Selective 1-hexene / 1-octene formation from 1-decene

Abstract

The process for producing 1-octene and 1-decene is (a) a mixture of 15 to 80 mol% C6 olefins, 20 to 80 mol% C8 olefins, and 5 to 20 mol% C 10 + olefin-containing oligomer product composition, a first oligomer composition containing C6 alkanes and at least 85 mol% C6 olefins (e.g., 1-hexene), a second oligomer composition containing at least 20 mol% C8 olefins (e.g., 1-octene), and a C 10 (b) contacting a metathesis catalyst system with the first oligomer composition to produce a C+ heavy stream containing olefins; 10 forming a first composition comprising a linear internal olefin; and (c) reacting the first composition with a C 10 and (d) purifying the second composition to isolate a third composition comprising at least 90 mole percent 1-decene. Processes for the production of 1-hexene and 1-decene are also described, as are related manufacturing systems and processes for producing higher carbon number normal alpha olefins from lower carbon number normal alpha olefins.

Description

[Technical Field]

[0001] REFERENCE TO RELATED APPLICATIONS This application was filed as a PCT international patent application on October 24, 2023, and claims the benefit of and priority to U.S. Patent Application No. 18 / 050,510, filed on October 28, 2022, the disclosure of which is incorporated herein by reference in its entirety.

[0002] The present disclosure relates generally to systems and methods for producing 1-decene in combination with 1-hexene, 1-octene, or both 1-hexene and 1-octene. [Background technology]

[0003] The synthesis of standard α-olefins with specific carbon numbers, especially 1-hexene, 1-octene, and 1-decene, is of great importance in the chemical industry. However, with current catalysts and reaction processes, it is difficult to selectively produce only the α-olefin fraction with the desired carbon number, rather than a complex mixture of olefin products. 10 It would be beneficial to develop new methods for producing desirable combinations of alpha olefins, and therefore, the present invention is generally directed to these ends. Summary of the Invention

[0004] This summary is provided to introduce some concepts in a simplified form that are further described herein. This summary is not intended to identify essential 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] The first process described herein can be used to produce 1-octene and 1-decene. The first process comprises: a) 15-80 mol % C6 olefins, 20-80 mol % C8 olefins, and 5-20 mol % C 10+ olefins, and a composition comprising the oligomer product comprising: i) a first oligomer composition comprising C6 alkanes and at least 85 mol% C6 olefins, where the C6 olefins comprise at least 80 mol% 1-hexene; ii) a second oligomer composition comprising at least 20 mol% C8 olefins, where the C8 olefins comprise at least 85 mol% 1-octene; and iii) a C6 olefin composition comprising at least 20 mol% C8 olefins, where the C8 olefins comprise at least 85 mol% 1-octene. 10 a) separating the first oligomer composition into a heavy stream containing olefins and a heavy stream containing olefins; and b) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to produce a C 10 forming a first composition comprising a linear internal olefin; and c) in the presence of actinic radiation, 10 contacting all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying the second composition to isolate a third composition comprising at least 90 mole % 1-decene.

[0006] The second process described herein can be used to produce 1-hexene and 1-decene. The second process includes: a) separating a composition comprising an oligomer product comprising at least 85 mol% C6 olefins and at least 5 mol% C8+ olefins into i) a first oligomer composition comprising C6 alkanes and at least 90 mol% C6 olefins, where the C6 olefins comprise at least 90 mol% 1-hexene, and ii) a heavy stream comprising C8+ olefins; and b) contacting all or a portion of the first oligomer composition with a metathesis catalyst system to produce C8+ olefins. 10 forming a first composition comprising a linear internal olefin; and c) in the presence of actinic radiation, 10 contacting all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying the second composition to isolate a third composition comprising at least 90 mole % 1-decene.

[0007] Related production systems are also disclosed herein. The first (1-octene and 1-decene) production system is an ethylene oligomerization system configured to: 1) oligomerize ethylene in the presence of a catalyst system or catalyst system components to form a composition comprising an oligomer product, the oligomer product comprising 15 to 80 mol% C6 olefins, 20 to 80 mol% C8 olefins, and 5 to 20 mol% C6 olefins; 10 + olefins, and 2) a composition comprising the oligomer product, said composition comprising: i) a first oligomer composition comprising 1-hexene, ii) a second oligomer composition comprising 1-octene, and iii) C 10 a fractionation system configured to separate the first oligomer composition into a heavy stream containing olefins and a heavy stream containing olefins; and 3) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to produce a C 10 a metathesis system configured to form a first composition comprising a linear internal olefin; and 4) in the presence of actinic radiation, 10 4) a catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and 5) a purification system configured to isolate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0008] The second (1-hexene and 1-decene) production system comprises: 1) an ethylene oligomerization system configured to oligomerize ethylene in the presence of a catalyst system or catalyst system components to form a composition comprising oligomer products, the oligomer products comprising at least 85 mol % C6 olefins and at least 5 mol % C8+ olefins; 2) a fractionation system configured to separate the composition comprising oligomer products into a first oligomer composition comprising 1-hexene and a heavier stream comprising C8+ olefins; and 3) a metathesis catalyst system configured to contact all or a portion of the first oligomer composition to form a C6 olefin-containing fraction. 10 a metathesis system configured to form a first composition comprising a linear internal olefin; and 4) in the presence of actinic radiation,10 4) a catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and 5) a purification system configured to isolate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0009] The third process described herein can be used to produce higher carbon number normal alpha olefins from lower carbon number normal alpha olefins. This process involves (i) the production of olefins with the structure CH(CH) n contacting a first normal alpha olefin having HC=CH with a metathesis catalyst system to produce a metathesis product of the structure CH(CH) n HC=CH(CH2) n (ii) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of actinic radiation to form a linear internal olefin having the structure CH(CH) 2n+1 and forming a second normal alpha olefin having HC=CH2. In this third process, n is an integer ranging from 0 to 15.

[0010] A fourth process described herein can be used to produce higher carbon number normal alpha olefins from two lower carbon number normal alpha olefins. This process involves (a) the formation of a olefin having the structure CH(CH) p a first normal alpha olefin having HC=CH2 and a second normal alpha olefin having the structure CH3(CH2) q A second normal alpha olefin having HC=CH2 is contacted with the metathesis catalyst system to produce a compound of the structure CH3(CH2) p HC=CH(CH2) q (b) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of actinic radiation to form a linear internal olefin having the structure CH(CH) p+q+1 and forming a third normal α-olefin having HC=CH2. In this fourth process, p and q are each integers ranging from 0 to 15. Although p and q can be the same integer, typically p and q are different integers.

[0011] Both the foregoing general description and the following detailed description are exemplary and explanatory only. Accordingly, the foregoing general description and the following detailed description are not to be construed as limiting. Furthermore, features or variations in addition to those described herein may be provided. For example, particular aspects may be directed to combinations and subcombinations of various features described in the detailed description.

[0012] The following drawings form part of the present specification and are included to further support certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description. [Brief explanation of the drawings]

[0013] [Figure 1] 1 illustrates a system for producing 1-octene / 1-decene according to an embodiment of the present disclosure. [Figure 2] 1 shows a system for producing 1-octene / 1-decene in accordance with another embodiment of the present disclosure. [Figure 3] 1 shows a system for producing 1-hexene / 1-decene in accordance with yet another embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0014] While the invention disclosed herein is susceptible to various modifications and alternative forms, only a few specific embodiments have been shown by way of example in the drawings and are hereinafter described. The drawings and detailed description of these specific embodiments are not intended in any way to limit the breadth or scope of the inventive concepts or the appended claims. Rather, the drawings and detailed description are provided to illustrate the inventive concepts to one of ordinary skill in the art and to enable such person to make and use the inventive concepts.

[0015] definition The following definitions are provided to more clearly define the terms used herein. Unless otherwise stated, the following definitions apply to the present disclosure. If a term used in this disclosure is not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997) can be applied, provided that the definition does not conflict with other disclosures or definitions applicable herein and does not make unclear or invalidate the claim to which the definition applies. If a definition or usage provided by a document incorporated by reference herein conflicts with the definition or usage provided herein, the definition or usage provided herein takes precedence.

[0016] The subject features may be described herein such that combinations of different features may be envisioned within a particular embodiment. For each and every aspect and / or feature disclosed herein, all combinations that do not adversely affect the design, configuration, process, and / or method described herein are contemplated, regardless of the explicit description of the specific combination. Furthermore, unless otherwise stated, any aspect and / or feature disclosed herein may be combined to describe inventive features consistent with the present disclosure.

[0017] In this disclosure, compositions, processes / methods, and systems are described in terms of "comprising" various materials, steps, and components; however, unless otherwise specified, the compositions, processes / methods, and systems may also "essentially comprise" or "comprise" various materials, steps, or components.

[0018] The terms "a," "an," and "the" are intended to include plural alternatives (e.g., at least one) unless otherwise specified. For example, disclosure of a "C olefin" or a "Bronsted base" is meant to encompass one C olefin or Bronsted base, respectively, or a combination of one or more C olefins or Bronsted bases, unless otherwise specified.

[0019] Generally, groups of elements are designated using the numbering system shown 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 elements in Group 1, alkaline earth metals for elements in Group 2, transition metals for elements in Groups 3-12, and halogens or halides for elements in Group 17.

[0020] 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 arise from a particular set of substituents, unless otherwise specified. A name or structure, unless otherwise specified, includes 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 skilled in the art. For example, the general term hexene (or hexenes) includes all straight- or branched-chain, acyclic or cyclic hydrocarbon compounds having six carbon atoms and one carbon-carbon double bond; the general term pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and the general term butyl group includes n-butyl, sec-butyl, iso-butyl, and t-butyl groups.

[0021] As used herein, the terms "contacting" and "combining" are used to describe compositions, processes / methods, and systems in which materials are contacted or combined in any order, in any manner, and for any length of time, unless otherwise specified. For example, materials may be blended, mixed, slurried, dissolved, reacted, treated, impregnated, compounded, or otherwise contacted or combined in some other manner or by any suitable method or technique.

[0022] The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like do not depend on 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 catalyst sites, or the outcome of the initial components after the components are mixed. 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, and this includes both heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like may be used interchangeably throughout this disclosure.

[0023] As used herein and in the claims, the term "hydrocarbon" always refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of a particular group within the hydrocarbon (e.g., a halogenated hydrocarbon indicates the presence of one or more halogen atoms replacing an equal number of hydrogen atoms within the hydrocarbon). As used herein, the term "hydrocarbyl group" is used according to the definition established by IUPAC and is a monovalent group formed by removing a hydrogen atom from a hydrocarbon. Similarly, a "hydrocarbylene group" refers to a group formed by removing two hydrogen atoms from a hydrocarbon (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms). Thus, as used herein, a "hydrocarbon group" refers to a generalized group formed by removing one or more hydrogen atoms (as many as necessary for the particular group) from a hydrocarbon. "Hydrocarbyl groups," "hydrocarbylene groups," and "hydrocarbon groups" may be acyclic or cyclic, and / or linear or branched. "Hydrocarbyl groups," "hydrocarbylene groups," and "hydrocarbon groups" can include rings, ring systems, aromatic rings, and aromatic ring systems containing only carbon and hydrogen. "Hydrocarbyl groups," "hydrocarbylene groups," and "hydrocarbon groups" include, for example, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups.

[0024] The term "alkane," when used throughout this specification and claims, refers to a saturated hydrocarbon compound. Other identifiers may be utilized to indicate the presence of a particular group within an alkane (e.g., a halogenated alkane indicates the presence of one or more halogen atoms replacing the same number of hydrogen atoms within the alkane). As used herein, the term "alkyl group" is used according to the definition established by IUPAC and is a monovalent group formed by removing a hydrogen atom from an alkane. Similarly, an "alkylene group" refers to a group formed by removing two hydrogen atoms from an alkane (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms). An "alkane group" is a general term that refers to a group formed by removing one or more hydrogen atoms (as many as required for the particular group) from an alkane. "Alkyl groups," "alkylene groups," and "alkane groups" may be acyclic or cyclic and / or straight-chain or branched unless otherwise specified. Primary, secondary, and tertiary alkyl groups are formed by removing hydrogen atoms from primary, secondary, and tertiary carbon atoms of an alkane, respectively. An n-alkyl group can be produced by removing a hydrogen atom from the terminal carbon atom of a straight-chain alkane.

[0025] 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. The term "olefin," unless otherwise specified, includes aliphatic and aromatic, cyclic and acyclic, and / or straight-chain and branched-chain hydrocarbons having at least one carbon-carbon double bond that is not part of an aromatic ring or ring system. Olefins with 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 identified by the position of the carbon-carbon double bond(s).

[0026] The term "alpha olefin," as used herein, refers to any olefin having a carbon-carbon double bond between the first and second carbon atoms in the longest continuous carbon atom chain. The term "alpha olefin," unless otherwise specified, includes straight-chain and branched-chain alpha olefins, as well as alpha olefins that may have multiple non-aromatic carbon-carbon double bonds. The term "standard alpha-olefin," as used herein, refers to a straight-chain aliphatic hydrocarbon monoolefin having a carbon-carbon double bond between the first and second carbon atoms. The term "linear internal olefin," as used herein, refers to a straight-chain aliphatic hydrocarbon monoolefin having a double bond that is not between the first and second carbon atoms.

[0027] "Aromatic compound" refers to a compound containing periodically bonded moieties according to the Huckel (4n+2) rule and containing (4n+2) pi electrons, where n is an integer from 1 to about 5. Aromatic compounds can be monocyclic or polycyclic unless otherwise specified. Non-limiting examples of aromatic compounds include benzene, naphthalene, and toluene, among others.

