Selective production of 1-hexene / 1-octene using 1-decene

Abstract

A process for producing 1-octene and 1-decene comprises (a) separating a composition comprising an oligomer product comprising 15 to 80 mol% of C6 olefins, 20 to 80 mol% of C8 olefins, and 5 to 20 mol% of C10 + olefins, the composition is separated into a first oligomer composition containing C6 alkanes and at least 85 mol% of C6 olefins (e.g., 1-hexene), a second oligomer composition containing at least 20 mol% of C8 olefins (e.g., 1-octene), and a heavy stream containing C10 + olefins, then (b) contacting a metathesis catalyst system with the first oligomer composition to form a first composition comprising C10 linear internal olefins, (c) contacting the C10 linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a second composition comprising 1-decene, and (d) purifying the second composition to isolate a third composition comprising at least 90 mol% 1-decene. Also described are methods of producing 1-hexene and 1-decene, as well as related manufacturing systems and methods of producing higher carbon number normal alpha olefins from lower carbon number normal alpha olefins.

Description

[0001] Citation of Related Applications

[0002] This application is filed as a PCT international patent application on October 24, 2023 and claims the benefit and priority of 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. Technical Field

[0003] The present disclosure generally relates to systems and methods for producing a combination of 1-decene with 1-hexene, 1-octene, or both 1-hexene and 1-octene. Background Art

[0004] The synthesis of normal alpha-olefins with specific carbon numbers (especially 1-hexene, 1-octene, and 1-decene) is of great significance in the chemical industry. However, with existing catalysts and reaction processes, it is difficult to selectively produce only the alpha-olefin fraction with the desired carbon number, rather than a complex mixture of olefin products. Developing new methods to produce the desired combination of specific C 6 -C 10 alpha-olefins would be beneficial. Accordingly, the present invention generally aims at these purposes. Summary of the Invention

[0005] The Summary of the Invention is provided to introduce a selection of concepts that are further described herein in a simplified form. The Summary of the Invention is not intended to identify essential or necessary features of the claimed subject matter. The Summary of the Invention is also not intended to be used to limit the scope of the claimed subject matter.

[0006] The first method described herein can be used to produce 1-octene and 1-decene. The first method can include a) separating a composition comprising an oligomer product, the oligomer product comprising 15 to 80 mole % C 6 olefins, 20 to 80 mole % C 8 olefins, and 5 to 20 mole % C 10 + olefins, separating the composition into i) a first oligomer composition comprising C 6 alkanes and at least 85 mole % C 6 olefins, the C 6 olefins comprising at least 80 mole % 1-hexene, ii) a second oligomer composition comprising at least 20 mole % C 8 olefins, the C 8 olefins comprising at least 85 mole % 1-octene, and iii) a heavy feed stream comprising C 10 + olefins, b) contacting all or a portion of the first oligomer composition with a metathesis catalyst system to form a composition comprising C 10A first composition of linear internal olefins, c) in the presence of photochemical irradiation, contacting all or a portion of the C 10 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] The second method described herein can be used to produce 1-hexene and 1-decene. The second method can include a) separating a composition comprising an oligomer product, the oligomer product comprising at least 85 mole % C 6 olefins and at least 5 mole % C 8 + olefins, separating the composition into i) a first oligomer composition comprising C 6 alkanes and at least 90 mole % C 6 olefins, the C 6 olefins comprising at least 90 mole % 1-hexene, and ii) a heavy stream comprising C 8 + olefins, b) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to form a first composition comprising C 10 linear internal olefins, c) in the presence of photochemical irradiation, contacting all or a portion of the C 10 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.

[0008] Also disclosed herein are related manufacturing systems. A first (1-octene and 1-decene) manufacturing system can include 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, the oligomer product comprising 15 to 80 mole % C 6 olefins, 20 to 80 mole % C 8 olefins and 5 to 20 mole % C 10 + olefins, 2) a fractionation system configured to separate the composition comprising the oligomer product into i) a first oligomer composition comprising 1-hexene, ii) a second oligomer composition comprising 1-octene, and iii) a heavy stream comprising C 10 + olefins, 3) a metathesis system configured to contact a metathesis catalyst system with all or a portion of the first oligomer composition to form a first composition comprising C 10 linear internal olefins, 4) a catalytic isomerization system configured to, in the presence of photochemical irradiation, contact C 10all or a portion of the linear internal olefins are contacted with a catalytic isomerization catalyst system to form a second composition comprising 1-decene, and 5) a purification system configured to separate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0009] The second (1-hexene and 1-decene) production system may include 1) an ethylene oligomerization system configured to oligomerize ethylene in the presence of a catalyst system or a catalyst system component to form a composition comprising an oligomer product, the oligomer product comprising at least 85 mol% C 6 Olefins and at least 5 mol% C 8 + olefins, 2) a fractionation system configured to separate a composition comprising the oligomer product into a first oligomer composition comprising 1-hexene and a second oligomer composition comprising C 8 3) a metathesis system configured to contact a metathesis catalyst system with all or a portion of the first oligomer composition to form a C 10 a first composition of linear internal olefins, 4) a catalytic isomerization system configured to, in the presence of photochemical irradiation, 10 all or a portion of the linear internal olefins are contacted with a catalytic isomerization catalyst system to form a second composition comprising 1-decene, and 5) a purification system configured to separate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0010] The third method described herein can be used to produce a higher carbon number normal alpha olefin from a lower carbon number normal alpha olefin. The method may include: (i) treating a olefin having a structure CH 3 (CH 2 ) n HC=CH 2 The first normal alpha olefin is contacted with a metathesis catalyst system to form a first normal alpha olefin having the structure CH 3 (CH 2 ) n HC=CH(CH 2 ) n CH 3 (ii) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a linear internal olefin having the structure CH 3 (CH 2 ) 2n+1 HC=CH 2 In the third method, n is an integer which may range from 0 to 15.

[0011] A fourth method described herein can be used to produce a higher carbon number normal alpha olefin from two lower carbon number normal alpha olefins. The method may include: (a) making a olefin having the structure CH 3(CH 2 ) p HC=CH 2 of a first normal alpha-olefin and having the structure CH 3 (CH 2 ) q HC=CH 2 of a second normal alpha-olefin is contacted with a metathesis catalyst system to form a linear internal olefin having the structure CH 3 (CH 2 ) p HC=CH(CH 2 ) q CH 3 , and (b) in the presence of photochemical irradiation, contacting the linear internal olefin with a catalytic isomerization catalyst system to form a third normal alpha-olefin having the structure CH 3 (CH 2 ) p+q+1 HC=CH 2 . In a fourth method, p and q are independently integers in the range from 0 to 15. Although p and q can be the same integer, typically p and q are different integers.

