 220° C. A deactivated catalyst system component is considered soluble if there is no visible precipitate at each temperature.

[0041] Typically, but not necessarily, the cocatalyst deactivator is added only once to contact the effluent stream or catalyst system, thereby deactivating the cocatalyst (e.g., terminating the polymerization of ethylene to hexene and / or octene and terminating the isomerization of hexene and / or octene) and terminating the pyrophoric activity of the cocatalyst (e.g., terminating air and moisture reactivity). Thus, advantageously, multiple injections of the same or different deactivators with different functions are not required.

[0042] Consistent with any of the methods / processes disclosed herein, these methods / processes can optionally further include a control system including steps of (i) determining the amount of catalytic activity remaining after the addition of the cocatalyst deactivator, and (ii) adjusting the amount of cocatalyst deactivator based on the catalytic activity. For example, if some catalytic activity remains after the addition of the cocatalyst deactivator, a larger number of moles of OH can be added. Conversely, if there is no catalytic activity, the amount added can be reduced. The amount of catalytic activity remaining after the addition of the cocatalyst deactivator can be determined by any suitable method, one such method being to test the resulting composition for isomerization of oligomer products, such as 1-octene isomerization. That is, to determine whether the resulting composition after the addition of the cocatalyst deactivator can catalyze the isomerization of 1-octene or 1-dodecene, as shown in the following examples.

[0043] Next, a method / process for contacting the effluent stream from an oligomerization reactor with a cocatalyst deactivator is described, often before the effluent stream is introduced into a separator to remove at least a portion of the unreacted ethylene. In this aspect, the contacting step occurs after discharge from the reactor and before at least a portion of the unreacted ethylene is flashed / removed from the effluent stream.

[0044] Alternatively, the effluent stream can be contacted with the co-catalyst deactivator after at least a portion of the unreacted ethylene has been removed from the effluent stream in the separator. In this aspect, the co-catalyst deactivator can be combined with the bottoms stream from the separator / flash vessel after the ethylene removal step.

[0045] Among other components, the effluent stream contains oligomeric products, such as hexenes, octenes, and other C4 +The oligomer product may contain linear α-olefins. The amount of octene in the oligomer product may typically be in the range of 20 to 99 wt %, based on the total amount of oligomers in the oligomer product. In one aspect, the minimum amount of octene in the oligomer product may be 20, 30, or 40 wt %. In another aspect, the maximum amount of octene in the oligomer product may be 99, 95, 92.5, 90, 87.5, or 85 wt %. Generally, the amount of octene in the oligomer product may range from any minimum amount of octene in the oligomer product to any maximum amount of octene in the oligomer product described herein. For example, the amount of octene in the oligomer product, based on the total weight of oligomers, can be 30-95 wt%, 40-95 wt%, 40-90 wt%, 20-90 wt%, 30-87.5 wt%, 30-85 wt%, 40-87.5 wt%, 40-85 wt%, 20-60 wt%, 30-55 wt%, or 40-55 wt% octene.

[0046] Additionally, or alternatively, the oligomer product can contain any suitable amount of hexene. In one aspect, the minimum amount of hexene in the oligomer product can be 15, 20, 25, 30, or 35 wt. %. In another aspect, the maximum amount of hexene in the oligomer product can be 75, 65, 60, 55, or 50 wt. %. Generally, the amount of hexene in the oligomer product can range from any minimum amount of hexene in the oligomer product to any maximum amount of hexene in the oligomer product described herein. For example, the amount of hexene, based on the total weight of oligomers in the oligomer product, can be 20-60 wt. %, 25-55 wt. %, or 30-50 wt. % hexene.

[0047] The ethylene conversion rate in the oligomerization reactor is not particularly limited, and generally, the minimum ethylene conversion rate can be at least 20, 30, 35, 40, 45, or 50 wt. %, and the maximum ethylene conversion rate can be 99, 95, 90, 80, 75, 70, or 65 wt. Generally, the ethylene conversion rate in the reactor can range from any minimum conversion rate to any maximum conversion rate described herein. For example, the ethylene conversion rate can range from 20 to 95 wt. %, 30 to 90 wt. %, 40 to 80 wt. %, 50 to 70 wt. %, or 55 to 65 wt. The ethylene conversion rate is calculated based on the amount of ethylene entering the reactor and the amount of ethylene in the effluent stream.