[0028] The term "substituted," when used to describe a compound or group, for example, when referring to a substituted analog of a particular compound or group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in the group and is intended to be open-ended. As used herein, one or more groups may also be referred to by equivalent terms such as "unsubstituted" or "unsubstituted," which refer to the original group in which a hydrogen in the group is not replaced with a non-hydrogen moiety. "Substituted," unless otherwise specified, is intended to be open-ended and includes inorganic or organic substituents.

[0029] The term oligomer refers to products 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 of the oligomerization reaction zone effluent stream, such as unreacted ethylene, organic reaction medium, and hydrogen, among other components.

[0030] The term "oligomerization" and its derivatives refer to a process that produces an oligomeric product containing at least 20%, 35%, 50%, or 60% by weight of the product containing 2 to 20 monomer units. In one example, an "oligomerization" process using ethylene as the monomer produces a product mixture that contains at least 20%, 35%, 50%, or 60% by weight of oligomers having 4 to 40 carbon atoms.

[0031] The term "reaction zone effluent" and its derivatives (e.g., oligomerization reaction zone effluent) generally refers to all of the materials exiting the reaction zone through the reaction zone outlet / vent that discharges the reaction mixture, and may include reaction zone feed(s) (e.g., ethylene, catalyst system, or catalyst system components, and / or solvent) and / or reaction product (e.g., oligomeric product, including oligomers and non-oligomers). The term "reaction zone effluent" and its derivatives can be modified to refer to a specific portion by using additional modifiers. For example, reaction zone effluent refers to all materials exiting the reaction zone through the reaction zone outlet / vent, while reaction zone oligomeric product effluent refers only to the oligomeric product in the reaction zone effluent.

[0032] As used herein, the term "solvent" refers to a substance that can dissolve a compound or dilute a component of a reaction. Thus, unless otherwise specified, the term "solvent" can encompass a substance that can act as a diluent. In the present invention, several types of ranges are disclosed. When any type of range is disclosed or claimed, the intent is to individually disclose or claim each possible number that such range can reasonably encompass, including not only the endpoints of the range, but also subranges and combinations of subranges therein. For example, when a chemical moiety having a specific number of carbon atoms is disclosed or claimed, the intent is to individually disclose or claim all possible numbers that such range encompasses and that are consistent with the disclosure herein. For example, in this specification, a moiety having a C1 to C 18 A disclosure of a hydrocarbyl group, or in other words a hydrocarbyl group having 1 to 18 carbon atoms, refers to a moiety that can have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as any range between those two numbers (e.g., a C1-C8 hydrocarbyl group), and also any combination of ranges between those two numbers (e.g., C2-C4 and C 12 ~C 16 Similarly, all other ranges disclosed herein should be interpreted similarly to this example.

[0033] In general, any amount, size, formulation, parameter, range, or other quantity or characteristic is "about" or "approximate," whether or not expressly stated as such. Whether or not modified by the term "about" or "approximately," the claims include the equivalent of that quantity or characteristic.

[0034] Features within the present disclosure that are provided as minimum values ​​may alternatively be described as "at least" or "greater than or equal to" any minimum value listed for the feature disclosed herein. Features within the present disclosure that are provided as maximum values ​​may alternatively be described as "less than or equal to" or "less than" the maximum value listed for the feature disclosed herein.

[0035] 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. All publications and patents mentioned herein are incorporated by reference in their entirety, for the purpose of describing and disclosing, for example, the structures and methodologies described in the publications and patents that might be used in connection with the inventions described herein.

[0036] Detailed Description Disclosed herein are systems and processes for producing 1-hexene, 1-octene, or 1-decene in combination with both 1-hexene and 1-octene, as well as a general process for producing higher carbon number normal alpha olefins from lower carbon number normal alpha olefins.

[0037] Developing a process that selectively synthesizes 1-decene is extremely challenging. Ethylene oligomerization processes used to produce 1-hexene and 1-octene often involve a metallacycle mechanism that is ineffective for 1-decene and its higher oligomers. Without being bound by theory, it is believed that the intermediate chromacycle is not stable and readily decomposes before allowing for the insertion of a fifth ethylene to form an 11-membered ring. Therefore, 1-decene is typically synthesized via chemical reactions using catalyst systems that are not selective for one specific molecule (1-decene) and instead produce a series of products that must be inefficiently separated or fractionated. Considering all of the other product fractions that are simultaneously produced, the ethylene efficiency of a process that produces 1-decene will be very low.

[0038] The first object of the present invention is a system and process for producing 1-octene and 1-decene, in which an ethylene oligomerization product stream containing 1-hexene and 1-octene is separated, with the 1-octene portion being the primary product, while the 1-hexene portion typically has a low purity (e.g., less than 95 mol% based on C6). Furthermore, the C6 fraction containing 1-hexene also contains internal and cyclic C6 materials that are difficult to separate without large, complex distillation columns and processes. Instead of purifying and removing the impure C6 stream, metathesis and catalytic isomerization are performed herein, ultimately converting most of the 1-hexene to 1-decene, achieving a selective octene / decene process. Alternatively, a dedicated 1-hexene system can be used to provide 1-hexene for metathesis followed by catalytic isomerization.

[0039] For example, many end uses of 1-hexene require a purity of 99 mole percent or greater (based on C6), but as shown in Table I for an exemplary C6 fraction from an ethylene oligomerization process, it is not uncommon for the 1-hexene purity to be approximately 90 mole percent, with other C6 species present having boiling points within 5-15°C of 1-hexene. Table I shows that the boiling points of the C6 species are so close that isolating 1-hexene at greater than 99 mole percent purity requires complex separations using large distillation columns. Advantageously, when the species in Table I are subjected to metathesis, only 1-hexene metathesizes to 5-decene, making the separation process much easier because alkane impurities (e.g., C6 alkanes generally do not metathesize) or metathesized olefin impurities (not to decene) are much easier to separate from 5-decene than from the C6 components shown in Table I. [Table I]

[0040] Furthermore, end uses of 1-hexene require purities of 99 mol% or greater, whereas most end uses of 1-decene require purities in the 95-98 mol% range (e.g., 96.5 mol% purity). This is due to the lower purity requirements for the desirable normal alpha olefins, compared to C6 hydrocarbons. 10 Further simplifying the hydrocarbon refining process.

[0041] A second object of the present invention is a system and process for producing 1-hexene and 1-decene that first produces a selective ethylene oligomerization product stream containing 1-hexene. A portion of the 1-hexene stream is then subjected to metathesis and catalytic isomerization to ultimately convert that portion of the 1-hexene to 1-decene, thus resulting in a selective hexene / decene process. An advantage of this hexene / decene system and process is that 1-hexene can be produced continuously, while 1-decene can be produced on demand or as needed.

[0042] The disclosed systems and processes provide for the co-production of 1-decene and 1-hexene, or 1-decene and 1-octene. Advantageously, the relative amount of 1-decene produced in these systems and processes can be varied based on market demand, production capacity, and the profitability of each normal alpha olefin (e.g., 1-decene and 1-hexene).

[0043] A third object of the present invention is a process for producing higher carbon number normal alpha olefins from lower carbon number normal alpha olefins, in which the lower carbon number normal alpha olefins are subjected to metathesis and then catalytic isomerization to produce higher carbon number alpha olefins. Advantageously, the lower carbon number normal alpha olefin is 1-butene and the higher carbon number normal alpha olefin is 1-hexene, or, for example, the lower carbon number alpha olefin can be 1-pentene (or 1-hexene, or 1-octene) and the higher carbon number normal alpha olefin can be 1-octene (or 1-decene, or 1-tetradecene).

[0044] Process for producing octene / decene or hexene / decene Aspects of the present invention relate to a process for producing 1-decene in combination with 1-octene or 1-hexene. A first process described herein can be used to produce 1-octene and 1-decene, the first process comprising: a) 15 to 80 mol % C6 olefins, 20 to 80 mol % C8 olefins, and 5 to 20 mol % C 10 + olefins, and a composition comprising the oligomer product comprising: i) a first oligomer composition comprising C6 alkanes and at least 85 mol% C6 olefins, where the C6 olefins comprise at least 80 mol% 1-hexene; ii) a second oligomer composition comprising at least 20 mol% C8 olefins, where the C8 olefins comprise at least 85 mol% 1-octene; and iii) a C6 olefin composition comprising at least 20 mol% C8 olefins, where the C8 olefins comprise at least 85 mol% 1-octene. 10 a) separating the first oligomer composition into a heavy stream containing olefins and a heavy stream containing olefins; and b) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to produce a C 10 forming a first composition comprising a linear internal olefin; and c) in the presence of actinic radiation, 10 contacting all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying the second composition to isolate a third composition comprising at least 90 mole % 1-decene.

[0045] A second process described herein may be used to produce 1-hexene and 1-decene, the second process comprising: a) separating a composition comprising an oligomeric product comprising at least 85 mol% C6 olefins and at least 5 mol% C8+ olefins into i) a first oligomeric composition comprising C6 alkanes and at least 90 mol% C6 olefins, where the C6 olefins comprise at least 90 mol% 1-hexene, and ii) a heavier stream comprising C8+ olefins; and b) contacting all or a portion of the first oligomeric composition with a metathesis catalyst system to produce 1-hexene and 1-decene. 10forming a first composition comprising a linear internal olefin; and c) in the presence of actinic radiation, 10 contacting all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying the second composition to isolate a third composition comprising at least 90 mole % 1-decene.

[0046] Generally, features of the first and second processes (e.g., the oligomeric product, the first oligomeric composition, the second oligomeric composition, the metathesis step, the catalytic isomerization step, and the purification step, among other features) are described independently herein, and these features can be combined in any combination to further describe these two processes. Furthermore, unless otherwise specified, additional process steps can be performed before, during, and / or after these process steps.

[0047] Referring now to the first process, step a) is a process for producing a olefin mixture of 15 to 80 mol% of C6 olefins, 20 to 80 mol% of C8 olefins, and 5 to 20 mol% of C 10 + olefins, and a composition comprising the oligomer product comprising: i) a first oligomer composition comprising C6 alkanes and at least 85 mol% C6 olefins, where the C6 olefins comprise at least 80 mol% 1-hexene; ii) a second oligomer composition comprising at least 20 mol% C8 olefins, where the C8 olefins comprise at least 85 mol% 1-octene; and iii) a C6 olefin composition comprising at least 20 mol% C8 olefins, where the C8 olefins comprise at least 85 mol% 1-octene. 10+ a heavy stream containing olefins. In step a) of the first process, the composition containing the oligomer product may be a reaction zone effluent from an ethylene oligomerization reactor / system and may be formed by contacting ethylene, a catalyst system or catalyst system components, optionally an organic reaction medium, and optionally hydrogen in the reaction zone. In one aspect, the catalyst system or catalyst system components may include a heteroatom ligand chromium compound complex and an alkyl aluminum compound, or a heteroatom ligand, a chromium compound, and an alkyl aluminum compound. Thus, in addition to the oligomer product, the composition (e.g., reaction zone effluent) may contain a catalyst (activated or deactivated) and an organic reaction medium. Separation (or fractionation) of the composition containing the oligomer product may occur in one or more steps (usually multiple steps) to form a first oligomer composition, a second oligomer composition, and a heavy stream. Representative patent literature relating to ethylene oligomerization processes and catalyst systems includes U.S. Pat. Nos. 9,962,689, 10,329,212, 10,414,698, 10,414,699, 10,435,336, 10,464,862, 10,493,422, 10,519,077, and 11,267,909.

[0048] For the first process, the oligomeric product of step a) is preferably 15-80 mol % C6 olefins, 20-80 mol % C8 olefins, and 5-20 mol % C6 olefins prior to separation (or fractionation). 10 + olefins. For example, the oligomer product may contain 25 to 75 mol % C6 olefins in one embodiment, 30 to 70 mol % C6 olefins in another embodiment, 35 to 65 mol % C6 olefins in yet another embodiment, and 40 to 60 mol % C6 olefins in yet another embodiment. Additionally or alternatively, the oligomer product may contain 25 to 75 mol % C8 olefins in one embodiment, 30 to 70 mol % C8 olefins in another embodiment, 35 to 65 mol % C8 olefins in yet another embodiment, and 40 to 60 mol % C8 olefins in yet another embodiment. Additionally or alternatively, the oligomer product may contain 5 to 18 mol % C10 + olefin or 5-15 mol% C 10 + olefin or 7-20 mol% C 10 + olefin or 7-18 mol% C 10 + olefins. As those skilled in the art will readily appreciate, the sum of these and other components does not exceed 100 mole %.

[0049] The composition containing the oligomer product comprises: i) a first oligomer composition comprising C6 alkanes and at least 85 mol% C6 olefins, where the C6 olefins comprise at least 80 mol% 1-hexene; ii) a second oligomer composition comprising at least 20 mol% C8 olefins, where the C8 olefins comprise at least 85 mol% 1-octene; and iii) a C8 olefin composition comprising at least 20 mol% C8 olefins, where the C8 olefins comprise at least 85 mol% 1-octene. 10+ a heavy stream containing olefins. Referring now to the first oligomer composition, in some embodiments, it can contain at least 85 mol%, at least 90 mol%, at least 93 mol%, or at least 95 mol% C6 olefins. Thus, typical ranges for the amount of C6 olefins in the first oligomer composition can include, but are not limited to, 85-99 mol%, 90-99.5 mol%, 93-98 mol%, 95-99 mol%, etc. While at least 80 mol% of the C6 olefins are 1-hexene, often the C6 olefins can contain at least 85 mol%, at least 90 mol%, or at least 95 mol% 1-hexene; thus, typical ranges include 80 mol%-98 mol%, 80 mol%-95 mol%, 85 mol%-95 mol%, or 90-99 mol% 1-hexene. In addition to 1-hexene, the C6 olefins can contain internal and cyclic C6 olefins (e.g., 2-hexene, 3-hexene, methylenecyclopentane, etc.), and the C6 olefins can often comprise 0.1 to 10 mol%, 0.5 to 8 mol%, 0.5 to 6 mol%, 1 to 8 mol%, or 1 to 6 mol% of the total internal and cyclic C6 olefins. C6 alkanes are also present in the first oligomer composition, and representative C6 alkanes include methylcyclopentane and n-hexane. Typically, the first oligomer composition contains 0.5 to 12 mol%, 0.5 to 10 mol%, 1 to 10 mol%, 1 to 8 mol%, 1.5 to 8 mol%, 2 to 8 mol%, or 2 to 6 mol% of the C6 alkanes.