[0012] The foregoing summary and the following detailed description both provide examples and are merely illustrative. Accordingly, the foregoing summary and the following detailed description should not be considered restrictive. Further, features or variations may be provided in addition to those features or variations described herein. For example, certain aspects may relate to various combinations and sub-combinations of features described in the detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The following drawings form a part of this specification and are included to further illustrate certain aspects of the present invention. The present invention can be better understood by referring to one or more of these drawings in conjunction with the detailed description.

[0014] Figure 1 Shows a 1-octene / 1-decene manufacturing system consistent with one aspect of the present disclosure.

[0015] Figure 2 Shows a 1-octene / 1-decene manufacturing system consistent with another aspect of the present disclosure.

[0016] Figure 3 Shows a 1-hexene / 1-decene manufacturing system consistent with another aspect of the present disclosure.

[0017] Although the inventions disclosed herein are susceptible to various modifications and alternative forms, only a few specific aspects have been shown by way of example in the drawings and are described in detail below. The drawings and the detailed description of these specific aspects are not intended in any way to limit the breadth or scope of the inventive concept or the appended claims. On the contrary, the drawings and the detailed description are provided to illustrate the inventive concept to those of ordinary skill in the art and to enable such persons to make and use the inventive concept.

[0018] Definitions

[0019] To more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in this disclosure but not specifically defined herein, the definitions in the IUPAC Compendium of Chemical Terminology, 2nd Edition (1997) may be applied, provided that such definitions do not conflict with any other disclosure or definition applied herein or render any claim to which such definition is applied indefinite or unenforceable. If any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein shall control.

[0020] In this disclosure, the features of a subject matter may be described such that different combinations of features may be contemplated within a particular aspect. For each aspect and / or feature disclosed herein, all combinations are considered that do not adversely affect the designs, compositions, processes, and / or methods described herein, with or without an express description of a particular combination. Additionally, unless otherwise expressly stated, any aspect and / or feature disclosed herein may be combined to describe inventive features consistent with this disclosure.

[0021] In this disclosure, although compositions, processes / methods, and systems are described in terms of "comprising" various materials, steps, and components, unless otherwise noted, the compositions, processes / methods, and systems may also "consist essentially of" or "consist of" the various materials, steps, or components.

[0022] Unless otherwise indicated, the terms "a / an" and "the" are intended to include plural alternatives, e.g., at least one. For example, unless otherwise indicated, the disclosure of "an C 8 alkene" or "a Bronsted base" is intended to cover, respectively, one C 8 alkene or Bronsted base, or more than one C 8 alkene or combination of Bronsted bases.

[0023] Generally, groups of elements are indicated using the numbering scheme indicated in the version of the periodic table published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, groups of elements may be indicated using the common name assigned to the group; for example, alkali metals indicate Group 1 elements, alkaline earth metals indicate Group 2 elements, transition metals indicate Groups 3-12 elements, and halogens or halide ions indicate Group 17 elements.

[0024] For any particular compound or group disclosed herein, unless otherwise indicated, any name or structure presented is intended to cover all conformational isomers, positional isomers, stereoisomers, and mixtures thereof that can be produced by a particular set of substituents. Unless otherwise specified, the name or structure also covers all enantiomers, diastereomers, and other optical isomers (if any), whether enantiomeric or racemic forms, and mixtures of stereoisomers, as known to those skilled in the art. For example, a general reference to a hexene (or hexenes) includes all straight-chain or branched-chain, acyclic or cyclic hydrocarbon compounds having six carbon atoms and 1 carbon-carbon double bond; a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane; and a general reference to butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl.

[0025] Unless otherwise indicated, the terms “contact” and “combine” are used herein to describe compositions, processes / methods, and systems in which materials are contacted or combined together in any order, in any manner, and for any length of time. For example, the materials can be blended, mixed, slurried, dissolved, reacted, treated, impregnated, compounded, or otherwise contacted or combined by any suitable method or technique.

[0026] The terms “catalyst composition,” “catalyst mixture,” “catalyst system,” etc. are not dependent on the actual product or composition produced by the contact or reaction of the initial components of the disclosed or claimed catalyst composition / mixture / system, the nature of the active catalytic sites, or the fate of the initial components after combination of the components. Thus, the terms “catalyst composition,” “catalyst mixture,” “catalyst system,” etc. cover the initial starting components of the composition, as well as any products that may be produced by contacting these initial starting components, and this includes heterogeneous and homogeneous catalyst systems or compositions. The terms “catalyst composition,” “catalyst mixture,” “catalyst system,” etc. may be used interchangeably throughout the present disclosure.

[0027] Whenever used in this specification and the claims, the term "hydrocarbon" refers to a compound containing only carbon and hydrogen. Other identifiers may be used to indicate the presence of specific groups in the hydrocarbon (e.g., halogenated hydrocarbon indicates the presence of one or more halogen atoms substituting an equal number of hydrogen atoms in the hydrocarbon). The term "hydrocarbyl group" is used herein according to the definition prescribed by IUPAC: a monovalent group formed by removing one hydrogen atom from a hydrocarbon. Similarly, "alkylene" 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 each of two different carbon atoms. Thus, according to the terms used herein, "hydrocarbyl group" refers to a generalized group formed by removing one or more hydrogen atoms (as required for a particular group) from a hydrocarbon. "Hydrocarbyl group", "alkylene", and "hydrocarbon group" may be acyclic or cyclic groups, and / or may be straight-chain or branched-chain. "Hydrocarbyl group", "alkylene", and "hydrocarbon group" may include rings, ring systems, aromatic rings, and aromatic ring systems containing only carbon and hydrogen. "Hydrocarbyl group", "alkylene", and "hydrocarbon group" include, for example, groups such as aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups as members.

[0028] Whenever used in this specification and the claims, the term "alkane" refers to a saturated hydrocarbon compound. Other identifiers may be used to indicate the presence of specific groups in the alkane (e.g., halogenated alkane indicates the presence of one or more halogen atoms substituting an equal number of hydrogen atoms in the alkane). The term "alkyl" is used herein according to the definition prescribed by IUPAC: a monovalent group formed by removing one hydrogen atom from an alkane. Similarly, "alkylene" refers to a group formed by removing two hydrogen atoms (two hydrogen atoms from one carbon atom or one hydrogen atom from each of two different carbon atoms) from an alkane. "Alkane group" is a general term that refers to a group formed by removing one or more hydrogen atoms (as required for a particular group) from an alkane. Unless otherwise specified, "alkyl", "alkylene", and "alkane group" may be acyclic or cyclic groups, and / or may be straight-chain or branched-chain. Primary alkyl, secondary alkyl, and tertiary alkyl are derived by removing a hydrogen atom from a primary carbon atom, secondary carbon atom, or tertiary carbon atom of an alkane, respectively. Normal alkyl may be derived by removing a hydrogen atom from the terminal carbon atom of a straight-chain alkane.