[0048] Referring now to step A) of the oligomerization process, ethylene, a transition metal-based catalyst system or catalyst system components, an organic reaction medium, and optionally hydrogen are introduced into an oligomerization reactor, wherein the transition metal-based catalyst system or catalyst system components include an aluminoxane and optionally a cocatalyst comprising an alkyl aluminum. Because the use of hydrogen is optional in step A), in one aspect, hydrogen is absent from step A), while in another aspect, hydrogen is present in step A). [Example]

[0049] The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the present invention in any way. After reading the description herein, various other aspects, modifications, and equivalents thereof may be suggested to those skilled in the art without departing from the spirit of the invention or the scope of the appended claims.

[0050] GC-FID data were collected on an Agilent Technologies 7890A instrument equipped with a 50 m long Agilent DB-5 GC column (0.32 mm internal diameter, 0.25 μm film thickness). Samples (0.05 μL) were syringe-injected into the inlet at 300 °C using helium as the carrier gas with a split ratio of 25:1. The initial column temperature was 40 °C, ramped to 80 °C at a rate of 3 °C / min, then ramped to 300 °C at a rate of 13 °C / min and held for 15 min. Peak integration was performed manually, and peak identification was performed using authentic samples.

[0051] Examples 1 to 5 In Examples 1-5, exemplary chromium / MAO / alkylaluminum catalyst systems were used to determine the amount of cocatalyst deactivator required to deactivate the cocatalyst component of the catalyst system, specifically the amount of cocatalyst deactivator required to prevent dimerization and / or isomerization of 1-dodecene at 175° C. In Example 1, a vial was filled with 18.2 mg of a representative chromium catalyst (N 2- The vial was charged with phosphinylguanidine chromium(III) trichloride tetrahydrofuran complex, 1 g of xylene, and 1 g of n-tridecane (internal standard), followed by the cocatalyst. The cocatalyst amounts were 60 equivalents of triethylaluminum (60:1 Al:Cr) and 400 equivalents of MMAO-21 (400:1 Al:Cr). MMAO-21 is a modified methylaluminoxane produced from a mixture of TMA and TIBA. After adding 10 g of 1-dodecene (approximately 95.2 wt%), the vial was heated to 175 °C over 30 min and then maintained at that temperature for 1 h. After cooling to room temperature, the contents of the vial were thoroughly quenched with water and then analyzed by GC.

[0052] Example 2 was a control sample of 1-dodecene starting material (approximately 95.2 wt% purity) with no other added materials. Examples 3-5 were performed similarly to Example 1, except that the cocatalyst deactivator 2-ethyl-1-hexanol was added after the 1-dodecene but before heating to 175°C. The amount of 2-ethyl-1-hexanol added in Example 3 was moles of OH equal to 1.95 times (moles of aluminum in the aluminoxane + moles of aluminum in the alkylaluminum) + moles of aluminum in the alkylaluminum). In Example 4, the number of moles of OH was 1.60 times {(number of moles of aluminum in the aluminoxane) + (number of moles of aluminum in the alkylaluminum) + (number of moles of aluminum in the alkylaluminum)}, and in Example 5, the number of moles of OH was 1.24 times {(number of moles of aluminum in the aluminoxane) + (number of moles of aluminum in the alkylaluminum) + (number of moles of aluminum in the alkylaluminum)}. Examples 1 to 5 are summarized in Figure 1 and Table 1 below.

[0053] As the data in Figure 1 and Table 1 show, significant isomerization and dimerization of 1-dodecene occurred in Example 1, as expected in the absence of cocatalyst deactivator. However, in the presence of cocatalyst deactivator, Examples 3-5 performed identically to Control Example 2 (the 1-dodecene control). No isomerization or dimerization was observed in Examples 3-5, and the purity of 1-dodecene was the same as the 1-dodecene control in Example 2.