[0050] In the first process, the second oligomer composition can comprise at least 20 mol% C8 olefins, and the C8 olefins can contain at least 85 mol% 1-octene. In some embodiments, the second oligomer composition can contain at least 50 mol%, at least 75 mol%, at least 90 mol%, at least 95 mol%, at least 96 mol%, or at least 97 mol% C8 olefins. Thus, typical ranges for the amount of C8 olefins in the second oligomer composition can include, but are not limited to, 20-99 mol%, 50-99 mol%, 75-99 mol%, 85-99 mol%, 90-99.5 mol%, 95-99.5 mol%, 97-99 mol%, etc. At least 85 mol% of the C8 olefins are 1-octene, but often the C8 olefins contain at least 90 mol%, at least 95 mol%, or at least 97 mol% 1-octene, with typical ranges therefore including 85 mol% to 98 mol%, 90 mol% to 99 mol%, 95 mol% to 98 mol%, or 97 to 99.5 mol% 1-octene.

[0051] Now, referring to step b) of the first process, contacting a metathesis catalyst system with all or a portion of the first oligomer composition to produce C 10 A first composition is formed that includes linear internal olefins. The first composition typically contains at least 85 mol%, at least 90 mol%, at least 92 mol%, or at least 95 mol% C6+ olefins, based on the C6+ olefins in the first oligomer composition. 10 Suitable metathesis catalyst systems for step b) are disclosed below, and any suitable conditions for metathesis step b) can be used, as will be appreciated by those skilled in the art in light of this disclosure, e.g., U.S. Pat. No. 8,765,984.

[0052] Optionally, prior to step c), the first process comprises at least 90 mol %, at least 93 mol %, or at least 96 mol % C 10The method may further include isolating the linear internal olefin-containing composition from the first composition. Any suitable technique, such as extraction, filtration, evaporation, distillation, or the like, as well as any combination thereof, may be used. Advantageously, the C6 alkanes in the first oligomer composition do not undergo metathesis, so these materials are readily isolated from the C6 alkanes. 10 It can be separated relatively easily from the linear internal olefins. Similarly, methylenecyclopentane is less reactive in metathesis, so this material can also be separated from C 10 They can be separated relatively easily from linear internal olefins. Furthermore, internal C6 olefins can be separated into non-C6 olefins by metathesis. 10 Forms olefins, also C 10 It is easily separated from the linear internal olefins.

[0053] In step c), C 10 All or a portion of the linear internal olefin (e.g., 5-decene) is contacted with a catalytic isomerization catalyst system in the presence of actinic radiation to form a second composition comprising 1-decene. Any suitable catalytic isomerization catalyst system can be used, provided it is suitable for chain transfer of the double bond to a terminal position. Suitable catalytic isomerization catalyst systems for step c) are disclosed in the following, and any suitable conditions for the catalytic isomerization step c) can be used, as will be recognized by those of skill in the art in light of this disclosure, e.g., J.Am.Chem.Soc. 2022, 144, 137-144; J.Am.Chem.Soc. 2022, 144, 145-152; J.Am.Chem.Soc. 2021, 143, 30, 11670-11678; Eur.J.Org.Chem.2017, 2056-2071; and Angewandte Chemie International Edition, Volume 51(23), June 4, 2012.

[0054] Generally, the molar yield of 1-decene in step c) can be at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, or at least 90%. The molar yield of 1-decene can be determined by the amount of C12 contacted with the catalytic isomerization catalyst system in the presence of actinic radiation in step c). 10Based on the initial amount of linear internal olefins.

[0055] In step d) of the first process, the second composition containing 1-decene can be purified to isolate a third composition containing at least 90 mol% 1-decene. The third composition containing 1-decene can be isolated or separated from the second composition using any suitable technique, such as extraction, filtration, evaporation, distillation, or any combination of two or more of these techniques. The third composition contains at least 90 mol% 1-decene, but in some embodiments, the third composition can contain at least 92 mol%, at least 95 mol%, at least 97 mol%, or at least 98 mol% 1-decene. Thus, typical ranges for the amount of 1-decene in the third composition include, but are not limited to, 90-99 mol%, 92-99.5 mol%, 95-99 mol%, 98-99.5 mol%, etc.

[0056] Optionally, the first process comprises contacting a metathesis catalyst system with all or a portion of a C olefin composition (a second oligomer composition comprising a C olefin) to produce a C 14 Optionally, the first process may further include contacting a metathesis catalyst with a light oligomer composition comprising C6 and C8 olefins to form an olefin composition. 10 ~C 14 The method may further include forming a composition comprising a linear internal olefin. The light oligomer composition may be formed by combining at least a portion of the first oligomer composition (containing 1-hexene) and the second oligomer composition (containing 1-octene) in any relative amounts.

[0057] Referring now to the second process, step a) separates (or fractionates) a composition containing an oligomer product, the oligomer product comprising at least 85 mol% C6 olefins and at least 5 mol% C8+ olefins, into: i) a first oligomer composition comprising C6 alkanes and at least 90 mol% C6 olefins, the C6 olefins comprising at least 90 mol% 1-hexene; and ii) a heavy products stream comprising C8+ olefins. As in the first process, in step a) of the second process, the composition containing the oligomer product can be a reaction zone effluent from an ethylene oligomerization reactor / system. In addition to the oligomer product, the composition (e.g., reaction zone effluent) can contain a catalyst (activated or deactivated) and an organic reaction medium. Separating (or fractionating) the composition containing the oligomer product can be carried out in one or more steps (usually multiple steps) to form the first oligomer composition and the heavy products stream.

[0058] It is important to note that the oligomer product in the second process is different from the oligomer product in the first process, and the resulting fractionated compositions are also different. In the first process, the oligomer product is 15-80 mol % C6 olefins, 20-80 mol % C8 olefins, and 5-20 mol % C 10 + olefins, while the oligomer product in the second process contains at least 85 mol % C6 olefins and at least 5 mol % C8+ olefins. In the first process, the oligomer product contains a first oligomer composition (predominantly C6), a second oligomer composition (predominantly C8), and C 10In the first process, the oligomeric product is separated into a heavy stream containing C6+ olefins, whereas the oligomeric product in the second process is separated into the first oligomeric composition (predominantly C6) and a heavy stream containing C8+ olefins. The composition containing the oligomeric product from the second process is often obtained from a 1-hexene process, whereas the composition containing the oligomeric product from the first process may be obtained from a 1-hexene / 1-octene process.

[0059] For the second process, the oligomer product of step a) contains at least 85 mol% C6 olefins and at least 5 mol% C8+ olefins prior to separation (or fractionation). For example, the oligomer product may contain at least 87 mol% C6 olefins in one embodiment, at least 90 mol% C6 olefins in another embodiment, at least 91 mol% C6 olefins in yet another embodiment, and at least 93 mol% C6 olefins in yet another embodiment. Additionally or alternatively, the oligomer product may contain 5-15 mol% C8+ olefins; alternatively, 5-12 mol% C8+ olefins; alternatively, 6-14 mol% C8+ olefins; or alternatively, 7-13 mol% C8+ olefins. As those skilled in the art will readily recognize, the sum of these and other components does not exceed 100 mol%.

[0060] The composition containing the oligomer product is separated into: i) a first oligomer composition comprising C6 alkanes and at least 90 mol% C6 olefins, the C6 olefins comprising at least 90 mol% 1-hexene; and ii) a heavies stream comprising C8+ olefins. Referring now to the first oligomer composition, in some embodiments, it can contain at least 92 mol%, at least 94 mol%, at least 96 mol%, or at least 98 mol% C6 olefins. Thus, typical ranges for the amount of C6 olefins in the first oligomer composition can include, but are not limited to, 92-99 mol%, 94-99.9 mol%, 96-99.9 mol%, 98-99.9 mol%, etc. At least 90 mol% of the C6 olefins are 1-hexene, but often the C6 olefins can contain at least 94 mol%, at least 96 mol%, or at least 98 mol% 1-hexene; thus, typical ranges include 90 mol% to 99 mol%, 94 mol% to 99.9 mol%, 96 mol% to 99.9 mol%, or 98 mol% to 99.9 mol% 1-hexene. In addition to 1-hexene, the C6 olefins often contain small amounts of internal and cyclic C6 olefins (e.g., 2-hexene, 3-hexene, methylenecyclopentane, etc.), and the C6 olefins often comprise 0.1 mol% to 3 mol%, 0.2 mol% to 2 mol%, or 0.25 mol% to 1 mol% of the total internal and cyclic C6 olefins. C6 alkanes are also often present in small amounts in the first oligomer composition; representative C6 alkanes include methylcyclopentane and n-hexane. Typically, the first oligomer composition in the second process contains 0.1 mol % to 1.5 mol %, 0.15 mol % to 1 mol %, or 0.2 mol % to 0.75 mol % of C6 alkanes.

[0061] Steps b), c), and d) of the second process may be carried out substantially as described herein for steps b), c), and d), respectively, of the first process.

[0062] Optionally, similar to the first process, the second process comprises extracting at least 90 mol%, at least 93 mol%, or at least 96 mol% C from the first composition prior to step c). 10 The method may further include isolating the composition containing linear internal olefins. Any suitable technique, such as extraction, filtration, evaporation, distillation, or the like, as well as any combination thereof, may be used. Advantageously, since the C6 alkanes in the first oligomer composition do not undergo metathesis, these materials are isolated from the C6 alkanes. 10 It can be separated relatively easily from the linear internal olefins. Similarly, methylenecyclopentane is less reactive in metathesis, so this material can also be separated from C 10 They can be separated relatively easily from linear internal olefins. Furthermore, internal C6 olefins can be separated into non-C6 olefins by metathesis. 10 Forms olefins, also C 10 It is easily separated from the linear internal olefins.

[0063] Metathesis catalyst system Without limitation, the metathesis catalyst systems disclosed herein can be used to convert 1-hexene in the first oligomer composition to C 10 A first composition containing a linear internal olefin can be formed. Any suitable metathesis catalyst system can be used in the metathesis step, non-limiting examples of which include a metal oxide-based metathesis catalyst system, a metal halide-based metathesis catalyst system, a metal carbene-based metathesis catalyst system, or any combination thereof. In one embodiment, the metathesis catalyst system can be a metal oxide-based metathesis catalyst system or a metal halide-based metathesis catalyst system, while in another embodiment, the metathesis catalyst can be a metal oxide-based metathesis catalyst system; alternatively, a metal halide-based metathesis catalyst system; or alternatively, a metal carbene-based metathesis catalyst system.

[0064] The metal oxide-based metathesis catalyst system may comprise (or consist essentially of, or consist of) cobalt oxide, molybdenum oxide, tungsten oxide, rhenium oxide, or any combination thereof. For example, the metal oxide-based catalyst system may comprise (or consist essentially of, or consist of) cobalt oxide; alternatively, molybdenum oxide; alternatively, tungsten oxide; or alternatively, rhenium oxide. Optionally, the metal oxide-based metathesis catalyst system may further comprise a support, or a metal alkyl activator, or both a support and a metal alkyl activator. Exemplary supports can include alumina, silica, silica-alumina, and aluminum phosphate, among other solid oxide materials. Thus, non-limiting examples of supported metal oxide-based metathesis catalyst systems can include molybdenum oxide on alumina (MoO3 / Al2O3), tungsten oxide on silica (WO3 / SiO2), rhenium oxide on alumina (Re2O7 / Al2O3), cobalt and molybdenum oxides on alumina (CoO / MoO3 / Al2O3), and rhenium oxide on alumina activated with tetramethyltin (Re2O7 / Al2O3 / SnMe4). Other suitable metal oxide-based metathesis catalyst systems are also known to those skilled in the art.

[0065] Additionally, the metal oxide-based metathesis catalyst system can include a metal alkyl activator, which may include an alkyllithium, alkylmagnesium, alkylaluminum, alkyltin compound, or any mixture thereof. In one embodiment, the metal alkyl activator can be an alkyllithium compound. In another embodiment, the metal alkyl activator can be an alkylmagnesium compound. In another embodiment, the metal alkyl activator can be an alkylaluminum compound. In yet another embodiment, the metal alkyl activator can be an alkyltin compound. Non-limiting examples of alkylaluminum compounds can include trialkylaluminum compounds and / or alkylaluminum halide compounds. The alkyl group on the metal alkyl activator can be any C1-C 10The alkyl group may include a hydrocarbyl group, or alternatively, any C1-C5 hydrocarbyl group. In various embodiments, the alkyl group of the metal alkyl activator may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, or tert-butyl; alternatively, methyl, ethyl, n-butyl, sec-butyl, or tert-butyl; alternatively, methyl; alternatively, ethyl; alternatively, n-butyl; alternatively, sec-butyl; or alternatively, tert-butyl. Representative examples of suitable trialkylaluminum compounds include trimethylaluminum, triethylaluminum, and triisobutylaluminum. The halide of the alkylaluminum halide compound may be chloride, bromide, or iodide; alternatively, chloride; alternatively, bromide; or alternatively, iodide. Examples of suitable alkylaluminum halide compounds include ethylaluminum dichloride, diethylaluminum chloride, and ethylaluminum sesquichloride. Suitable, non-limiting examples of alkyltin compounds include tetramethyltin, tetraethyltin, and tetrabutyltin.