[0029] As used throughout this specification and the claims, the term "olefin" refers to a hydrocarbon having at least one carbon-carbon double bond that is not part of an aromatic ring or aromatic ring system. Unless otherwise specifically stated, the term "olefin" 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 having only one, only two, only three, etc. carbon-carbon double bonds can be identified by using the terms "mono", "di", "tri", etc. in the name of the olefin. Olefins can be further identified by the position of one or more carbon-carbon double bonds.

[0030] As used herein, the term "α-olefin" refers to any olefin having a carbon-carbon double bond between the first and second carbon atoms of the longest continuous carbon atom chain. Unless otherwise explicitly stated, the term "α-olefin" includes straight-chain and branched-chain α-olefins and α-olefins that can have more than one non-aromatic carbon-carbon double bond. The term "normal α-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 "internal branched 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.

[0031] "Aromatic compound" refers to a compound containing a cyclic conjugated moiety that follows Hückel's (4n + 2) rule and contains (4n + 2) π electrons, where n is an integer from 1 to about 5. Unless otherwise specified, aromatic compounds can be monocyclic or polycyclic. Non-limiting examples of aromatic compounds include benzene, naphthalene, and toluene, etc.

[0032] The term "substituted", when used to describe a compound or group, e.g., when referring to a substituted analogue of a particular compound or group, is intended to describe any non-hydrogen moiety that formally replaces the hydrogen in the group, and is intended to be non-limiting. A group or groups can also be referred to herein as "unsubstituted", or equivalent terms such as "non-substituted", which refers to the original group in which the non-hydrogen moiety does not replace the hydrogen in the group. Unless otherwise specified, "substituted" is intended to be non-limiting and includes inorganic substituents or organic substituents.

[0033] The term oligomer refers to a product containing 2 to 20 monomer units. The terms "oligomeric product" and "oligomer product" include all products prepared by an "oligomerization" process, including "oligomers" and products that are not "oligomers" (e.g., products containing more than 20 monomer units, or solid polymers), but exclude other non-oligomeric components of the oligomerization reaction zone effluent stream, such as unreacted ethylene, organic reaction medium, and hydrogen, as well as other components.

[0034] The term "oligomerization" and its derivatives refer to a process for producing an oligomeric product that comprises at least 20 wt%, 35 wt%, 50 wt% or 60 wt% of a product containing 2 to 20 monomer units. In one example, an "oligomerization" process using ethylene as the monomer produces a product mixture that comprises at least 20 wt%, 35 wt%, 50 wt% or 60 wt% of an oligomer having 4 to 40 carbon atoms.

[0035] The term "reaction zone effluent" and its derivatives (e.g., oligomerization reaction zone effluent) generally refer to all materials that leave the reaction zone through the reaction zone outlet / discharge port of the reaction mixture and may include reaction zone feeds (e.g., ethylene, catalyst system or catalyst system components, and / or solvent), and / or reaction products (e.g., an oligomeric product comprising oligomers and non-oligomers). The term "reaction zone effluent" and its derivatives may be qualified by using additional qualifying terms to refer to certain portions. For example, the reaction zone effluent refers to all materials that leave the reaction zone through the reaction zone outlet / discharge port, while the reaction zone oligomeric product effluent refers only to the oligomeric product within the reaction zone effluent.

[0036] As used herein, the term "solvent" applies to a material that can dissolve a compound or a material that can dilute reaction components. Thus, unless otherwise specified, the term "solvent" may encompass materials that can act as diluents.

[0037] The present invention discloses several types of ranges. When any type of range is disclosed or claimed, it is intended that every possible number that such range could reasonably encompass be disclosed or claimed individually, including the endpoints of the range and any sub-ranges and combinations of sub-ranges subsumed therein. For example, when a chemical moiety having a certain number of carbon atoms is disclosed or claimed, it is intended that every possible number that such range could encompass, consistent with the disclosure herein, be disclosed or claimed individually. For example, as used herein, the disclosure of a moiety being C 1 to C 18 hydrocarbyl or in other words, a hydrocarbyl having 1 to 18 carbon atoms is meant to refer 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 these two numbers (e.g., C 1 to C 8 hydrocarbyl), and also includes any combination of ranges between these two numbers (e.g., C 2 to C 4 and C 12 to C 16 hydrocarbyl). Similarly, all other ranges disclosed herein should be interpreted in a manner similar to this example.

[0038] Generally, quantities, sizes, formulations, parameters, ranges, or other numerical or characteristic values are “about” or “approximately”, whether or not expressly stated as such. The claims include equivalents of the numerical or characteristic values whether or not modified by the term “about” or “approximately”.

[0039] Features provided as minimum values within the present disclosure may alternatively be phrased as “at least” or “greater than or equal to” any recited minimum value of the features disclosed herein. Features provided as maximum values within the present disclosure may alternatively be phrased as “less than or equal to” or “below” any recited maximum value of the features disclosed herein.

[0040] Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, typical methods and materials are described herein.

[0041] All publications and patents mentioned herein are incorporated herein by reference in their entirety for the purpose of description and disclosure, e.g., to describe and disclose constructs and methods described in the publications and patents, which constructs and methods can be used in conjunction with the presently described invention. Detailed Description

[0042] Systems and methods for producing 1-decene in combination with 1-hexene, 1-octene, or a combination of 1-hexene and 1-octene are disclosed herein, as well as general methods for producing higher carbon number normal alpha-olefins from lower carbon number normal alpha-olefins.

[0043] The development of methods for the selective synthesis of 1-decene presents unique challenges. Ethylene oligomerization methods for generating 1-hexene and 1-octene typically involve a metal cycle mechanism that does not operate efficiently for higher oligomers (e.g., 1-decene and above). Without wishing to be bound by theory, it is believed that the intermediate chromacycle is unstable and prone to decomposition before allowing the insertion of a 5th ethylene to form an 11-membered ring. Thus, 1-decene is typically synthesized through chemical reactions and using a catalyst system that is not selective for a particular molecule (1-decene), but rather produces a range of materials that must be inefficiently separated or fractionated. Considering all of the other product fractions produced simultaneously, the ethylene efficiency of methods for producing 1-decene would be very low.

[0044] A first object of the present invention is a system and method for producing 1-octene and 1-decene, wherein an ethylene oligomerization product stream containing 1-hexene and 1-octene is separated, wherein the 1-octene fraction is the primary product, while the 1-hexene fraction typically has a lower purity (e.g., based on C 6 less than 95 mol %). Additionally, the C 6 fraction containing 1-hexene also contains internal and cyclic C 6materials that are difficult to separate without large and complex distillation columns and processes. Instead of purifying and cleaning the impure C 6 feed stream, which is metathesized and catalytically isomerized herein to ultimately convert most of the 1-hexene to 1-decene, thereby producing a selective octene / decene process. Alternatively, a dedicated 1-hexene system can be used to supply 1-hexene for metathesis and subsequent catalytic isomerization.