[0054] While the suppression of isomerization / dimerization using 1.95 moles in Example 3 was expected, the similar effect of the much lower amount of 1.24 used in Example 5 was unexpected. This data demonstrates that much lower amounts of cocatalyst deactivator can be used to deactivate a catalyst system without introducing excess OH into the oligomerization reaction system, resulting in cost and performance issues. [Table 1]

[0055] Examples 6 to 10 Examples 6-10 were carried out similarly to Examples 1-5, except that in Examples 6-10, an exemplary MAO catalyst system was used to determine the amount of cocatalyst deactivator needed to deactivate the aluminoxane component of the catalyst system (no alkylaluminum component was present in the catalyst system), specifically to determine the amount needed to prevent the dimerization and / or isomerization of 1-dodecene at 170°C. In Example 6, a vial containing 10 g of 7 wt% MMAO-3A in n-heptane was used. MMAO-3A is a modified methylaluminoxane produced from a mixture of TMA and TIBA. After adding 12.5 mL of 1-dodecene (approximately 95-96 wt%), the vial was heated to 170°C for 15 minutes and then maintained at that temperature for 1 hour. After cooling to room temperature, the contents of the vial were thoroughly quenched with water and then analyzed by GC.

[0056] Example 7 was a control sample of 1-dodecene starting material (approximately 95-96 wt.% purity) with no other added materials. Examples 8-10 were carried out similarly to Example 6, except that the cocatalyst deactivator 2-ethyl-1-hexanol was added after 1-dodecene but before heating to 170°C. The amount of 2-ethyl-1-hexanol added in Example 8 was a number of moles of OH equal to 1.0 times {(moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum)}. Example 9 was carried out with a number of moles of OH equal to 0.8 times {(moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum)}. Example 10 was carried out with moles of OH equal to 0.6 times {(moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum)}. Note that no alkylaluminum cocatalyst was present in the catalyst systems of Examples 6-10. Examples 6-10 are summarized in Table 2 below.

[0057] As the data in Table 2 show, in Example 6, significant isomerization and dimerization of 1-dodecene occurred in the absence of cocatalyst deactivator. However, in the presence of cocatalyst deactivator, Examples 8-10 behaved exactly like Control Example 7 (the 1-dodecene control). No isomerization or dimerization was observed in Examples 8-10. The GC data for Examples 6-10 was also confirmed using NMR, which demonstrated that Examples 7-10 each contained the same amount of α-olefins and internal olefins (no isomerization).

[0058] It was surprising that the use of 1.0 and 0.8 moles in Examples 8 and 9, respectively, completely suppressed isomerization / dimerization. However, it was even more unexpected that the use of an effective amount of quench OH equal to 0.6 in Example 10 would work as well. This data demonstrates that a much smaller amount of cocatalyst deactivator can be used to deactivate a catalyst system without introducing excess OH into the oligomerization reaction system, resulting in cost and performance issues. [Table 2]

[0059] The present invention has been described herein with reference to numerous aspects and specific examples. Many variations will be suggested to those skilled in the art in light of the detailed description. All such obvious variations are within the fully intended scope of the appended claims. Other aspects of the invention may include, but are not limited to (although an aspect may be described as "comprising," it may alternatively be "consisting essentially of" or "consisting of"):

[0060] Aspect 1. A method for deactivating a transition metal-based catalyst system (e.g., a residual catalyst system) containing a co-catalyst comprising an aluminoxane and, optionally, an alkylaluminum, the method comprising: The catalyst system is a C4 to C 18The method comprises contacting the alcohol-based co-catalyst deactivator with the co-catalyst deactivator in an amount in which the number of moles of OH in the co-catalyst deactivator is in the range of 0.5 to 1.5 times {(the number of moles of aluminum in the aluminoxane) + (the number of moles of aluminum in the alkylaluminum) + (the number of moles of aluminum in the alkylaluminum)}.