[0066] The metal halide-based metathesis catalyst system may comprise (or consist essentially of, or consist of) a tungsten halide, a molybdenum halide, or a combination thereof. For example, the metal halide-based metathesis catalyst system may comprise (or consist essentially of, or consist of) a tungsten halide, or alternatively, a molybdenum halide. The halide of the metal halide-based metathesis catalyst system may be a chloride, bromide, or iodide. In one embodiment, the halide may be a chloride; in another embodiment, the halide may be a bromide; and in yet another embodiment, the halide may be an iodide. Thus, the metal halide-based metathesis catalyst system may comprise (or consist essentially of, or consist of) tungsten chloride, molybdenum chloride, or a mixture thereof; alternatively, tungsten chloride; or alternatively, molybdenum chloride. Optionally, the metal halide-based metathesis catalyst system may further comprise a metal alkyl activator (as described herein), oxygen, an alcohol, or any combination thereof; alternatively, a metal alkyl activator; alternatively, oxygen; or alternatively, an alcohol. Non-limiting examples of metal halide-based metathesis catalyst systems may include tungsten chloride / tetrabutyltin (WCl / SnMe), tungsten chloride / ethylaluminum dichloride (WCl / EtAlCl), tungsten chloride / ethylaluminum dichloride / ethyl alcohol (WCl / EtAlCl / EtOH), molybdenum chloride / triethylaluminum (MoCl / AlEt), and molybdenum chloride / triethylaluminum / O (MoCl / AlEt / O). Other suitable metal halide-based metathesis catalyst systems are known to those skilled in the art.

[0067] Metal carbene-based metathesis catalyst systems can comprise (or consist essentially of, or consist of) tungsten, tantalum, osmium, molybdenum, ruthenium, or any combination thereof. For example, metal carbene-based metathesis catalyst systems can comprise (or consist essentially of, or consist of) tungsten; alternatively, tantalum; alternatively, osmium; alternatively, molybdenum; or alternatively, ruthenium. These metal carbene-based metathesis catalyst systems can contain compounds that have a stable metal-carbon double bond or can form a metal-carbon double bond in situ from a metal precursor that has a stable metal-carbon single bond. In one aspect, the ruthenium carbene-based metathesis catalyst system has the structure L 1 L 2 X2Ru=CHR 1 In some cases, the compound may include a compound having the formula 1 and L 2 can be an organic ligand, X can be a halide, and R can be hydrogen or a hydrocarbyl group. 1 L 2 X2Ru=CHR 1 The compounds of the ruthenium carbene-based metathesis catalyst system having the formula: 1 , L 2 , X or R 1 can be described using any combination of

[0068] Generally, L 1 and L 2 can independently be R'3P, an imidazolinylidene group, or an imidazolidinylidene group. 1 and L 2 can be R'3P, or L 1 can be R'3P, and L 2 can be an imidazolinylidene or imidazolidinylidene group, or L 1 can be R'3, and L 2 can be an imidazolinylidene group, or L 1 can be R'3P, and L2 can be an imidazolidinylidene group, or L 1 and L 2 can be an imidazolinylidene group, or L 1 and L 2 can be an imidazolidinylidene group. In embodiments of the invention, R' can be a hydrocarbyl group, where each R' in R'3P can be the same, or each R' in R'3P can be different, or one R' in R'3P can be different from the other two R' groups. In some embodiments, each R' in R'3P is independently C1 to C 15 or a hydrocarbyl group of C1 to C 10In other embodiments, each hydrocarbyl R' in R'P can independently be an alkyl group or an aromatic group, or an alkyl group or an aromatic group. In one embodiment, each alkyl R' in R'P can independently be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a neopentyl group, a cyclopentyl group, or a cyclohexyl group. In some embodiments, one or more R' groups in R'P can be a phenyl group or a substituted phenyl group. In one embodiment, the R substituents of any substituted phenyl group can independently be a C1-C5 organyl group or a C1-C5 hydrocarbyl group. In some embodiments, R'P can be a trialkylphosphine or triphenylphosphine, alternatively a trialkylphosphine, or alternatively a triphenylphosphine. In one aspect, R'3P can be trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-tert-butylphosphine, tri-neopentylphosphine, tricyclopentylphosphine, tricyclohexylphosphine or triphenylphosphine, alternatively triisopropylphosphine, tri-tert-butylphosphine, tri-neopentylphosphine, tricyclopentylphosphine, tricyclohexylphosphine or triphenylphosphine, alternatively tricyclopentylphosphine, tricyclohexylphosphine or triphenylphosphine, alternatively tricyclopentylphosphine or tricyclohexylphosphine, alternatively tricyclopentylphosphine, alternatively tricyclohexylphosphine, or alternatively triphenylphosphine.

[0069] In one embodiment, the imidazolinylidene or imidazolidinylidene group is a C3-C 80 an imidazolinylidene or imidazolidinylidene group; alternatively, a C3-C 50 an imidazolinylidene or imidazolidinylidene group; or alternatively, a C5-C 40It may be an imidazolinylidene group or an imidazolidinylidene group. In some embodiments, the imidazolinylidene group may be a 1,3-disubstituted imidazolinylidene group. In some embodiments, the imidazolidinylidene group may be a 1,3-disubstituted imidazolidinylidene group. In one embodiment, the 1,3-substituents of the 1,3-disubstituted imidazolinylidene group or the 1,3-disubstituted imidazolidinylidene group may independently be any suitable hydrocarbyl group. In one embodiment, the 1,3-substituents of the 1,3-disubstituted imidazolinylidene group or the 1,3-disubstituted imidazolidinylidene group may independently be C1 to C6. 30 In some embodiments, the 1,3-substituents of the 1,3-disubstituted imidazolinylidene group or the 1,3-disubstituted imidazolidinylidene group can be independently C6 to C6 20 Aromatic group or C1-C 10 In another embodiment, the 1,3-substituents of the 1,3-disubstituted imidazolinylidene group or the 1,3-disubstituted imidazolidinylidene group are independently C6 to C6 alkyl groups. 20 Aromatic groups, or alternatively C1-C 10 It can be an alkyl group. In one embodiment, each aromatic group in the 1,3-disubstituted imidazolinylidene group or 1,3-disubstituted imidazolidinylidene group can independently be a substituted aromatic group. In some embodiments, the substituted aromatic group in the 1,3-disubstituted imidazolinylidene group or 1,3-disubstituted imidazolidinylidene group can be a 2-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group; alternatively, a 2,6-disubstituted phenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group. Suitable substituents for any substituted phenyl group in the 1,3-disubstituted imidazolinylidene group or 1,3-disubstituted imidazolidinylidene group include any C1-C 10

[0023] The 1,3-disubstituted imidazolinylidene or 1,3-disubstituted imidazolidinylidene groups may each independently be a 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl group; alternatively, a 2,6-diisopropylphenyl group; or alternatively, a 2,4,6-trimethylphenyl group. In some embodiments, each hydrocarbyl substituent may independently be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; alternatively, a methyl group, an ethyl group, an isopropyl group, or alternatively, a tert-butyl group. In some embodiments, each substituted aromatic group of the 1,3-disubstituted imidazolinylidene or 1,3-disubstituted imidazolidinylidene group may independently be a 2,6-diisopropylphenyl group or a 2,4,6-trimethylphenyl group; alternatively, a 2,6-diisopropylphenyl group; or alternatively, a 2,4,6-trimethylphenyl group.

[0070] In various embodiments, the structure L 1 L 2 X2Ru=CHR 1 Each X in the compound having structure L can independently be chloride, bromide, or iodide. In one embodiment, X can be chloride. In another embodiment, X can be bromide. In yet another embodiment, X can be iodide. 1 L 2 X2Ru=CHR 1 R of a compound having 1 is hydrogen or C1-C 20 In some embodiments, R 1 can be a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a 2-methyl-2-propene group, or a 2,2-diphenylethene group. 1 may be a tert-butyl group, a phenyl group, a 2-methyl-2-propene group, or a 2,2-diphenylethene group, alternatively a hydrogen, alternatively a tert-butyl group, alternatively a phenyl group, alternatively a tert-butyl group, alternatively a phenyl group, alternatively a 2-methyl-2-propene group, or alternatively a 2,2-diphenylethene group.

[0071] In some non-limiting embodiments, the ruthenium carbene-based metathesis catalyst system can include dichloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium, dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine)ruthenium, dichloro(3-methyl-2-butenylidene)bis(tricyclopentylphosphine)ruthenium, 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene)dichloro(tricyclohexylphosphine)ruthenium, or 1,3-bis-(2,6-diisopropylphenyl)-2-(imidazolidinylidene)(phenylmethylene)dichloro(tricyclohexylphosphine)ruthenium. In some embodiments, the ruthenium carbene-based metathesis catalyst system may comprise dichloro(phenylmethylene)bis(tricyclohexylphosphine)ruthenium; alternatively, dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine)ruthenium; alternatively, 1,3-bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(phenylmethylene)dichloro(tricyclohexylphosphine)ruthenium; or alternatively, 1,3-bis-(2,6-diisopropylphenyl)-2-(imidazolidinylidene)(phenylmethylene)dichloro(tricyclohexylphosphine)ruthenium.

[0072] In one embodiment, the molybdenum carbene-based metathesis catalyst system has the structure Mo(=CHR 2 )(NAr)(OR 3 )2, wherein R 2 is hydrogen or a hydrocarbyl group, Ar is a substituted aromatic ring, and R 3 is a hydrocarbyl group or a halogenated hydrocarbyl group. Generally, the structure Mo(=CHR 2 )(NAr)(OR 3 The compounds in the molybdenum carbene-based metathesis catalyst system having the R 2 , Ar, and R 3 can be described using any combination of

[0073] In some embodiments, the structure Mo(=CHR 2 )(NAr)(OR 3 )2 of the compound R 2 is hydrogen or C1-C 20 a hydrocarbyl group, or alternatively a C1-C 20 In some embodiments, R 2 can be a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a phenyl group, a 2-methyl-2-propene group, or a 2,2-diphenylethene group. 2 may be a tert-butyl group, a phenyl group, a 2-methyl-2-propene group, or a 2,2-diphenylethene group, alternatively a tert-butyl group or a phenyl group, alternatively a hydrogen, alternatively a tert-butyl group, alternatively a phenyl group, alternatively a 2-methyl-2-propene group, or alternatively a 2,2-diphenylethene group.

[0074] In one embodiment, the structure Mo(=CHR 2 )(NAr)(OR 3 The substituted aromatic ring Ar of the compound having 2 is C6-C 30 Aromatic groups, or alternatively C6-C 20 In some embodiments, each substituent of the substituted aromatic ring Ar is independently a C-C 20 Hydrocarbyl groups, C1-C 10In some embodiments, the substituted aromatic ring Ar can be a 2-substituted phenyl group, a 2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group. In one embodiment, each substituent on the substituted aromatic ring can independently be a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a neopentyl group; alternatively, a methyl group, an isopropyl group, or a tert-butyl group; alternatively, a methyl group or an isopropyl group. In some embodiments, each substituent on the substituted aromatic ring can independently be a methyl group; alternatively, an isopropyl group, or alternatively, a tert-butyl group. In some non-limiting embodiments, the substituted aromatic ring Ar can be a 2-tert-butylphenyl group, a 2,6-dimethylphenyl group, a 2,6-diisopropylphenyl group, or a 2,4,6-trimethylphenyl group; alternatively, a 2-tert-butylphenyl group; alternatively, a 2,6-dimethylphenyl group; alternatively, a 2,6-diisopropylphenyl group; or alternatively, a 2,4,6-trimethylphenyl group.

[0075] In one embodiment, the structure Mo(=CHR 2 )(NAr)(OR 3 Each R3 in the compound having 2 is independently C1 to C 10 In some embodiments, the alkyl group may be a C1-C5 organic group, or alternatively, a C1-C5 organic group. 10 Alternatively, the C1-C5 organic group may be a hydrocarbylhalyl group (a group consisting of hydrogen, carbon, and halogen atoms), alternatively a hydrocarbylfluoryl group (a group consisting of hydrogen, carbon, and fluorine atoms), or alternatively a hydrocarbyl group. In one aspect, the halogen atoms of the hydrocarbylhalyl group may be fluorine, chlorine, bromine, iodine, or any combination thereof; alternatively, fluorine; alternatively, chlorine; alternatively, bromine; or alternatively, iodine. In some aspects, each R 3 may independently be a tert-butyl group or a hexafluoro-tert-butyl group. 3 )2 can represent a single organic group, where two R 3The groups are connected via a bond between any divalent, trivalent, or tetravalent atom within the R group. In further embodiments, (OR) can represent a single organic group, where two R atoms bonded to an oxygen atom 3 The group consists of two R 3 The group is connected via a carbon-carbon bond between any carbon atoms of the group.

[0076] In one embodiment, the molybdenum carbene-based metathesis catalyst system may include Mo(=CH-C(CH3)3)(N-2,6-diisopropylphenyl)(OC(CH3)3), Mo(=CH-C(CH3)2(CH6H5))(N-2,6-diisopropylphenyl)(OC(CH3)3), Mo(=CH-C(CH3)3)(N-2,6-diisopropylphenyl)(OC(CH3)(CF3)2), or Mo(=CH-C(CH3)2(CH6H5))(N-2,6-diisopropylphenyl)(OC(CH3)(CF3)2). In other embodiments, the molybdenum carbene-based metathesis catalyst system can include Mo(=CH-C(CH3)3)(N-2,6-diisopropylphenyl)(OC(CH3)3), alternatively Mo(=CH-C(CH3)2(CH6H5))(N-2,6-diisopropylphenyl)(OC(CH3)3), alternatively Mo(=CH-C(CH3)3)(N-2,6-diisopropylphenyl)(OC(CH3)(CF3)2), or alternatively Mo(=CH-C(CH3)2(CH6H5))(N-2,6-diisopropylphenyl)(OC(CH3)(CF3)2).