[0045] For example, many end uses of 1-hexene require a purity of 99 mole % or higher (based on C 6 ), but as shown in the exemplary C 6 fraction from an ethylene oligomerization process in Table I, it is not uncommon for the purity of 1-hexene to be approximately 90 mole %, and the boiling points of other C 6 substances present are within 5-15 °C of 1-hexene. As is evident from Table I, the boiling points of the C 6 substances are very close, resulting in the need for complex separation using large distillation columns to isolate 1-hexene with a purity exceeding 99 mole %. Advantageously, metathesis of the substances in Table I will result in an easier separation process because only 1-hexene is metathesized to 5-decene, and separating alkane impurities (e.g., C 6 alkanes generally do not undergo metathesis) or metathesized olefin impurities (which do not produce decene) from 5-decene is significantly easier than separating them as C 6 components as shown in Table I.

[0046] Table I

[0047]

[0048] In addition, contrary to the end uses of 1-hexene that require a purity of 99 mole % or higher, most end use applications of 1-decene only require a purity in the range of 95-98 mole % (e.g., 96.5 mole % purity). Compared to C 6 hydrocarbons, this further simplifies the purification process of C 10 hydrocarbons because the purity requirements for the desired normal alpha olefins are lower.

[0049] A second object of the present invention is a system and method for producing 1-hexene and 1-decene, wherein a selective ethylene oligomerization product stream containing 1-hexene is first produced. Then a portion of the 1-hexene stream is metathesized and catalytically isomerized to ultimately convert the 1-hexene portion into 1-decene, thereby producing a selective hexene / decene process. The benefit of such a hexene / decene system and method is that 1-hexene can be continuously produced, while 1-decene can be produced on demand or as needed.

[0050] These disclosed systems and methods provide for the simultaneous 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 methods can vary based on market demand, production capacity, and the profit margins of the corresponding normal alpha olefins (e.g., 1-decene and 1-hexene).

[0051] A third object of the present invention is a method for producing higher carbon number normal alpha olefins from lower carbon number normal alpha olefins, wherein 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 can be 1-butene, and the higher carbon number normal alpha olefin can be 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).

[0052] Method for preparing octene / decene or hexene / decene

[0053] Aspects of the present invention relate to methods for producing a combination of 1-decene and 1-octene or 1-hexene. The first method described herein can be used to produce 1-octene and 1-decene, and the first method can include the following steps (or consist essentially of the following steps, or consist of the following steps): a) separating a composition comprising an oligomer product, the oligomer product comprising 15 to 80 mole % C 6 olefins, 20 to 80 mole % C 8 olefins, and 5 to 20 mole % C 10 + olefins, separating the composition into i) a first oligomer composition comprising C 6 alkanes and at least 85 mole % C 6 olefins, the C 6 olefins comprising at least 80 mole % 1-hexene, ii) a second oligomer composition comprising at least 20 mole % C 8 olefins, the C 8 olefins comprising at least 85 mole % 1-octene, and iii) a heavy feed stream comprising C 10 + olefins, b) contacting all or a portion of the first oligomer composition with a metathesis catalyst system to form a first composition comprising C 10 linear internal olefins, c) contacting all or a portion of the C 10 linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a second composition comprising 1-decene, and d) purifying the second composition to separate a third composition comprising at least 90 mole % 1-decene.

[0054] The second method described herein can be used to produce 1-hexene and 1-decene, and the second method can include the following steps (or consist essentially of the following steps, or consist of the following steps): a) separating a composition comprising an oligomer product, the oligomer product comprising at least 85 mole % C 6 olefins and at least 5 mole % C 8 + olefins, separating the composition into i) a first oligomer composition comprising C 6 alkanes and at least 90 mole % C 6 olefins, the C 6 olefins comprising at least 90 mole % 1-hexene, and ii) a heavy feed stream comprising C 8 + olefins, b) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to form a first composition comprising C 10 linear internal olefins, c) contacting all or a portion of the C 10 linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation 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.

[0055] Generally, the features of the first and second methods (e.g., features such as the oligomer product, the first oligomer composition, the second oligomer composition, the metathesis step, the catalytic isomerization step, and the purification step, etc.) are described independently herein, and these features can be combined in any combination to further describe the two methods. Additionally, unless otherwise stated, additional method steps can be performed before, during, and / or after the steps of these methods.

[0056] Now referring to the first method, step a) separates (or fractionates) a composition comprising an oligomer product, the oligomer product comprising 15 to 80 mole % C 6 olefins, 20 to 80 mole % C 8 olefins, and 5 to 20 mole % C 10 + olefins, separating (or fractionating) the composition into i) a first oligomer composition comprising C 6 alkanes and at least 85 mole % C 6 olefins, the C 6 olefins comprising at least 80 mole % 1-hexene, ii) a second oligomer composition comprising at least 20 mole % C 8 olefins, the C 8 olefins comprising at least 85 mole % 1-octene, and iii) a composition comprising C 10+ Heavy feed stream of olefins. In step a) of the first process, the composition containing the oligomer product can be the reaction zone effluent from an ethylene oligomerization reactor / system and can be formed by contacting ethylene, a catalyst system or catalyst system components (optional organic reaction medium and optional hydrogen) in the reaction zone. In one aspect, the catalyst system or catalyst system components can comprise a heteroatom ligand chromium compound complex and an alkylaluminum compound, or a heteroatom ligand, a chromium compound, and an alkylaluminum compound. Thus, in addition to the oligomer product, the composition (e.g., reaction zone effluent) can contain the catalyst (activated or deactivated) and the organic reaction medium. The separation (or fractionation) of the composition containing the oligomer product can be carried out in one or more steps (usually in multiple steps) to form a first oligomer composition, a second oligomer composition, and a heavy feed stream. Representative patent documents related to ethylene oligomerization processes and catalyst systems include U.S. Patent 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.

[0057] For the first process, the oligomer product in step a) contains 15 to 80 mol% C 6 olefins, 20 to 80 mol% C 8 olefins, and 5 to 20 mol% C 10 + olefins. For example, the oligomer product can contain 25 to 75 mol% C 6 olefins in one aspect, 30 to 70 mol% C 6 olefins in another aspect, 35 to 65 mol% C 6 olefins in yet another aspect, and 40 to 60 mol% C 6 olefins in still another aspect. Additionally or alternatively, the oligomer product can contain 25 to 75 mol% C 8 olefins in one aspect, 30 to 70 mol% C 8 olefins in another aspect, 35 to 65 mol% C 8 olefins in yet another aspect, and 40 to 60 mol% C 8 olefins in still another aspect. Additionally or alternatively, the oligomer product can contain 5 to 18 mol% C 10 + olefins; alternatively, 5 to 15 mol% C 10 + olefins; alternatively, 7 to 20 mol% C 10 + olefins; or alternatively, 7 to 18 mol% C 10 + olefins. As will be readily appreciated by those skilled in the art, the sum of these and other components does not exceed 100 mol%.