[0061] Aspect 2. A method for deactivating a residual transition metal-based catalyst system comprising an aluminoxane and, optionally, an alkylaluminum cocatalyst, contained in an effluent stream from an oligomerization reactor, the method comprising: The effluent stream, comprising unreacted ethylene, oligomeric products, the residual transition metal-based catalyst system comprising the aluminoxane and optionally the cocatalyst comprising the alkylaluminum, and the organic reaction medium, is treated with a C4-C 18 the method, comprising contacting the alcohol-based co-catalyst deactivator with the co-catalyst deactivator in an amount in which the number of moles of OH in the co-catalyst deactivator is in the range of 0.5 to 1.5 times {(the number of moles of aluminum in the aluminoxane) + (the number of moles of aluminum in the alkylaluminum) + (the number of moles of aluminum in the alkylaluminum)}.

[0062] Aspect 3. An oligomerization process comprising: A) introducing ethylene, a transition metal-based catalyst system or catalyst system components, an organic reaction medium, and optionally hydrogen into an oligomerization reactor, wherein the transition metal-based catalyst system or catalyst system components comprises a cocatalyst comprising an aluminoxane and optionally an alkyl aluminum; B) forming an oligomer product comprising hexene and octene in said oligomerization reactor; C) discharging an effluent stream from the oligomerization reactor, the effluent stream comprising unreacted ethylene, the oligomer product, residual transition metal-based catalyst system (including the aluminoxane and optionally the cocatalyst comprising the alkylaluminum), and the organic reaction medium; and D) The effluent stream is converted to C4~C 18The process, comprising contacting the alcohol-based co-catalyst deactivator with the alcohol-based co-catalyst deactivator in an amount in the range of 0.5 to 1.5 times the number of moles of OH of the co-catalyst deactivator: {(number of moles of aluminum in the aluminoxane) + (number of moles of aluminum in the alkylaluminum) + (number of moles of aluminum in the alkylaluminum)}.

[0063] Aspect 4. The method or process as defined in Aspect 2 or 3, wherein the effluent stream is contacted with the cocatalyst deactivator before the effluent stream is introduced into a separator to remove at least a portion of the unreacted ethylene.

[0064] Aspect 5. The method or process defined in Aspect 2 or 3, wherein the effluent stream is contacted with the cocatalyst deactivator after at least a portion of the unreacted ethylene is removed from the effluent stream in a separator.

[0065] Aspect 6. The method or process defined in any one of the preceding aspects, wherein the alkyl aluminum comprises trimethyl aluminum (TMA), triethyl aluminum (TEA), tri-n-propyl aluminum (TNPA), tri-n-butyl aluminum (TNBA), triisobutyl aluminum (TIBA), tri-n-hexyl aluminum, tri-n-octylaluminum, or any combination thereof.

[0066] Aspect 7. The method or process defined in any one of the preceding aspects, wherein the aluminoxane comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or any combination thereof.

[0067] Aspect 8. The method or process defined in any one of the preceding aspects, within any range disclosed herein, wherein the molar ratio of aluminoxane:alkylaluminum, based on aluminum, is, e.g., 100:1 to 1:100, 20:1 to 1:20, 10:1 to 1:10, 5:1 to 1:5, 10:1 to 1:1, or 8:1 to 2:1.

[0068] Aspect 9. The method or process defined in any one of the preceding aspects, wherein the transition metal-based catalyst system comprises chromium, iron, cobalt, vanadium, titanium, zirconium, hafnium, or a combination thereof.

[0069] Aspect 10. The method or process defined in any one of the preceding aspects, wherein the cocatalyst deactivator comprises a monoalcohol compound, a diol compound, a polyol compound (or alternatively, a monoalcohol compound), and the cocatalyst deactivator is a C4-C 18 Alcohols, C6-C 16 Alcohol or C8-C 12 The method or process comprising an alcohol.

[0070] Aspect 11. The method or process defined in any one of the preceding aspects, wherein the cocatalyst deactivator comprises butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, or a mixture thereof.

[0071] Aspect 12. The method or process defined in any one of the preceding aspects, wherein the cocatalyst deactivator is 1-butanol, 2-butanol, isobutanol, sec-butanol, t-butanol, 1-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, or 1-octanol. , 2-octanol, 3-octanol, 4-octanol, 2-ethyl-1-hexanol, 2-methyl-3-heptanol, 1-nonanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 1-undecanol, 2-undecanol, 7-methyl-2-decanol, 1-dodecanol, 2-dodecanol, 2-ethyl-1-decanol, or mixtures thereof.