[0077] Optionally, the metal carbene-based metathesis catalyst system may further comprise a support. Exemplary supports include alumina, silica, silica-alumina, and aluminum phosphate, among other solid oxide materials. Additionally, the support may comprise a polymer, and the metal carbene metathesis catalyst compound may be bound to the support via any ligand that does not contain a metal-carbon double bond.

[0078] Catalytic isomerization catalyst system In step c), C 10All or a portion of a linear internal olefin (e.g., 5-decene) is contacted with a catalytic isomerization catalyst system in the presence of actinic radiation to form a second composition containing 1-decene. Any suitable catalytic isomerization catalyst system can be used as long as it can efficiently transfer a double bond to a terminal position. In one aspect, the catalytic isomerization catalyst system can include a photocatalyst, a hydrogen atom transfer agent, a metal ion, and a proton donor. Referring first to the photocatalyst, the photocatalyst can include a transition metal complex, an organic dye (e.g., 3,6-di-tert-butyl-9-mesityl-10-phenylacridinium tetrafluoroborate), 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, or a semiconductor (e.g., TiO). Exemplary transition metal complexes include iridium-based photocatalysts (e.g., [Ir(dF(CF3)ppy)2(5,5'-d(CF3)bpy)]PF6), ruthenium-based photocatalysts, and the like. Although not limited thereto, suitable photocatalysts often have a redox potential in the range of 0.7 V to 2.0 V relative to Fc / Fc in MeCN, and in some cases, the redox potential may be in the range of 1.3 to 1.8 V.

[0079] The hydrogen atom transfer agent can be a Bronsted base, which in some embodiments can include an organic base, while in other embodiments the Bronsted base can include a pyridine base (e.g., 4,4'-di-tert-butyl-2,2'-dipyridine) or a pyridyl ligand of a metal ion (e.g., 4,4'-di-tert-butyl-2,2'-dipyridyl). Other illustrative, non-limiting examples of transfer agents can include cytochrome p450, iron porphyrin, iron cyclam, chromyl chloride, MnO, iron zeolite, and the like, and any combination thereof.

[0080] The metal ion component of the catalytic isomerization catalyst system can include chromium ions (e.g., chromium(II) ions, chromium(III) ions), and for example, the metal ions can include metal salts (e.g., chromium(II) dihalide, chromium(III) trihalide). The proton donor can include alcohols (e.g., primary alcohols, secondary alcohols, aliphatic alcohols, primary aliphatic alcohols, fluorinated alcohols), carboxylic acids, water, and the like, and combinations thereof. Thus, the proton donor can often include C1-C8 primary aliphatic alcohols, examples of which include methanol, ethanol, n-propanol, isopropanol, and the like.

[0081] The relative amounts of the photocatalyst, hydrogen atom transfer agent, metal ion, and proton donor in the catalytic isomerization catalyst system are not particularly limited. However, the molar ratio of the Bronsted base (or other transfer agent) to the photocatalyst is often in the range of 5:1 to 1:1 (e.g., 3:1), and additionally or alternatively, the molar ratio of the metal ion to the photocatalyst is often in the range of 3:1 to 1:1 (e.g., 2:1), and additionally or alternatively, the molar ratio of the proton donor to the photocatalyst is often in the range of 3:1 to 1:1 (e.g., 1:1).

[0082] The amount of photocatalyst in the catalytic isomerization catalyst system is C 10 There is no particular limitation on the amount of linear internal olefin. For example, 10 The amount of photocatalyst based on the linear internal olefin can range from 0.1 mol % to 10 mol % in one embodiment, from 0.5 mol % to 8 mol % in another embodiment, and from 1 mol % to 5 mol % in yet another embodiment.

[0083] In this catalyst system, step c) optionally comprises reacting the catalyst system with C in the presence of a solvent. 10The linear internal olefin may be contacted with the olefin. Organic solvents such as, but not limited to, acetonitrile, dioxane, trifluorobenzene, and mixtures thereof may be utilized. Step c) may be carried out at any suitable temperature. In some non-limiting embodiments, the temperature may range from 0°C to 100°C, alternatively from 0°C to 60°C, alternatively from 0°C to 40°C, alternatively from 15°C to 75°C, alternatively from 15°C to 50°C, alternatively from 15°C to 40°C, alternatively from 20°C to 40°C, or alternatively from 30°C to 40°C. These temperature ranges are intended to encompass situations in which step c) is carried out at a series of different temperatures within each temperature range, rather than at a single fixed temperature.

[0084] Similarly, any suitable actinic radiation can be used in step c) The actinic radiation can include light of any suitable wavelength(s), such as blue light (e.g., light from a blue light source), and the actinic radiation can include wavelengths in the range of 450-495 nm, such as at or near 456 nm.

[0085] In another embodiment, the catalytic isomerization catalyst system can include a photocatalyst, a metal-containing cocatalyst, and an optional disulfide compound. In this embodiment, the photocatalyst can include, but is not limited to, a decatungstate, such as sodium decatungstate or tetrabutylamine decatungstate. The metal-containing cocatalyst can include, for example, a cobalt-based cocatalyst, one example of which is cobaloxime (Co(dmgH(dmgH2)Br2). When present, any suitable disulfide can be utilized, with a representative example being 2,4,6-triisopropylbenzene disulfide.

[0086] The relative amounts of the photocatalyst, metal-containing co-catalyst, and disulfide compound (if present) are not particularly limited, but the molar ratio of photocatalyst to co-catalyst is often in the range of 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, or 1.3:1 to 1:1.3, etc.

[0087] In this catalyst system, step c) optionally comprises reacting the catalyst system with C in the presence of a solvent. 10The catalyst system can be contacted with a linear internal olefin. Organic solvents, such as, but not limited to, acetonitrile, acetone, and mixtures thereof, can also be utilized. Step c) can be carried out at any suitable temperature with this catalyst system. In some non-limiting embodiments, the temperature can range from 0°C to 100°C, alternatively from 0°C to 60°C, alternatively from 0°C to 40°C, alternatively from 15°C to 75°C, alternatively from 15°C to 50°C, alternatively from 15°C to 40°C, alternatively from 20°C to 40°C, or alternatively from 20°C to 30°C. These temperature ranges are intended to encompass situations in which step c) is carried out at a series of different temperatures within each temperature range, rather than at a single fixed temperature.

[0088] As described above, step c) can use actinic radiation appropriate for the catalyst system, which can often include light of any suitable wavelength(s) in the range of 300-500 nm, or 350-450 nm, for example, around 390 nm.

[0089] Manufacturing Systems The first (1-octene and 1-decene) production system provided herein is an ethylene oligomerization system configured to: 1) oligomerize ethylene in the presence of a catalyst system or catalyst system components to form a composition comprising an oligomer product, the oligomer product comprising 15 to 80 mol% C6 olefins, 20 to 80 mol% C8 olefins, and 5 to 20 mol% C6 olefins; 10 + olefins, and 2) a composition comprising the oligomer product, said composition comprising: i) a first oligomer composition comprising 1-hexene, ii) a second oligomer composition comprising 1-octene, and iii) C 10 a fractionation system configured to separate the first oligomer composition into a heavy stream containing olefins and a heavy stream containing olefins; and 3) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to produce a C 10 a metathesis system configured to form a first composition comprising a linear internal olefin; and 4) in the presence of actinic radiation, 104) a catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and 5) a purification system configured to isolate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0090] The second system for producing (1-hexene and 1-decene) provided by the present invention includes: 1) an ethylene oligomerization system configured to oligomerize ethylene in the presence of a catalyst system or catalyst system components to form a composition comprising oligomer products, the oligomer products comprising at least 85 mol % C olefins and at least 5 mol % C olefins; 2) a fractionation system configured to separate the composition comprising oligomer products into a first oligomer composition comprising 1-hexene and a heavier stream comprising C olefins; and 3) a metathesis catalyst system configured to contact all or a portion of the first oligomer composition to produce C olefins. 10 a metathesis system configured to form a first composition comprising a linear internal olefin; and 4) in the presence of actinic radiation, 10 4) a catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and 5) a purification system configured to isolate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0091] Generally, the features of the first and second manufacturing systems are the same as those generally described herein for the respective first and second processes, and therefore, any feature of the first and second processes may be applied to the respective first and second manufacturing systems.

[0092] Optionally, the first production system (or the second production system) comprises a catalytic isomerization system for isomerizing C from the first composition prior to the catalytic isomerization system. 10The method may further include a metathesis purification system configured to isolate the composition comprising the linear internal olefin, which may include, for example, extraction, filtration, evaporation, distillation, or the like, and any combination thereof.

[0093] Reference is now made to FIG. 1 , which illustrates a 1-octene / 1-decene production system 100 consistent with one embodiment of the present disclosure. System 100 may include an ethylene oligomerization system 110, a fractionation system 120, a metathesis system 130, a catalytic isomerization system 150, and a purification system 160. In FIG. 1 , an ethylene feed stream 105 enters ethylene oligomerization system 110. Other feed streams to ethylene oligomerization system 110, such as a catalyst system or catalyst system components, a reaction medium (if used), and hydrogen (if used), are not specifically shown in FIG. 1 . Those skilled in the art will appreciate that there can be many different inputs to an ethylene oligomerization system, and the present disclosure is not limited to only the options described with reference to FIG. 1 or disclosed herein. In ethylene oligomerization system 110, ethylene introduced via ethylene feed stream 105 is oligomerized in the presence of a catalyst system (or catalyst system components) to form a composition 115 comprising oligomeric products that exits ethylene oligomerization system 110. Typically, the oligomeric products comprise 15-80 mol % C6 olefins, 20-80 mol % C8 olefins, and 5-20 mol % C 10 +Contains olefins.

[0094] This composition 115 containing oligomeric products enters a fractionation system 120, which separates composition 115 into C 10+ a heavy stream 122 containing olefins (and optionally spent catalyst), a second oligomer composition 124 containing 1-octene, and a first oligomer composition 125 containing 1-hexene. The first oligomer composition 125 containing 1-hexene may be split into a 1-hexene product stream 126 and a 1-hexene feed stream 128. Accordingly, all or a portion of the first oligomer composition 125 may be fed to a metathesis system 130, contacted with a suitable metathesis catalyst system, and C 10 A first composition 135 comprising linear internal olefins can be formed and discharged from the metathesis system 130 .

[0095] In Figure 1, C 10 Composition 135 comprising linear internal olefins enters catalytic isomerization system 150 where it is contacted with a catalytic isomerization catalyst system in the presence of actinic radiation to form second composition 155 comprising 1-decene. Optionally, system 100 of FIG. 1 can include purification system 160. Second composition 155 comprising 1-decene exits catalytic isomerization system 150 and enters purification system 160, where third composition 165 comprising at least 90 mole % 1-decene is produced and discharged from purification system 160.

[0096] 2, which illustrates another 1-octene / 1-decene production system 200 consistent with one embodiment of the present disclosure. System 200 includes an ethylene oligomerization system 210, a fractionation system 220, a metathesis system 230, a catalytic isomerization system 250, a purification system 260, an ethylene feed stream 205, a composition 215 comprising oligomer products, a C 10+ a heavy stream 222 comprising olefins (and optionally spent catalyst), a second oligomer composition 224 comprising 1-octene, a first oligomer composition 225 comprising 1-hexene (which may be split into a 1-hexene product stream 226 and a 1-hexene feed stream 228), a second composition 255 comprising 1-decene, and a third composition 265 comprising at least 90 mole % 1-decene, which are generally the same as those described for like-numbered components in FIG. 1 .

[0097] In Figure 2, C 10 A composition 235 comprising linear internal olefins exits the metathesis system 230 and is converted into C 10 The product stream 245 enters a metathesis purification system 240 configured to isolate a composition 245 comprising linear internal olefins, exits the metathesis purification system 240, and enters a catalytic isomerization system 250. A by-product stream 242 comprising C6 olefins exits the metathesis purification system 240 and is combined with the 1-hexene product stream 226.

[0098] 3, which illustrates a 1-hexene / 1-decene production system 300 consistent with one embodiment of the present disclosure. System 300 includes a metathesis system 330, a catalytic isomerization system 350, a purification system 360, an ethylene feed stream 305, a C 10 The composition includes a first composition 335 comprising a linear internal olefin, a second composition 355 comprising 1-decene, and a third composition 365 comprising at least 90 mole % 1-decene, which are generally the same as those described for like-numbered components in FIG. 1.

[0099] In FIG. 3 , ethylene feed stream 305 enters ethylene oligomerization system 310. Other feed streams to ethylene oligomerization system 310, such as a catalyst system or catalyst system components, a reaction medium (if used), and hydrogen (if used), are not specifically shown in FIG. 3 . Those skilled in the art will appreciate that there can be many different inputs to an ethylene oligomerization system, and the present disclosure is not limited to only the options described with reference to FIG. 3 or other options disclosed herein. In ethylene oligomerization system 310, ethylene introduced via ethylene feed stream 305 is oligomerized in the presence of a catalyst system (or catalyst system components) to form composition 315 comprising an oligomer product, which exits ethylene oligomerization system 310. Unlike FIGS. 1-2 , the oligomer product in FIG. 3 typically comprises at least 85 mol % C olefins and at least 5 mol % C olefins (selective 1-hexene production).

[0100] This oligomeric product composition 315 enters a fractionation system 320, which separates composition 315 into a heavies stream 322 containing C8+ olefins (and optionally spent catalyst) and a first oligomeric composition 325 containing 1-hexene. The first oligomeric composition 325 containing 1-hexene may be split into a 1-hexene product stream 326 and a 1-hexene feed stream 328. Accordingly, all or a portion of first oligomeric composition 325 may be fed to a metathesis system 330 and contacted with a suitable metathesis catalyst system to produce C8+ olefins. 10 A first composition 335 comprising linear internal olefins can be formed and discharged from the metathesis system 330 .