[0058] Separate the composition containing the oligomer product into i) a first oligomer composition comprising C 6 alkanes and at least 85 mol% C 6 olefins, said C 6 olefins comprising at least 80 mol% 1-hexene, ii) a second oligomer composition comprising at least 20 mol% C 8 olefins, said C 8 olefins comprising at least 85 mol% 1-octene, and iii) a heavy stream comprising C 10 + olefins. Now referring to the first oligomer composition, in some aspects it may contain at least 85 mol%, at least 90 mol%, at least 93 mol% or at least 95 mol% C 6 olefins. Thus, the typical range of the amount of C 6 olefins in the first oligomer composition can include but is not limited to 85 to 99 mol%, 90 to 99.5 mol%, 93 to 98 mol%, 95 to 99 mol%, etc. At least 80 mol% C 6 olefins are 1-hexene, but more commonly, C 6 olefins contain at least 85 mol%, at least 90 mol% or at least 95 mol% 1-hexene; thus, the typical ranges include 80 mol% to 98 mol%, 80 mol% to 95 mol%, 85 mol% to 95 mol% or 90 to 99 mol% 1-hexene. In addition to 1-hexene, C 6 olefins may also contain internal and cyclic C 6 olefins (e.g., 2-hexene, 3-hexene, methylenecyclopentane, etc.), and C 6 olefins typically may contain 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 total internal and cyclic C 6 olefins. C 6 alkanes are also present in the first oligomer composition; representative C 6 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% C 6 alkanes.

[0059] In the first method, the second oligomer composition may comprise at least 20 mol% C 8 olefins, and the C 8 olefins may contain at least 85 mol% 1-octene. In some aspects, the second oligomer composition may 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, the amount of C 8 olefins in the second oligomer composition can typically range from, but is not limited to, 20 to 99 mol%, 50 to 99 mol%, 75 to 99 mol%, 85 to 99 mol%, 90 to 99.5 mol%, 95 to 99.5 mol%, 97 to 99 mol%, etc. At least 85 mol% C 8 olefins are 1-octene, but more commonly, the C 8 olefins contain at least 90 mol%, at least 95 mol% or at least 97 mol% 1-octene; thus, typical ranges include 85 mol% to 98 mol%, 90 mol% to 99 mol%, 95 mol% to 98 mol% or 97 to 99.5 mol% 1-octene.

[0060] Now referring to step b) of the first method, contacting the metathesis catalyst system with all or a portion of the first oligomer composition to form a first composition comprising C 10 linear internal olefins. Based on the C 6 + olefins in the first oligomer composition, the first composition typically can comprise at least 85 mol%, at least 90 mol%, at least 92 mol% or at least 95 mol% C 10 linear internal olefins. Suitable metathesis catalyst systems for step b) are disclosed below, and any suitable conditions for the metathesis step b) can be employed, as would be recognized by those skilled in the art based on the present disclosure and, for example, U.S. Patent No. 8,765,984.

[0061] Optionally, prior to step c), the first method can further comprise the step of separating from the first composition a composition comprising at least 90 mol%, at least 93 mol% or at least 96 mol% C 10 linear internal olefins. Any suitable technique can be used, such as extraction, filtration, evaporation, distillation, etc., and any combination thereof. Advantageously, the C 6 alkanes in the first oligomer composition do not undergo metathesis, so these materials will be relatively easy to separate from the C 10 linear internal olefins. Similarly, methylenecyclopentane does not react in metathesis, so this material is also relatively easy to separate from the C 10 linear internal olefins. In addition, internal C 6 olefins undergo metathesis to form non-C 10 olefins, which also become easier to separate from the C 10 linear internal olefins.

[0062] In step c), in the presence of photochemical irradiation, C 10All or a portion of the linear internal olefin (e.g., 5-decene) is contacted with a catalytic isomerization catalyst system to form a second composition comprising 1-decene. Any suitable catalytic isomerization catalyst system can be used, provided that it is suitable for chain-walking the double bond to the terminal position. Suitable catalytic isomerization catalyst systems for step c) are disclosed below, and any suitable conditions for the catalytic isomerization step c) can be employed, as will be recognized by those skilled in the art based on the present disclosure and, for example, the following: 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.

[0063] Typically, 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 this 1-decene is based on the initial amount of the linear internal olefin that is contacted with the catalytic isomerization catalyst system in the presence of photochemical irradiation in step c). 10 Initial amount of linear internal olefin.

[0064] In step d) of the first method, the second composition comprising 1-decene can be purified to isolate a third composition containing at least 90 mole% 1-decene. Any suitable technique, such as extraction, filtration, evaporation, distillation, or any combination of two or more of these techniques, can be used to separate or isolate the third composition containing 1-decene from the second composition. Although the third composition contains at least 90 mole% 1-decene, in some aspects, the third composition can contain at least 92 mole%, at least 95 mole%, at least 97 mole%, or at least 98 mole% 1-decene. Thus, typical ranges for the amount of 1-decene in the third composition can include, but are not limited to, 90 to 99 mole%, 92 to 99.5 mole%, 95 to 99 mole%, 98 to 99.5 mole%, etc.

[0065] Optionally, the first method can further comprise contacting a metathesis catalyst system with all or a portion of an olefin composition (comprising a second oligomer composition of C 8 olefins) to form a C 8 olefin composition. Optionally further, the first method can further comprise contacting a metathesis catalyst with a composition comprising C 14 and C 6 and C 8Contacting a light oligomer composition of olefins to form a composition comprising C 10 -C 14 A step of a composition of linear internal olefins. The light oligomer composition can be formed by combining at least a portion of a first oligomer composition (containing 1-hexene) and a second oligomer composition (containing 1-octene) in any relative amounts.

[0066] Now referring to the second method, in step a) separating (or fractionating) a composition comprising an oligomer product, said oligomer product comprising at least 85 mol% C 6 Olefins and at least 5 mol% C 8 + Olefins, separating (or fractionating) said composition into i) a first oligomer composition comprising C 6 Alkanes and at least 90 mol% C 6 Olefins, said C 6 Olefins comprising at least 90 mol% 1-hexene, and ii) a heavy stream comprising C 8 + Olefins. As in the first method, in step a) of the second method, the composition containing the oligomer product can be the effluent from the reaction zone of an ethylene oligomerization reactor / system. In addition to the oligomer product, the composition (e.g., the reaction zone effluent) can also contain a catalyst (activated or deactivated) and an organic reaction medium. The separation (or fractionation) of the composition containing the oligomer product can be carried out in one or more steps (usually in multiple steps) to form a first oligomer composition and a heavy stream.