[0072] Aspect 13. The method or process defined in any one of the preceding aspects, wherein the cocatalyst deactivator comprises 2-ethyl-hexanol.

[0073] Aspect 14. The method or process defined in any one of the preceding aspects, wherein the cocatalyst deactivator has a boiling point (under 1 atmosphere pressure) in any range disclosed herein, e.g., at least 130°C, at least 140°C, at least 150°C, at least 160°C, or at least 170°C, and not more than 300°C, not more than 280°C, not more than 250°C, or not more than 220°C.

[0074] Aspect 15. The method or process defined in any one of Aspects 2-14, wherein contact with the cocatalyst deactivator forms a deactivated catalyst system component (e.g., an alkoxide), and the deactivated catalyst system component is soluble in the effluent stream (e.g., an organic reaction medium, a hydrocarbon) at any temperature disclosed herein, e.g., at least 130°C, at least 140°C, at least 150°C, at least 160°C, or at least 170°C, and no more than 300°C, no more than 280°C, no more than 250°C, or no more than 220°C.

[0075] Aspect 16. The method or process defined in any one of the preceding aspects, wherein contact with the cocatalyst deactivator both deactivates the cocatalyst (e.g., stops the oligomerization of ethylene to hexene and / or octene, or the isomerization of hexene and / or octene) and stops the pyrophoricity of the cocatalyst (e.g., stops reactivity with air and moisture) by a single addition.

[0076] Aspect 17. The method or process defined in any one of the preceding aspects, wherein the method or process is performed continuously.

[0077] Aspect 18. The method or process defined in any one of the preceding aspects, wherein the transition metal-based catalyst system or catalyst system component comprises (i) a heteroatom-ligand transition metal compound complex and the co-catalyst, or (ii) a heteroatom ligand, a transition metal compound, and the co-catalyst.

[0078] Aspect 19. The method or process defined in any one of the preceding aspects, wherein the transition metal-based catalyst system or catalyst system component comprises (i) a heteroatom-ligand chromium compound complex and the cocatalyst, or (ii) a heteroatom ligand, a chromium compound, and the cocatalyst.

[0079] Aspect 20. The method or process defined in any one of Aspects 2-19, wherein the oligomer product comprises any amount of octene disclosed herein, e.g., at least 20, 30, or 40 wt%, and up to 99, 95, 92.5, 90, 87.5, or 85 wt%, or 20-99 wt%, 30-95 wt%, 40-95 wt%, 40-90 wt%, 20-90 wt%, 30-87.5 wt%, 30-85 wt%, 40-87.5 wt%, 40-85 wt%, 20-60 wt%, 30-55 wt%, or 40-55 wt%, based on the total amount of octene in the oligomer product.

[0080] Aspect 21. The method or process defined in any one of Aspects 2-20, wherein the oligomer product comprises any amount of hexene disclosed herein, e.g., at least 15, 20, 25, 30, or 35 wt.%, up to 75, 65, 60, 55, or 50 wt.%, or 20 to 60 wt.%, 25 to 55 wt.%, or 30 to 50 wt.%, of hexene, based on the total amount of the oligomers in the oligomer product.

[0081] Aspect 22. The process defined in any one of Aspects 3-21, wherein the oligomerization reactor comprises any ethylene conversion disclosed herein, e.g., a conversion of at least 20, 30, 35, 40, 45, or 50 wt%, up to 99, 95, 90, 80, 75, 70, or 65 wt%, or 20-95 wt%, 30-90 wt%, 40-80 wt%, 50-70 wt%, or 55-65 wt%, based on the amount of ethylene entering the reactor and the amount of ethylene in the effluent stream.

[0082] Aspect 23. The process defined in any one of Aspects 3 to 22, wherein hydrogen is present in step A).

[0083] Aspect 24. The method or process defined in any one of the preceding aspects, further comprising: (i) measuring the residual amount of catalyst activity after adding the cocatalyst deactivator (e.g., testing the product for isomerization of oligomeric products, such as 1-octene isomerization); and (ii) adjusting the amount of the cocatalyst deactivator based on the catalyst activity.