[0101] Synthesis of normal alpha olefins Embodiments of the present invention are also directed to processes for purifying normal alpha olefins. For example, a third process described herein includes: (i) a process for purifying normal alpha olefins of the structure CH3(CH2) n contacting a first normal alpha olefin having HC=CH with a metathesis catalyst system to produce a metathesis product of the structure CH(CH) nHC=CH(CH2) n (ii) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of actinic radiation to form a linear internal olefin having the structure CH(CH) 2n+1 and forming a second normal alpha olefin having HC=CH2. In this third process, n is an integer ranging from 0 to 15. Generally, the process features (e.g., the first normal alpha olefin, the metathesis catalyst, the linear internal olefin, the catalytic isomerization catalyst system, the second normal olefin, and the conditions under which each step is performed, among other features) are described individually herein, and these features can be combined in any combination to further describe the disclosed normal alpha olefin synthesis process. Furthermore, unless otherwise specified, additional process steps can be performed before, during, and / or after any step of any of the processes disclosed herein.

[0102] As described herein, n is an integer ranging from 0 to 15. In one embodiment consistent with the present invention, n can be an integer from 0 to 10, in another embodiment, n can be an integer from 0 to 7, in yet another embodiment, n can be an integer from 1 to 7, and in yet another embodiment, n can be an integer from 1 to 5. For example, n can be equal to 1, 2, 3, 4, etc.

[0103] In some embodiments of the present invention, the first normal alpha olefin can comprise (consist essentially of, or consist of) propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof; alternatively, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or any combination thereof; or alternatively, 1-butene, 1-pentene, 1-hexene, or any combination thereof. In other embodiments, the first normal alpha olefin may comprise (consist essentially of, or consist of) propylene, alternatively 1-butene, alternatively 1-pentene, alternatively 1-hexene, alternatively 1-heptene, alternatively 1-octene, alternatively 1-nonene, alternatively 1-decene, alternatively 1-dodecene, alternatively 1-tetradecene, alternatively 1-hexadecene, or alternatively 1-octadecene.

[0104] In one aspect of the invention, the first normal alpha olefin can comprise (or consist essentially of, or consist of) 1-butene, and the second normal alpha olefin can comprise (or consist essentially of, or consist of) 1-hexene. In another aspect of the invention, the first normal alpha olefin can comprise (or consist essentially of, or consist of) 1-pentene, and the second normal alpha olefin can comprise (or consist essentially of, or consist of) 1-octene. In yet another aspect of the invention, the first normal alpha olefin can comprise (or consist essentially of, or consist of) 1-hexene, and the second normal alpha olefin can comprise (or consist essentially of, or consist of) 1-decene. In yet another aspect of the invention, the first normal alpha olefin can comprise (or consist essentially of, or consist of) 1-octene and the second normal alpha olefin can comprise (or consist essentially of, or consist of) 1-tetradecene.

[0105] The integer n, the first normal alpha olefin, and the second normal alpha olefin are described herein, and their characteristics can be utilized without limitation to further describe the normal alpha olefin synthesis process disclosed herein. Other suitable values ​​of the integer n, and the selection of the first normal alpha olefin and the second normal alpha olefin, will be readily apparent from this disclosure.

[0106] Step (i) of the third process is often referred to as the catalysis step, in which a compound of the structure CH3(CH2) n A first normal alpha olefin having HC=CH2 is contacted with a metathesis catalyst system to produce a compound of the structure CH3(CH2) n HC=CH(CH2) n A linear internal olefin having CH is formed. Any suitable metathesis catalyst system or any metathesis catalyst system disclosed herein, as described herein in connection with the first and second processes, can be used in the metathesis step of the third process.

[0107] Step (ii) of the third process is often referred to as the catalytic isomerization step, in which a linear internal olefin is contacted with a catalytic isomerization catalyst system in the presence of actinic radiation to produce an olefin of the structure CH(CH) 2n+1 A second linear alpha olefin having HC=CH2 is formed. Any suitable catalytic isomerization catalyst system or any catalytic isomerization catalyst system disclosed herein, as described herein in connection with the first and second processes, can be used in the catalytic isomerization step of the third process.

[0108] Furthermore, the features of steps (i) and (ii) of the third process can be any of those described herein for the metathesis and catalytic isomerization steps of the first and second processes, respectively, and therefore any feature of the first and second processes can be applied to the third process.

[0109] A fourth process is provided herein, which also relates to the production of normal alpha olefins. The fourth process comprises (a) a process for producing normal alpha olefins having the structure CH3(CH2) p a first normal alpha olefin having HC=CH2 and a second normal alpha olefin having the structure CH3(CH2) q A second normal alpha olefin having HC=CH2 is contacted with the metathesis catalyst system to produce a compound of the structure CH3(CH2) p HC=CH(CH2) q (b) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of actinic radiation to form a linear internal olefin having the structure CH(CH) p+q+1 and forming a third normal alpha olefin having HC=CH2. In this fourth process, p and q are each integers ranging from 0 to 15. Generally, the process features (e.g., the first normal alpha olefin, the second normal alpha olefin, the metathesis catalyst, the linear internal olefin, the catalytic isomerization catalyst system, the third normal olefin, and the conditions under which each step is carried out, among other features) are described individually herein, and these features can be combined in any combination to further describe the disclosed normal alpha olefin synthesis process. Furthermore, unless otherwise specified, additional process steps can be performed before, during, and / or after any step of any of the processes disclosed herein.

[0110] In this process for synthesizing normal alpha olefins, p and q can each be an integer ranging from 0 to 15. In one embodiment consistent with the present invention, p and q can independently be integers from 0 to 10, while in another embodiment, p and q can independently be integers from 1 to 10. In yet another embodiment, p and q can independently be integers from 1 to 7, and in yet another embodiment, p and q can independently be integers from 1 to 5. For example, p and q can independently be equal to 1, 2, 3, or 4. Typically, but not necessarily, p and q are different integers.

[0111] The third normal alpha olefin produced in this process has the structure CH3(CH2) p+q+1 The third normal alpha olefin has HC=CH2, but is not particularly limited thereto. However, in one embodiment of the present invention, the third normal alpha olefin can comprise (consist of, or consist of) 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof, alternatively 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof, or alternatively 1-hexene, 1-octene, 1-decene, or any combination thereof. In another embodiment, the third normal alpha olefin can comprise (consist of, or consist of) 1-butene, alternatively 1-hexene, alternatively 1-octene, alternatively 1-decene, alternatively 1-dodecene, alternatively 1-tetradecene, alternatively 1-hexadecene, or alternatively 1-octadecene. In yet another embodiment, the third normal alpha olefin can comprise (can consist of, or can consist of) 1-hexene, 1-octene, 1-decene, or any combination thereof.

[0112] In one aspect of the invention, the first normal alpha olefin can comprise 1-butene, the second normal alpha olefin can comprise 1-octene, and the third normal alpha olefin can comprise 1-decene. In another aspect of the invention, the first normal alpha olefin can comprise 1-butene, the second normal alpha olefin can comprise 1-hexene, and the third normal alpha olefin can comprise 1-octene. In yet another aspect of the invention, the first normal alpha olefin can comprise propylene, the second normal alpha olefin can comprise pentene, and the third normal alpha olefin can comprise 1-hexene.

[0113] The integers p and q, the first normal alpha olefin, the second normal alpha olefin, and the third normal alpha olefin are described herein, and their characteristics can be utilized without limitation to further describe the normal alpha olefin synthesis processes disclosed herein. Other suitable values ​​of the integers p and q, and the selection of the first normal alpha olefin, the second normal alpha olefin, and the third normal alpha olefin, will be readily apparent from this disclosure.

[0114] Steps (a) and (b) of the fourth process may also have any of the features and attributes (e.g., catalyst systems, reaction conditions, etc.) described herein for steps (i) and (ii), respectively, of the third process, as well as any of the features or attributes described for the analogous steps of the first and second processes. [Example]

[0115] The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention in any way. After reading the description herein, various other embodiments, modifications, and equivalents will become apparent to those skilled in the art without departing from the spirit of the invention or the scope of the appended claims.

[0116] Configuration example A Construction Example A shows the conversion of 1-hexene to 1-decene via metathesis (homogeneous) and reverse isomerization pathways as shown in the synthesis scheme below (n=3). [ka]

[0117] The reaction scheme for the homogeneous metathesis process is shown below. [ka]

[0118] The metathesis process can be carried out as follows. In a drybox under a N2 atmosphere, place 1-hexene (250 mL, 168 g, approximately 2 mol) in a 500 mL round-bottom flask equipped with a magnetic stir bar. The flask is placed on an aluminum block on a heating plate temperature-controlled at approximately 50 °C and allowed to equilibrate. To this stirred solution, Grubbs Second Generation catalyst (dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 4.2 mg, 4.9 μmol) is added to initiate the reaction. The progress of the reaction can be monitored by taking aliquot samples and analyzing them for reaction equilibrium by GC-FID. This typically takes 4-8 h. Since the flask is left uncapped in the glovebox, any ethylene produced will bubble out of the flask. After completion of the reaction, the solution is cooled, filtered, and the reaction contents are distilled to isolate 5-decene. The reaction yield is about 40-50% 5-decene by fractionation.

[0119] The reaction scheme for the photochemically induced isomerization process is shown below. [ka]

[0120] The reverse isomerization process can be carried out as follows: 1 mole of 5-decene is placed in a continuously stirred autoclave under a nitrogen atmosphere. To this vessel, Ir(dF(CF3)ppy)2(5,5'-d(CF3)bpy)]PF6 (40 mmol, 4.0 mol%), 4,4'-di-tert-butyl-2,2'-dipyridyl (150 mmol, 15.0 mol%), and CrCl2 (100 mmol, 10 mol%) are added. Next, a solution of PhCF3 (6 L), MeCN (24 L), and MeOH (12 L) is added through the addition port. The autoclave contains a light cell for irradiating at approximately 450 nm for 18 hours. The autoclave can have a temperature-controlled cooling jacket attached to a process cooler that maintains the reaction temperature at 35 °C. After the reaction is complete, the light source is turned off, and the reactor is vented through a silica filter plug to remove any remaining solids and polar compounds. Analysis of the mixture by GC-FID revealed greater than 90 mol% conversion to 1-decene. This material can be purified by fractionation using a BR Instruments automated distillation system monitoring the atmospheric distillation temperature of 172°C.

[0121] Configuration example B Configuration B is similar to Configuration A, except that a different reverse isomerization pathway is used. The reaction scheme for the photochemically induced isomerization step is shown below. [ka]

[0122] The reverse isomerization process can be carried out as follows: 1 mole of 5-decene is placed in a continuously stirred autoclave under a nitrogen atmosphere. Co(dmgh)(dmgh)(Br) (50 mmol, 5.0 mol%) and decatungstate catalyst (40 mmol, 4.0 mol%) are added to the vessel. MeCN solution (10 L) is then added through the addition port. The autoclave contains a light cell for irradiating at approximately 390 nm for 18 hours. The autoclave can have a temperature-controlled cooling jacket attached to a process cooler that maintains the reaction temperature at room temperature (18-22 °C). After the reaction is complete, the light source is turned off, and the reactor is vented through a silica filter plug to remove any remaining solids and polar compounds. Analysis of the mixture by GC-FID revealed a conversion to 1-decene of greater than 90 mol%. This material can be purified by fractionation using a BR Instruments automated distillation system monitoring atmospheric distillation at 172 °C.

[0123] The present invention is described herein with reference to numerous embodiments and specific examples. Many variations will occur to those skilled in the art in light of the detailed description. All such obvious variations are fully included within the intended scope of the appended claims. Other embodiments of the present invention include, but are not limited to, the following (although embodiments may be described as "comprising," they may alternatively be described as "consisting essentially of" or "consisting of"):

[0124] Embodiment 1. A process (e.g., for producing 1-octene / 1-decene) comprising: a) 15-80 mol % C olefins, 20-80 mol % C olefins, and 5-20 mol % C 10 + olefins, the composition comprising the oligomer product comprising: i) a first oligomer composition comprising a C6 alkane and at least 85 mol% of a C6 olefin, the C6 olefin comprising at least 80 mol% of 1-hexene; ii) a second oligomer composition comprising at least 20 mol% of a C8 olefin, the C8 olefin comprising at least 85 mol% of 1-octene; and iii) a C6 olefin composition comprising at least 20 mol% of a C8 olefin, the C8 olefin comprising at least 85 mol% of 1-octene.10 a) separating the first oligomer composition into a heavy stream containing olefins and a heavy stream containing olefins; and b) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to produce a C 10 forming a first composition comprising a linear internal olefin; and c) reacting said C in the presence of actinic radiation. 10 contacting all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying the second composition to isolate a third composition comprising at least 90 mole % 1-decene.

[0125] Embodiment 2. The process of embodiment 1, wherein the oligomeric product comprises 30-70 mol % or 35-65 mol % C olefins (or any other minimum, maximum, or range as described herein).

[0126] Embodiment 3. The process of embodiment 1 or 2, wherein the oligomeric product comprises 30-70 mol % or 35-65 mol % C olefins (or any other minimum, maximum, or range described herein).

[0127] Aspect 4. The oligomer product has 5 to 18 mol % or 7 to 20 mol % C 10 + olefin (or any other minimum, maximum, or range described herein).

[0128] Embodiment 5. The process of any one of embodiments 1-4, wherein the first oligomer composition comprises at least 90 mol%, at least 93 mol%, or at least 95 mol% C olefins (or any other minimum, maximum, or range as described herein).

[0129] Embodiment 6. The process of any one of embodiments 1-5, wherein the first oligomer composition comprises 0.5-12 mol%, 1-10 mol%, 1.5-8 mol%, or 2-6 mol% C6 alkanes (or any other minimum, maximum, or range described herein).