[0067] It is noted that the oligomer product in the second method is different from the oligomer product in the first method, and the resulting fractionated compositions are also different. In the first method, the oligomer product comprises 15 to 80 mol% C 6 Olefins, 20 to 80 mol% C 8 Olefins and 5 to 20 mol% C 10 + Olefins, while the oligomer product in the second method comprises at least 85 mol% C 6 Olefins and at least 5 mol% C 8 + Olefins. In the first method, the oligomer product is separated into a first oligomer composition (mainly C 6 ), a second oligomer composition (mainly C 8 ) and a heavy stream comprising C 10 + Olefins, while the oligomer product in the second method is separated into a first oligomer composition (mainly C 6 ) and a heavy stream comprising C 8 + Olefins. The composition containing the oligomer product from the second method can generally be produced by a 1-hexene process, while the composition containing the oligomer product from the first method can be produced by a 1-hexene / 1-octene process.

[0068] For the second process, the oligomer product in step a) contains at least 85 mol% C 6 olefins and at least 5 mol% C 8 + olefins. For example, the oligomer product may contain on the one hand at least 87 mol% C 6 olefins, on the other hand at least 90 mol% C 6 olefins, on yet another hand at least 91 mol% C 6 olefins, and on still another hand at least 93 mol% C 6 olefins. Additionally or alternatively, the oligomer product may contain 5 to 15 mol% C 8 + olefins; alternatively, 5 to 12 mol% C 8 + olefins; alternatively, 6 to 14 mol% C 8 + olefins; or alternatively, 7 to 13 mol% C 8 + olefins. As will be readily appreciated by those skilled in the art, the sum of these and other components does not exceed 100 mol%.

[0069] Separate the composition containing the oligomer product into i) a first oligomer composition comprising C 6 alkanes and at least 90 mol% C 6 olefins, wherein the C 6 olefins comprise at least 90 mol% 1 - hexene, and ii) a heavy material stream comprising C 8 + olefins. Now referring to the first oligomer composition, in some aspects it may contain at least 92 mol%, at least 94 mol%, at least 96 mol% or at least 98 mol% C 6 olefins. Thus, typical ranges for the amount of C 6 olefins in the first oligomer composition may include but are not limited to 92 to 99.9 mol%, 94 to 99.9 mol%, 96 to 99.9 mol%, 98 to 99.9 mol%, etc. At least 90 mol% C 6 olefins is 1 - hexene, but more commonly, the C 6 olefins 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 to 99.9 mol% 1 - hexene. In addition to 1 - hexene, the C 6 olefins may also contain a generally minimal amount of internal and cyclic C 6 olefins (e.g., 2 - hexene, 3 - hexene, methylenecyclopentane, etc.), and the C 6 olefins generally may contain 0.1 mol% to 3 mol%, 0.2 mol% to 2 mol% or 0.25 mol% to 1 mol% of total internal and cyclic C6 Olefins. C 6 Alkanes are also present in the first oligomer composition in generally minimal amounts; representative C 6 alkanes include methylcyclopentane and n-hexane. Generally, 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% C 6 alkanes.

[0070] Steps b), c), and d) of the second process can generally be carried out as described herein for the corresponding steps b), c), and d) of the first process.

[0071] Optionally, similar to the first process, the second process may further include, before step c), separating from the first composition a composition comprising at least 90 mol%, at least 93 mol%, or at least 96 mol% C 10 linear internal olefins. Any suitable technique can be used, such as extraction, filtration, evaporation, distillation, etc., and any combination thereof. Advantageously, the C 6 alkanes in the first oligomer composition do not undergo metathesis, so these materials will be relatively easy to separate from the C 10 linear internal olefins. Similarly, methylenecyclopentane does not react in metathesis, so this material is also relatively easy to separate from the C 10 linear internal olefins. In addition, internal C 6 olefins undergo metathesis to form non-C 10 olefins, which also become easier to separate from the C 10 linear internal olefins.

[0072] Metathesis catalyst system

[0073] Although not limited thereto, the metathesis catalyst systems disclosed herein can be used to convert 1-hexene in the first oligomer composition to form a first composition containing C 10 linear internal olefins. Any suitable metathesis catalyst system can be used for the metathesis step, and non-limiting examples of such metathesis catalyst systems can include metal oxide-based metathesis catalyst systems, metal halide-based metathesis catalyst systems, metal carbene-based metathesis catalyst systems, or any combination thereof. In one aspect, the metathesis catalyst system can be a metal oxide-based metathesis catalyst system or a metal halide-based metathesis catalyst system, while in another aspect, the metathesis catalyst system 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.

[0074] The metathesis catalyst system based on metal oxides 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 metathesis catalyst system based on metal oxides may further comprise a support or an alkylmetal activator or both a support and an alkylmetal activator. Exemplary supports may include solid oxide materials such as alumina, silica, silica-alumina, and aluminum phosphate. Thus, non-limiting examples of supported metal-oxide-based metathesis catalyst systems may include molybdenum oxide / alumina (MoO 3 / Al 2 O 3 ), tungsten oxide / silica (WO 3 / SiO 2 ), rhenium oxide / alumina (Re 2 O 7 / Al 2 O 3 ), cobalt oxide and molybdenum oxide / alumina (CoO / MoO 3 / Al 2 O 3 ), and tetramethyltin-activated rhenium oxide / alumina (Re 2 O 7 / Al 2 O 3 / SnMe 4 ). Other suitable metal-oxide-based metathesis catalyst systems are known to those skilled in the art.

[0075] In addition, the metathesis catalyst system based on metal oxides may include an alkylmetal activator, which may include an alkyllithium, an alkylmagnesium, an alkylaluminum, an alkyltin compound, or any mixture thereof. In one aspect, the alkylmetal activator may be an alkyllithium compound. In another aspect, the alkylmetal activator may be an alkylmagnesium compound. In another aspect, the alkylmetal activator may be an alkylaluminum compound. In yet another aspect, the alkylmetal activator may be an alkyltin compound. Non-limiting examples of alkylaluminum compounds may include trialkylaluminum compounds and / or alkylaluminum halide compounds. The alkyl group on the alkylmetal activator may include any C 1 -to-C 10 hydrocarbyl group, or alternatively, any C 1 -to-C 5Hydrocarbyl. In various aspects, the alkyl group of the metal alkyl activator can 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 can include trimethylaluminum, triethylaluminum and triisobutylaluminum. The halide of the alkylaluminum halide compound can be chloride, bromide or iodide; alternatively, chloride; alternatively, bromide; or alternatively, iodide. Examples of suitable alkylaluminum halide compounds can include ethylaluminum dichloride, diethylaluminum chloride and ethylaluminum sesquichloride. Suitable and non-limiting examples of alkyltin compounds can include tetramethyltin, tetraethyltin and tetrabutyltin.