[0084] Aspect 25. The method or process defined in any one of the preceding aspects, wherein the number of moles of OH is within any range disclosed herein, e.g., at least 0.6 times, at least 0.7 times, at least 0.8 times, at least 0.9 times, at least 1 time, or at least 1.1 times, and no more than 1.5 times, no more than 1.4 times, no more than 1.3 times, or no more than 1.2 times {(moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum)}.

[0085] Aspect 26. The method or process defined in any one of the preceding aspects, wherein the co-catalyst comprises the aluminoxane and the alkylaluminum (or alternatively, the aluminoxane and no alkylaluminum).

Claims

1. 1. A method for deactivating a transition metal-based catalyst system containing a co-catalyst comprising an aluminoxane and optionally an alkylaluminum, the method comprising: The catalyst system is ４ ~C １８ contacting the alcohol-based co-catalyst deactivator with the alcohol-based co-catalyst deactivator in an amount in the range of 0.5 to 1.5 times the number of moles of OH of the co-catalyst deactivator, where the number of moles of OH is 0.5 to 1.5 times {(the number of moles of aluminum in the aluminoxane) + (the number of moles of aluminum in the alkylaluminum) + (the number of moles of aluminum in the alkylaluminum)}; The method.

2. 1. A method for deactivating a residual transition metal-based catalyst system comprising an aluminoxane and optionally an alkylaluminum cocatalyst contained in an effluent stream from an oligomerization reactor, the method comprising: the effluent stream comprising unreacted ethylene, oligomeric products, the residual transition metal-based catalyst system comprising the cocatalyst comprising the aluminoxane and optionally the alkylaluminum, and the organic reaction medium, is subjected to a process comprising: ４ ~C １８ contacting the alcohol-based co-catalyst deactivator with the alcohol-based co-catalyst deactivator in an amount in the range of 0.5 to 1.5 times the number of moles of OH of the co-catalyst deactivator, i.e., {(the number of moles of aluminum in the aluminoxane) + (the number of moles of aluminum in the alkylaluminum) + (the number of moles of aluminum in the alkylaluminum)}; The method.

3. 1. An oligomerization process comprising: A) introducing ethylene, a transition metal-based catalyst system or catalyst system components, an organic reaction medium, and optionally hydrogen into an oligomerization reactor, wherein the transition metal-based catalyst system or catalyst system components comprises a cocatalyst comprising an aluminoxane and optionally an alkyl aluminum; B) forming an oligomer product comprising hexene and octene in said oligomerization reactor; C) discharging an effluent stream from the oligomerization reactor, the effluent stream comprising unreacted ethylene, the oligomer product, residual transition metal-based catalyst system, and the organic reaction medium; and D) The effluent stream is subjected to ４ ~C １８ contacting the alcohol-based co-catalyst deactivator with the alcohol-based co-catalyst deactivator in an amount in the range of 0.5 to 1.5 times the number of moles of OH of the co-catalyst deactivator, i.e., {(the number of moles of aluminum in the aluminoxane) + (the number of moles of aluminum in the alkylaluminum) + (the number of moles of aluminum in the alkylaluminum)}; The process.

4. 4. The method or process of claim 2 or 3, wherein the effluent stream is contacted with the cocatalyst deactivator before the effluent stream is introduced into a separator to remove at least a portion of the unreacted ethylene.

5. 4. The method or process of claim 2 or 3, wherein at least a portion of the unreacted ethylene is removed from the effluent stream in a separator before the effluent stream is contacted with the cocatalyst deactivator.

6. 10. The method or process of any one of the preceding claims, wherein the alkyl aluminum comprises trimethyl aluminum (TMA), triethyl aluminum (TEA), tri-n-propyl aluminum (TNPA), tri-n-butyl aluminum (TNBA), triisobutyl aluminum (TIBA), tri-n-hexyl aluminum, tri-n-octylaluminum, or any combination thereof.

7. 10. The method or process of any one of the preceding claims, wherein the aluminoxane comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, or any combination thereof.