[0130] Embodiment 7. The process of any one of embodiments 1-6, wherein the C6 olefins comprise at least 85 mol%, at least 90 mol%, at least 95 mol%, 80 mol% to 98 mol%, 80 mol% to 95 mol%, or 85 mol% to 95 mol% 1-hexene (or any other minimum, maximum, or range described herein).

[0131] Embodiment 8. The process of any one of embodiments 1-7, wherein the C6 olefins comprise 0.1 to 10 mol%, 0.5 to 8 mol%, or 1 to 6 mol% internal and cyclic C6 olefins (or any other minimum, maximum, or range described herein).

[0132] Embodiment 9. The process of any one of embodiments 1-8, wherein the second oligomer composition comprises at least 50 mol%, at least 75 mol%, at least 90 mol%, at least 95 mol%, at least 96 mol%, or at least 97 mol% C olefins (or any other minimum, maximum, or range as described herein).

[0133] Embodiment 10. The process of any one of embodiments 1-9, wherein the C8 olefins comprise at least 90 mol%, at least 95 mol%, or at least 97 mol% 1-octene (or any other minimum, maximum, or range described herein).

[0134] Embodiment 11. Prior to step c), at least 90 mol%, at least 93 mol%, or at least 96 mol% C are extracted via any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation, or any combination thereof. 10 11. The process of any one of aspects 1-10, further comprising isolating a composition comprising a linear internal olefin from said first composition.

[0135] Aspect 12. The metathesis catalyst system is contacted with all or a portion of a second oligomer composition comprising C8 olefins to produce C8 olefins. 1412. The process of any one of embodiments 1 to 11, further comprising forming an olefin composition.

[0136] Aspect 13. The metathesis catalyst is contacted with a light oligomer composition comprising C6 and C8 olefins to form a C 10 ~C 14 13. The process of any one of embodiments 1 to 12, further comprising forming a composition comprising a linear internal olefin.

[0137] Embodiment 14. A process (e.g., for producing 1-hexene / 1-decene) comprising: a) separating a composition comprising an oligomeric product comprising at least 85 mol% C6 olefins and at least 5 mol% C8+ olefins into i) a first oligomeric composition comprising C6 alkanes and at least 90 mol% C6 olefins, said C6 olefins comprising at least 90 mol% 1-hexene, and ii) a heavier stream comprising C8+ olefins; and b) contacting a metathesis catalyst system with all or a portion of the first oligomeric composition to produce a C8+ olefin. 10 forming a first composition comprising a linear internal olefin; and c) reacting said C in the presence of actinic radiation. 10 contacting all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying the second composition to isolate a third composition comprising at least 90 mole % 1-decene.

[0138] Embodiment 15. The process of embodiment 14, wherein the oligomeric product comprises at least 85 mol%, at least 87 mol%, at least 90 mol%, at least 91 mol%, or at least 93 mol% C olefins (or any other minimum, maximum, or range as described herein).

[0139] Embodiment 16. The process of embodiment 14 or 15, wherein the oligomeric product comprises 5-15 mol % or 5-12 mol % C8+ olefins (or any other minimum, maximum, or range described herein).

[0140] Embodiment 17. The process of any one of embodiments 14-16, wherein the first oligomer composition comprises at least 94 mol%, at least 96 mol%, or at least 98 mol% C6 olefins (or any other minimum, maximum, or range as described herein).

[0141] Embodiment 18. The process of any one of embodiments 14-17, wherein the first oligomer composition comprises between 0.1 mol% and 1.5 mol%, between 0.15 mol% and 1 mol%, or between 0.2 mol% and 0.75 mol% of C6 alkanes (or any other minimum, maximum, or range described herein).

[0142] Embodiment 19. The process of any one of embodiments 14-18, wherein the C6 olefins comprise at least 94 mol%, at least 96 mol%, or at least 98 mol% 1-hexene (or any other minimum, maximum, or range described herein).

[0143] Embodiment 20. The process of any one of embodiments 14-19, wherein the C6 olefins comprise 0.1 mol% to 3 mol%, 0.2 mol% to 2 mol%, or 0.25 mol% to 1 mol% internal and cyclic C6 olefins (or any other minimum, maximum, or range described herein).

[0144] Embodiment 21. Prior to step c), at least 90 mol%, at least 93 mol%, or at least 96 mol% of C are extracted from the first composition by any suitable technique such as extraction, filtration, evaporation, distillation, or any combination thereof, or any technique disclosed herein. 10 21. The process of any one of embodiments 14 to 20, comprising isolating the composition comprising the linear internal olefin.

[0145] Embodiment 22. The process of any one of embodiments 1-21, wherein the third composition comprises at least 95 mol % or at least 98 mol % 1-decene (or any other minimum, maximum, or range as described herein).

[0146] Embodiment 23. The process of any one of embodiments 1 to 22, wherein the purification in step d) comprises any suitable technique such as extraction, filtration, evaporation, distillation, or any combination thereof, or any technique disclosed herein.

[0147] Embodiment 24. The process of any one of embodiments 1 to 23, wherein the metathesis catalyst system is a metal oxide-based metathesis catalyst system, a metal halide-based metathesis catalyst system, a metal carbene-based metathesis catalyst system, or any combination thereof.

[0148] Embodiment 25. The process of embodiment 24, wherein the metal oxide-based metathesis catalyst system comprises cobalt oxide, molybdenum oxide, tungsten oxide, rhenium oxide, or any combination thereof.

[0149] Embodiment 26. The process of embodiment 25, wherein the metal oxide-based metathesis catalyst system further comprises a support and / or a metal alkyl activator.

[0150] Embodiment 27. The process of embodiment 24, wherein the metal halide-based metathesis catalyst system comprises a tungsten halide, a molybdenum halide, or any combination thereof.

[0151] Embodiment 28. The process of embodiment 27, wherein the metal halide-based metathesis catalyst system further comprises a metal alkyl activator and / or oxygen or an alcohol.

[0152] Embodiment 29. The process of embodiment 24, wherein the metal carbene-based metathesis catalyst system comprises tungsten, tantalum, osmium, molybdenum, ruthenium, or any combination thereof.

[0153] Embodiment 30. The process of embodiment 29, wherein the metal carbene-based metathesis catalyst system further comprises a support.

[0154] Embodiment 31. The process of any one of embodiments 1 to 30, wherein the catalytic isomerization catalyst system comprises a photocatalyst, a hydrogen atom transfer agent, a metal ion, and a proton donor.

[0155] Embodiment 32. The process of embodiment 31, wherein the photocatalyst comprises a transition metal complex, an organic dye (e.g., 3,6-di-tert-butyl-9-mesityl-10-phenylacridinium tetrafluoroborate), 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, or a semiconductor (e.g., TiO2).

[0156] Embodiment 33. The process of embodiment 32, wherein the transition metal complex comprises an iridium-based photocatalyst (e.g., [Ir(dF(CF3)ppy)2(5,5'-d(CF3)bpy)]PF6) or a ruthenium-based photocatalyst.

[0157] Embodiment 34. The process of any one of embodiments 31 to 33, wherein the photocatalyst has a redox potential in the range of 0.7 V to 2.0 V, or 1.3 to 1.8 V, relative to Fc+ / Fc in MeCN.

[0158] Embodiment 35. The process of any one of embodiments 31 to 34, wherein the transfer agent is a Bronsted base, including an organic base.

[0159] Embodiment 36. The process of any one of embodiments 31 to 35, wherein the transfer agent is a Bronsted base, including a pyridine base (e.g., 4,4'-di-tert-butyl-2,2'-dipyridine), or a pyridyl ligand of the metal ion (e.g., 4,4'-di-tert-butyl-2,2'-dipyridyl).

[0160] Embodiment 37. The process of any one of embodiments 31 to 34, wherein the transfer agent comprises a cytochrome p450, iron porphyrin, iron cyclam, chromyl chloride, MnO4, iron zeolite, or any combination thereof.

[0161] Embodiment 38. The process of any one of embodiments 31 to 37, wherein the metal ion comprises a chromium ion (e.g., a chromium(II) ion, a chromium(III) ion), or the metal ion comprises a metal salt (e.g., a chromium(II) dihalide, a chromium(III) trihalide).

[0162] Embodiment 39. The process of any one of embodiments 31 to 38, wherein the proton donor comprises an alcohol (e.g., a primary alcohol, a secondary alcohol, an aliphatic alcohol, a primary aliphatic alcohol, a fluorinated alcohol), a carboxylic acid, or water.

[0163] Embodiment 40. The process of any one of embodiments 31 to 38, wherein the proton donor comprises a C1 to C8 primary aliphatic alcohol (e.g., methanol, ethanol, n-propanol, isopropanol).

[0164] Embodiment 41 The process of any one of embodiments 31 to 40, wherein the catalyst system further comprises a solvent (e.g., an organic solvent such as acetonitrile, dioxane, trifluorobenzene, or a mixture thereof).

[0165] Embodiment 42. The process of any one of embodiments 31 to 41, wherein step c) is carried out at a temperature ranging from 0 to 40°C (e.g., about 35°C, or any other minimum temperature, maximum temperature, or temperature range disclosed herein).

[0166] Embodiment 43. The process of any one of embodiments 31 to 42, wherein the molar ratio of the Bronsted base to the photocatalyst is in the range of 5:1 to 1:1 (e.g., 3:1), and / or the molar ratio of the metal ion to the photocatalyst is in the range of 3:1 to 1:1 (e.g., 2:1), and / or the molar ratio of the proton donor to the photocatalyst is in the range of 3:1 to 1:1 (e.g., 1:1), as well as any other minimum ratio, maximum ratio, or ratio range disclosed herein.

[0167] Aspect 44. The C 10

[0047] Aspect 44. The process of any one of aspects 31-43, wherein the amount of photocatalyst in the catalyst system based on linear internal olefin ranges from 0.1 mol% to 10 mol%, or from 1 mol% to 5 mol% (or any other minimum amount, maximum amount, or amount range disclosed herein).

[0168] Embodiment 45. The process of any one of embodiments 31 to 44, wherein the actinic irradiation comprises light of any suitable wavelength(s), or any wavelength disclosed herein, e.g., blue light at 450-495 nm, or about 456 nm.

[0169] Embodiment 46 The process of any one of embodiments 1 to 30, wherein the catalytic isomerization catalyst system comprises a photocatalyst, a metal-containing cocatalyst, and an optional disulfide compound.

[0170] Embodiment 47. The process of embodiment 46, wherein the photocatalyst comprises a decatungstate (e.g., sodium decatungstate, tetrabutylamine decatungstate).

[0171] Embodiment 48. The process of embodiment 46 or 47, wherein the cocatalyst comprises a cobalt-based cocatalyst (e.g., cobaloxime).

[0172] Aspect 49. The process of aspect 46 or 47, wherein the co-catalyst comprises a cobaloxime (e.g., Co(dmgH(dmgH2)Br2).

[0173] Embodiment 50. The process of any one of embodiments 46 to 49, wherein the disulfide compound comprises 2,4,6-triisopropylbenzene disulfide.

[0174] Embodiment 51. The process of any one of embodiments 46 to 50, wherein the catalyst system further comprises a solvent (e.g., an organic solvent such as acetonitrile, acetone, or a mixture thereof).

[0175] Embodiment 52. The process of any one of embodiments 46 to 51, wherein step c) is carried out at a temperature ranging from 0 to 40°C (e.g., about 25°C, or any other minimum temperature, maximum temperature, or temperature range disclosed herein).

[0176] Embodiment 53. The process of any one of embodiments 46-52, wherein the molar ratio of the photocatalyst to the co-catalyst is in the range of 2:1 to 1:2 (or any other minimum ratio, maximum ratio, or range of ratios disclosed herein).

[0177] Embodiment 54. The process of any one of embodiments 46 to 53, wherein the actinic irradiation comprises any suitable wavelength(s) of light or any wavelength disclosed herein, e.g., 300-500 nm, 350-450 nm, or about 390 nm.

[0178] Aspect 55. A (1-octene / 1-decene) production system, comprising: 1) an ethylene oligomerization system configured to: 1) oligomerize ethylene in the presence of the catalyst system or catalyst system components to form a composition comprising an oligomer product; wherein the oligomer product comprises 15 to 80 mol% C6 olefins, 20 to 80 mol% C8 olefins, and 5 to 20 mol% C6 olefins. 10 + olefins; and 2) separating the composition comprising the oligomer product from i) a first oligomer composition comprising 1-hexene, ii) a second oligomer composition comprising 1-octene, and iii) C 10 a fractionation system configured to separate a heavy stream containing olefins into a heavy stream containing olefins and a heavy stream containing olefins; and 3) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to produce a C 10 a metathesis system configured to form a first composition comprising a linear internal olefin; and 4) in the presence of said actinic radiation, 105) a catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and 6) a purification system configured to isolate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0179] Aspect 56. A (1-hexene / 1-decene) production system, comprising: 1) an ethylene oligomerization system configured to oligomerize ethylene in the presence of the catalyst system or catalyst system components to form a composition comprising an oligomer product, the oligomer product comprising at least 85 mol % C6 olefins and at least 5 mol % C8+ olefins; 2) a fractionation system configured to separate the composition comprising the oligomer product into a first oligomer composition comprising 1-hexene and a heavier stream comprising C8+ olefins; and 3) a metathesis catalyst system configured to contact all or a portion of the first oligomer composition to produce a C6 olefin. 10 a metathesis system configured to form a first composition comprising a linear internal olefin; and 4) in the presence of said actinic radiation, 10 5) a catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form the second composition comprising 1-decene; and 6) a purification system configured to isolate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0180] Aspect 57. The catalytic isomerization system comprises: 10 57. The manufacturing system of any one of embodiments 55 to 56, further comprising a metathesis purification system configured to isolate the composition comprising the linear internal olefin, wherein the purification system comprises extraction, filtration, evaporation, distillation, or any combination thereof.