[0076] The metathesis catalyst system based on metal halide can include (or consist essentially of or consist of): halides of tungsten, halides of molybdenum or a combination thereof. For example, the metathesis catalyst system based on metal halide can include (or consist essentially of or consist of): halides of tungsten, or alternatively, halides of molybdenum. The halide of the metathesis catalyst system based on metal halide can be chloride, bromide or iodide. In one aspect, the halide can be chloride, and in another aspect, the halide can be bromide, and in yet another aspect, the halide can be iodide. Thus, the metathesis catalyst system based on metal halide can include (or consist essentially of, or consist of): tungsten chloride, molybdenum chloride or a mixture thereof; alternatively, tungsten chloride; or alternatively, molybdenum chloride.

[0077] Optionally, the metathesis catalyst system based on metal halide can further contain a metal alkyl activator (as described herein), oxygen, alcohol or any combination thereof; alternatively, a metal alkyl activator; alternatively, oxygen; or alternatively, alcohol. Non-limiting examples of the metathesis catalyst system based on metal halide can include tungsten chloride / tetrabutyltin (WCl 6 / SnMe 4 ), tungsten chloride / diethylaluminum chloride (WCl 6 / EtAlCl 2 ), tungsten chloride / diethylaluminum chloride / ethanol (WCl 6 / EtAlCl 2 / EtOH), molybdenum chloride / triethylaluminum (MoCl 5 / AlEt 3 ), and molybdenum chloride / triethylaluminum / O 2 (MoCl 5 / AlEt 3 / O 2)。Other suitable metathesis catalyst systems based on metal halides are known to those skilled in the art.

[0078] A metathesis catalyst system based on metal carbenes can include (or consist essentially of or consist of): tungsten, tantalum, osmium, molybdenum, ruthenium, or any combination thereof. For example, a metathesis catalyst system based on metal carbenes can include (or consist essentially of, or consist of): tungsten; alternatively, tantalum; alternatively, osmium; alternatively, molybdenum; or alternatively, ruthenium. These metathesis catalyst systems based on metal carbenes can contain compounds having a stable metal-carbon double bond, or can form a metal-carbon double bond in situ from a metal precursor having a stable metal-carbon single bond.

[0079] On the one hand, a ruthenium carbene-based metathesis catalyst system can contain a compound having the structure L 1 L 2 X 2 Ru=CHR 1 where L 1 and L 2 can be organic ligands, X can be a halide ion, and R 1 can be hydrogen or a hydrocarbon group. Generally, the compound having the structure L 1 L 2 X 2 Ru=CHR 1 in the ruthenium carbene-based metathesis catalyst system can be described using any combination of the L 1 , L 2 , X, or R 1 described herein.

[0080] Generally, L 1 and L 2 can independently be R’ 3 P, an imidazolinyl group, or an imidazolidinyl group. In some aspects, L 1 and L 2 can be R’ 3 P; alternatively, L 1 can be R’ 3 P and L 2 can be an imidazolinyl group or an imidazolidinyl group; alternatively, L 1 can be R’ 3 P and L 2 can be an imidazolinyl group; alternatively, L 1 can be R’ 3 P and L 2 can be an imidazolidinyl group; alternatively, L 1 and L 2 can be an imidazolinyl group; or alternatively, L 1 and L2 can be imidazolidinyl. In aspects of the present invention, R' can be a hydrocarbon group, where R' 3 each R' of P can be the same; alternatively, R' 3 each R' in P can be different; or alternatively, R' 3 one R' in P can be different from the other two R' groups. In some aspects, R' 3 each R' of P can independently be a C 1 to C 15 hydrocarbon group; or alternatively, a C 1 to C 10 hydrocarbon group. In other aspects, R' 3 each hydrocarbon R' of P can independently be an alkyl or aromatic group; alternatively, an alkyl group; or alternatively, an aromatic group. In one aspect, R' 3 each alkyl R' of P can independently be methyl, ethyl, n-propyl, isopropyl, tert-butyl, neopentyl, cyclopentyl or cyclohexyl. In some aspects, one or more R' groups of R' 3 P can be phenyl, or alternatively, a substituted phenyl. In one aspect, the substituents of any substituted phenyl can independently be a C 1 -C 5 organic group, or alternatively, a C 1 -C 5 hydrocarbon group. In some aspects, R' 3 P can be a trialkylphosphine or triphenylphosphine; alternatively, a trialkylphosphine; or alternatively, triphenylphosphine. In one aspect, R' 3 P can be trimethylphosphine, triethylphosphine, triisopropylphosphine, tributylphosphine, trineopentylphosphine, tricyclopentylphosphine, tricyclohexylphosphine or triphenylphosphine; alternatively, triisopropylphosphine, tributylphosphine, trineopentylphosphine, tricyclopentylphosphine, tricyclohexylphosphine or triphenylphosphine; alternatively, tricyclopentylphosphine, tricyclohexylphosphine or triphenylphosphine; alternatively, tricyclopentylphosphine or tricyclohexylphosphine; alternatively, tricyclopentylphosphine; alternatively, tricyclohexylphosphine; or alternatively, triphenylphosphine.

[0081] In one aspect, the imidazolinyl or imidazolidinyl can be a C 3 to C 80 imidazolinyl or imidazolidinyl; alternatively, a C 3 to C 50 imidazolinyl or imidazolidinyl; or alternatively, a C 5 to C 40Imidazolinyl or imidazolidinyl. In some aspects, the imidazolinyl can be a 1,3-disubstituted imidazolinyl. In some aspects, the imidazolidinyl can be a 1,3-disubstituted imidazolidinyl. In one aspect, the 1,3-substituents of the 1,3-disubstituted imidazolinyl or 1,3-disubstituted imidazolidinyl can independently be any suitable hydrocarbyl group. In one aspect, the 1,3-substituents of the 1,3-disubstituted imidazolinyl or 1,3-disubstituted imidazolidinyl can independently be a C 1 to C 30 hydrocarbyl group. In some aspects, the 1,3-substituents of the 1,3-disubstituted imidazolinyl or 1,3-disubstituted imidazolidinyl can independently be a C 6 to C 20 aromatic group or a C 1 to C 10 alkyl group. In other aspects, the 1,3-substituents of the 1,3-disubstituted imidazolinyl or 1,3-disubstituted imidazolidinyl can independently be a C 6 to C 20 aromatic group, or alternatively, a C 1 to C 10 alkyl group. In one aspect, each aromatic group in the 1,3-disubstituted imidazolinyl or 1,3-disubstituted imidazolidinyl can independently be a substituted aromatic group. In some aspects, the substituted aromatic group of the 1,3-disubstituted imidazolinyl or 1,3-disubstituted imidazolidinyl can be a 2-disubstituted phenyl, 2,6-disubstituted phenyl or 2,4,6-trisubstituted phenyl; alternatively, 2,6-disubstituted phenyl; or alternatively, 2,4,6-trisubstituted phenyl. Suitable substituents for any substituted phenyl within the 1,3-disubstituted imidazolinyl or 1,3-disubstituted imidazolidinyl can include any C 1 to C 10 hydrocarbyl group, or alternatively, any C 1 to C 5 hydrocarbyl group. In some aspects, each hydrocarbyl substituent can independently 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, isopropyl; or alternatively, tert-butyl. In some aspects, each substituted aromatic group of the 1,3-disubstituted imidazolinyl or 1,3-disubstituted imidazolidinyl can independently be 2,6-diisopropylphenyl or 2,4,6-trimethylphenyl; alternatively, 2,6-diisopropylphenyl; or alternatively, 2,4,6-trimethylphenyl.