8. 10. The method or process of any one of the preceding claims, wherein the cocatalyst deactivator comprises butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, or mixtures thereof.

9. 10. The method or process of any one of the preceding claims, wherein the cocatalyst deactivator has a boiling point (under 1 atmosphere pressure) of at least 130°C, at least 140°C, at least 150°C, at least 160°C, or at least 170°C, and not more than 300°C, not more than 280°C, not more than 250°C, or not more than 220°C.

10. 10. The method or process of any one of the preceding claims, wherein the cocatalyst deactivator comprises 2-ethyl-1-hexanol.

11. 10. The method or process of any one of the preceding claims, wherein the catalyst system comprises chromium, iron, cobalt, vanadium, titanium, zirconium, hafnium, or combinations thereof.

12. 10. The method or process of any one of the preceding claims, wherein the transition metal-based catalyst system or catalyst system component comprises (i) a heteroatom-ligand chromium compound complex and the co-catalyst, or (ii) a heteroatom-ligand, a chromium compound, and the co-catalyst.

13. The method or process of any one of claims 1 to 12, wherein the co-catalyst comprises the aluminoxane and the alkylaluminum.

14. 14. The method or process of claim 13, wherein the molar ratio of aluminoxane to alkylaluminum (based on aluminum) is in the range of from 100:1 to 1:100, from 20:1 to 1:20, from 10:1 to 1:10, from 5:1 to 1:5, from 10:1 to 1:1, or from 8:1 to 2:

1.

15. The method or process of any one of claims 1 to 12, wherein the co-catalyst comprises the aluminoxane but does not comprise the aluminum alkyl.

16. 10. A method or process according to any one of the preceding claims, further comprising: (i) measuring the residual amount of catalytic activity after adding the cocatalyst deactivator; and (ii) adjusting the amount of the cocatalyst deactivator based on the catalyst activity; The method or process comprising the steps of:

17. 10. The method or process of any one of the preceding claims, wherein the number of moles of OH is at least 0.6, at least 0.7, at least 0.8, at least 0.9, at least 1, or at least 1.1 times {(moles of aluminum in the aluminoxane) + (moles of aluminum in the alkylaluminum) + (moles of aluminum in the alkylaluminum)}, and is not more than 1.5, not more than 1.4, not more than 1.3, or not more than 1.2 times.

18. 10. A method or process according to any one of the preceding claims, comprising: the number of moles of OH is 0.6 to 1.5 times {(the number of moles of aluminum in the aluminoxane) + (the number of moles of aluminum in the alkylaluminum) + (the number of moles of aluminum in the alkylaluminum)}, the number of moles of OH is 0.6 to 1.4 times {(the number of moles of aluminum in the aluminoxane) + (the number of moles of aluminum in the alkylaluminum) + (the number of moles of aluminum in the alkylaluminum)}; or The method or process, wherein the number of moles of OH is 0.6 to 1.3 times {(number of moles of aluminum in the aluminoxane) + (number of moles of aluminum in the alkylaluminum) + (number of moles of aluminum in the alkylaluminum)}.

19. 19. The method or process of any one of claims 2 to 18, wherein the oligomeric product comprises: 20 to 99 wt%, 30 to 95 wt%, 40 to 95 wt%, 40 to 90 wt%, 20 to 90 wt%, 30 to 87.5 wt%, 30 to 85 wt%, 40 to 87.5 wt%, 40 to 85 wt%, 20 to 60 wt%, 30 to 55 wt%, or 40 to 55 wt% octene, based on the total amount of oligomers in the oligomer product; and The method or process comprising 20 to 60 wt. %, 25 to 55 wt. %, or 30 to 50 wt. % hexene based on the total amount of oligomers in the oligomer product.

20. A process according to any one of claims 3 to 19, comprising: Hydrogen is present in step A), and / or the oligomerization reactor has an ethylene conversion of 20 to 95 wt%, 30 to 90 wt%, 40 to 80 wt%, 50 to 70 wt%, or 55 to 65 wt%, based on the amount of ethylene entering the reactor and the amount of ethylene in the effluent stream.

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