[0181] Aspect 58. The production system of any one of Aspects 55 to 57, wherein the catalyst system or catalyst system component comprises a heteroatom-ligand chromium compound complex and an alkylaluminum compound, or a heteroatom-ligand, a chromium compound, and an alkylaluminum compound.

[0182] Embodiment 59. The production system according to any one of embodiments 55 to 58, wherein the metathesis catalyst system is as described in any one of embodiments 24 to 30.

[0183] Aspect 60. The production system of any one of Aspects 55 to 59, wherein the catalytic isomerization catalyst system is as described in any one of Aspects 31 to 54.

[0184] 61. A process comprising: (i) a compound having the structure CH3(CH2) n contacting a first normal alpha olefin having HC=CH with a metathesis catalyst system to produce a metathesis product of the structure CH(CH) n HC=CH(CH2) n (ii) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of actinic radiation to form a linear internal olefin having the structure CH(CH) 2n+1 forming a second normal alpha olefin having HC=CH2, wherein n is an integer from 0 to 15.

[0185] Embodiment 62. The process of embodiment 61, wherein n is an integer from 1 to 10.

[0186] Embodiment 63. The process of embodiment 61, wherein n is an integer from 1 to 7.

[0187] Aspect 64. The process of aspect 61, wherein the first normal alpha olefin comprises propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof.

[0188] Aspect 65. The process of aspect 61, wherein the first normal alpha olefin comprises 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or any combination thereof.

[0189] Aspect 66. The process of aspect 61, wherein the first normal alpha olefin comprises 1-butene and the second normal alpha olefin comprises 1-hexene.

[0190] Aspect 67. The process of aspect 61, wherein the first normal alpha olefin comprises 1-pentene and the second normal alpha olefin comprises 1-octene.

[0191] Aspect 68. The process of aspect 61, wherein the first normal alpha olefin comprises 1-hexene and the second normal alpha olefin comprises 1-decene.

[0192] Aspect 69. The process of aspect 61, wherein the first normal alpha olefin comprises 1-octene and the second normal alpha olefin comprises 1-tetradecene.

[0193] Embodiment 70. A process comprising: (a) forming a compound of the structure CH3(CH2) p a first normal alpha olefin having HC=CH2 and a second normal alpha olefin having the structure CH3(CH2) q A second normal alpha olefin having HC=CH2 is contacted with the metathesis catalyst system to produce a compound of the structure CH3(CH2) p HC=CH(CH2) q (b) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of actinic radiation to form a linear internal olefin having the structure CH(CH) p+q+1 and forming a third normal alpha olefin having HC=CH2, wherein p and q are each an integer from 0 to 15.

[0194] Embodiment 71. The process of embodiment 70, wherein p and q are each an integer from 1 to 10.

[0195] Embodiment 72. The process of embodiment 70, wherein p and q are each an integer from 1 to 7.

[0196] Embodiment 73. The process of embodiment 70, wherein the third normal alpha olefin comprises 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, or any combination thereof.

[0197] Embodiment 74. The process of embodiment 70, wherein the first normal alpha olefin comprises 1-butene, the second normal alpha olefin comprises 1-octene, and the third normal alpha olefin comprises 1-decene.

[0198] Aspect 75. The process of aspect 70, wherein the first normal alpha olefin comprises 1-butene, the second normal alpha olefin comprises 1-hexene, and the third normal alpha olefin comprises 1-octene.

[0199] Aspect 76. The process of aspect 70, wherein the first normal alpha olefin comprises propylene, the second normal alpha olefin comprises pentene, and the third normal alpha olefin comprises 1-hexene.

[0200] Embodiment 77. The process of any one of embodiments 61 to 76, wherein the metathesis catalyst system is described in any one of embodiments 24 to 30.

[0201] Embodiment 78. The process of any one of embodiments 61 to 77, wherein the catalytic isomerization catalyst system is described in any one of embodiments 31 to 54.

Claims

1. A process comprising: a) 15 to 80 mol% C ６ Olefins, 20 to 80 mol% C ８ Olefins and 5 to 20 mol% C １０ + a composition comprising an oligomeric product comprising an olefin, i) C ６ Alkanes and at least 85 mol % C ６ A first oligomer composition comprising an olefin, ６ the first oligomer composition, wherein the olefin comprises at least 80 mole percent 1-hexene; ii) at least 20 mol % C ８ A second oligomer composition comprising an olefin, ８ the second oligomer composition, wherein the olefin comprises at least 85 mole percent 1-octene; and iii) C １０ + a heavy stream containing olefins; b) contacting a metathesis catalyst system with all or a portion of said first oligomer composition to form C １０ forming a first composition comprising a linear internal olefin; c) in the presence of actinic radiation, １０ contacting all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying said second composition to isolate a third composition comprising at least 90 mole percent 1-decene.

2. The oligomer product is 30 to 70 mol % or 35 to 65 mol % C ６ an olefin; 30 to 70 mol % or 35 to 65 mol % C ８ an olefin; 5 to 18 mol % or 7 to 20 mol % C １０ + an olefin.

3. The first oligomer composition comprises: At least 90 mol%, at least 93 mol%, or at least 95 mol% C ６ an olefin; 0.5 to 12 mol%, 1 to 10 mol%, 1.5 to 8 mol%, or 2 to 6 mol% C ６ an alkane; and Said C ６ The olefin is at least 85 mol%, at least 90 mol%, at least 95 mol%, 80 mol% to 98 mol%, 80 mol% to 95 mol%, or 85 mol% to 95 mol% 1-hexene; 0.1 to 10 mol %, 0.5 to 8 mol %, or 1 to 6 mol % of internal and cyclic C ６ 3. The process of claim 1 or 2, comprising:

4. The second oligomer composition may comprise at least 50 mol%, at least 75 mol%, at least 90 mol%, at least 95 mol%, at least 96 mol%, or at least 97 mol% C ８ Contains olefins, Said C ８ The process of any one of claims 1 to 3, wherein the olefins comprise at least 90 mol%, at least 95 mol%, or at least 97 mol% 1-octene.

5. Prior to step c), at least 90 mol%, at least 93 mol%, or at least 96 mol% of C are extracted from the first composition. １０ 5. The process of any one of claims 1 to 4, further comprising isolating the internal olefin composition comprising linear internal olefins.

6. A process comprising: a) at least 85 mol % C ６ Olefin and at least 5 mol% C ８ + a composition comprising an olefin-containing oligomer product, i) C ６ Alkanes and at least 90 mol % C ６ A first oligomer composition comprising an olefin, ６ the first oligomer composition, wherein the olefin comprises at least 90 mole percent 1-hexene; and ii) C ８ + a heavy stream containing olefins; b) contacting a metathesis catalyst system with all or a portion of said first oligomer composition to form C １０ forming a first composition comprising a linear internal olefin; c) in the presence of actinic radiation, １０ contacting all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying said second composition to isolate a third composition comprising at least 90 mole percent 1-decene.

7. The oligomer product is At least 85 mol%, at least 87 mol%, at least 90 mol%, at least 91 mol%, or at least 93 mol% C ６ an olefin; 5 to 15 mol % or 5 to 12 mol % C ８ + an olefin.

8. The first oligomer composition comprises: At least 94 mol%, at least 96 mol%, or at least 98 mol% C ６ an olefin; 0.1 mol % to 1.5 mol %, 0.15 mol % to 1 mol %, or 0.2 mol % to 0.75 mol % C ６ an alkane; and Said C ６ The olefin is at least 94 mol%, at least 96 mol%, or at least 98 mol% 1-hexene; 0.1 mol % to 3 mol %, 0.2 mol % to 2 mol %, or 0.25 mol % to 1 mol % of internal and cyclic C ６ 8. The process of claim 6 or 7, comprising:

9. Prior to step c), at least 90 mol%, at least 93 mol%, or at least 96 mol% of C are extracted from the first composition. １０ 9. The process of any one of claims 6 to 8, further comprising the step of isolating the internal olefin composition comprising linear internal olefins.

10. The process of any one of claims 1 to 9, wherein the third composition comprises at least 95 mol % or at least 98 mol % 1-decene.

11. 1. A 1-octene / 1-decene production system comprising: 1) An ethylene oligomerization system configured to oligomerize ethylene in the presence of a catalyst system or catalyst system components to form a composition comprising an oligomer product, said oligomer product comprising 15 to 80 mol % C ６ Olefins, 20 to 80 mol% C ８ Olefins and 5 to 20 mol% C １０ + olefins; and 2) separating the composition comprising the oligomer product from i) a first oligomer composition comprising 1-hexene, ii) a second oligomer composition comprising 1-octene, and iii) C １０ a fractionation system configured to separate the olefins into a heavy stream containing olefins; 3) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to form C １０ a metathesis system configured to form a first composition comprising a linear internal olefin; 4) In the presence of actinic radiation, １０ a catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and 5) a purification system configured to isolate a third composition comprising at least 90 mole percent 1-decene from the second composition.

12. 1. A 1-hexene / 1-decene production system comprising: 1) An ethylene oligomerization system configured to oligomerize ethylene in the presence of a catalyst system or catalyst system components to form a composition comprising an oligomer product, said oligomer product having at least 85 mol % C ６ Olefins and at least 5 mol % C ８ + olefins; and 2) separating the composition comprising the oligomer product from a first oligomer composition comprising 1-hexene and C ８ a fractionation system configured to separate the olefins into a heavy stream containing olefins; 3) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to form C １０ a metathesis system configured to form a first composition comprising a linear internal olefin; 4) In the presence of actinic radiation, １０ a catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and 5) a purification system configured to isolate a third composition comprising at least 90 mole percent 1-decene from the second composition.

13. prior to the catalytic isomerization system, １０ 13. The system of claim 11 or 12, further comprising a metathesis purification system configured to isolate the composition comprising the linear internal olefin.

14. 14. The system of claim 13, wherein the purification system comprises extraction, filtration, evaporation, distillation, or any combination thereof.

15. 15. The system of any one of claims 11 to 14, wherein the catalyst system or catalyst system component comprises a heteroatom-ligand chromium compound complex and an alkylaluminum compound, or a heteroatom-ligand, a chromium compound, and an alkylaluminum compound.

16. A process comprising: (i) Structure CH ３ (CH ２ ) ｎ HC=CH ２ contacting a first normal alpha olefin having the structure CH with a metathesis catalyst system to produce a metathesis product; ３ (CH ２ ) ｎ HC=CH(CH ２ ) ｎ CH ３ forming a linear internal olefin having (ii) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of actinic radiation to produce a linear internal olefin of the structure CH ３ (CH ２ ) ２ｎ＋１ HC=CH ２ and forming a second normal alpha olefin having In the formula, n is an integer from 0 to 15; or (a) Structure CH ３ (CH ２ ) ｐ HC=CH ２ and a first normal alpha olefin having the structure CH ３ (CH ２ ) ｑ HC=CH ２ and contacting a second normal alpha olefin having the structure CH ３ (CH ２ ) ｐ HC=CH(CH ２ ) ｑ CH ３ forming a linear internal olefin having (b) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of actinic radiation to produce a linear internal olefin of the structure CH ３ (CH ２ ) ｐ＋ｑ＋１ HC=CH ２ and forming a third normal alpha olefin having wherein p and q are each an integer from 0 to 15.

17. 17. The process of claim 16, wherein the process comprises steps (i) and (ii).

18. the first normal alpha olefin comprises 1-butene and the second normal alpha olefin comprises 1-hexene; or the first normal alpha olefin comprises 1-pentene and the second normal alpha olefin comprises 1-octene; or the first normal alpha olefin comprises 1-hexene and the second normal alpha olefin comprises 1-decene; or 18. The process of claim 17, wherein the first normal alpha olefin comprises 1-octene and the second normal alpha olefin comprises 1-tetradecene.

19. 17. The process of claim 16, wherein the process comprises steps (a) and (b).

20. the first normal alpha olefin comprises 1-butene, the second normal alpha olefin comprises 1-octene, and the third normal alpha olefin comprises 1-decene; or the first normal alpha olefin comprises 1-butene, the second normal alpha olefin comprises 1-hexene, and the third normal alpha olefin comprises 1-octene; or 20. The process of claim 19, wherein the first normal alpha olefin comprises propylene, the second normal alpha olefin comprises pentene, and the third normal alpha olefin comprises 1-hexene.

21. 21. The process or system of any one of claims 1 to 20, wherein the metathesis catalyst system is a metal oxide-based metathesis catalyst system, a metal halide-based metathesis catalyst system, a metal carbene-based metathesis catalyst system, or any combination thereof.

22. 22. The process or system of any one of claims 1 to 21, wherein the catalytic isomerization catalyst system comprises a photocatalyst, a hydrogen atom transfer agent, a metal ion, and a proton donor.

23. the molar ratio of the metal ions to the photocatalyst is in the range of 3:1 to 1:1; or the molar ratio of the proton donor to the photocatalyst is in the range of 3:1 to 1:1; or Said C １０ the amount of the photocatalyst in the catalyst system based on linear internal olefin ranges from 0.1 mol % to 10 mol %, or from 1 mol % to 5 mol %, or 23. The process or system of claim 22, any combination thereof.

24. 24. The process or system of claim 22 or 23, wherein the actinic radiation comprises a wavelength of light in the range of 450 to 495 nm.

25. 22. The process or system of any one of claims 1 to 21, wherein the catalytic isomerization catalyst system comprises a photocatalyst, a metal-containing cocatalyst, and an optional disulfide compound.

26. 26. The process or system of claim 25, wherein the molar ratio of the photocatalyst to the co-catalyst ranges from 2:1 to 1:

2.

27. 27. The process or system of claim 25 or 26, wherein the actinic radiation comprises wavelengths of light in the range of 300 to 500 nm.

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