[0082] In various aspects, having the structure L 1 L 2 X 2 Ru=CHR1 Each X of the compound can independently be a chloride ion, a bromide ion, or an iodide ion. In one aspect, X can be a chloride ion. In another aspect, X can be a bromide ion. In yet another aspect, X can be an iodide ion. Having the structure L 1 L 2 X 2 Ru=CHR 1 For the compound of R 1 can be hydrogen or C 1 to C 20 hydrocarbyl. In some aspects, R 1 can be methyl, ethyl, isopropyl, tert-butyl, phenyl, 2-methyl-2-propenyl, or 2,2-diphenylethynyl. In other aspects, R 1 can be tert-butyl, phenyl, 2-methyl-2-propenyl, or 2,2-diphenylethynyl; alternatively, hydrogen; alternatively, tert-butyl; alternatively, phenyl; alternatively, tert-butyl; alternatively, phenyl; alternatively, 2-methyl-2-propenyl; or alternatively, 2,2-diphenylethynyl.

[0083] In some non-limiting aspects, 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)dichlorotricyclohexylphosphine ruthenium, or 1,3-bis-(2,6-diisopropylphenyl)-2-(imidazolidinylidene)(phenylmethylene)dichlorotricyclohexylphosphine ruthenium. In some aspects, the ruthenium carbene-based metathesis catalyst system can include 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)dichlorotricyclohexylphosphine ruthenium; or alternatively, 1,3-bis-(2,6-diisopropylphenyl)-2-(imidazolidinylidene)(phenylmethylene)dichlorotricyclohexylphosphine ruthenium.

[0084] In one aspect, the molybdenum carbene-based metathesis catalyst system can include a compound having the structure Mo(=CHR 2 )(NAr)(OR 3 ) 2 wherein R 2 is hydrogen or hydrocarbyl, Ar is a substituted aromatic ring, and R 3 is hydrocarbyl or halohydrocarbyl. Generally, in the molybdenum carbene-based metathesis catalyst system, the compound having the structure Mo(=CHR 2 )(NAr)(OR3 ) 2 The compounds of 2 can be described using any combination of R, Ar, and R 3 .

[0085] In some aspects, for a compound having the structure Mo(=CHR 2 )(NAr)(OR 3 ), 2 R 2 can be hydrogen or a C 1 to C 20 hydrocarbyl group, or alternatively, a C 1 to C 20 hydrocarbyl group. In some aspects, R 2 can be methyl, ethyl, isopropyl, tert-butyl, phenyl, 2-methyl-2-propenyl, or 2,2-diphenylethynyl. In other aspects, R 2 can be tert-butyl, phenyl, 2-methyl-2-propenyl, or 2,2-diphenylethynyl; alternatively, tert-butyl or phenyl; alternatively, hydrogen; alternatively, tert-butyl; alternatively, phenyl; alternatively, 2-methyl-2-propenyl; or alternatively, 2,2-diphenylethynyl.

[0086] In one aspect, for a compound having the structure Mo(=CHR 2 )(NAr)(OR 3 ), 2 the substituted aromatic ring Ar can be a C 6 to C 30 aromatic group, or alternatively, a C 6 to C 20 aromatic group. In some aspects, each substituent of the substituted aromatic ring Ar can independently be a C 6 to C 20 hydrocarbyl group, a C 1 to C 10 hydrocarbyl group, or a C 1 to C 5Hydrocarbyl. In some aspects, the substituted aromatic ring Ar can be 2-substituted phenyl, 2,6-disubstituted phenyl, or 2,4,6-trisubstituted phenyl. In one aspect, each substituent of the substituted aromatic ring can independently be methyl, ethyl, isopropyl, tert-butyl, or neopentyl; alternatively, methyl, isopropyl, or tert-butyl; alternatively, methyl or isopropyl. In some aspects, each substituent of the substituted aromatic ring can independently be methyl; alternatively, isopropyl; or alternatively, tert-butyl. In some non-limiting aspects, the substituted aromatic ring Ar can be 2-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, or 2,4,6-trimethylphenyl; alternatively, 2-tert-butylphenyl; alternatively, 2,6-dimethylphenyl; alternatively, 2,6-diisopropylphenyl; or alternatively, 2,4,6-trimethylphenyl.

[0087] In one aspect, each R of the compound having the structure Mo(=CHR 2 )(NAr)(OR 3 ) 2 can independently be a C 3 to C 1 organic group, or alternatively, a C 10 to C 1 organic group. In some aspects, the C 5 to C 1 or C 10 to C 1 organic group can be a hydrocarbylhalo group (a group composed of hydrogen, carbon, and halogen atoms); alternatively, a hydrocarbylfluoro group (a group composed of hydrogen, carbon, and fluorine atoms); or alternatively, a hydrocarbyl group. In one aspect, the halogen atom of the hydrocarbylhalo group can be fluorine, chlorine, bromine, iodine, or any combination thereof; alternatively, fluorine; alternatively, chlorine; alternatively, bromine; or alternatively, iodine. In some aspects, each R 5 can independently be tert-butyl or hexafluorotert-butyl. In other aspects, (OR 3 ) 3 can represent a single organic group, wherein the two R 2 groups attached to the oxygen atom are connected via a bond between any divalent, trivalent, or tetravalent atom within the R 3 group. In a further aspect, (OR 3 ) 3 can represent a single organic group, wherein the two R 2 groups attached to the oxygen atom are connected via a carbon-carbon bond between any carbon atoms of the two R 3 groups.

[0088] In one aspect, the molybdenum carbene-based metathesis catalyst system can comprise Mo(=CH-C(CH 3 3 ))3 )(N-2,6-diisopropylphenyl)(OC(CH 3 )) 3 ), Mo(=CH-C(CH 3 )) 2 (C 6 H 5 ))(N-2,6-diisopropylphenyl)(OC(CH 3 )) 3 ), Mo(=CH-C(CH 3 )) 3 )(N-2,6-diisopropylphenyl)(OC(CH 3 )(CF 3 )) 2 ), or Mo(=CH-C(CH 3 )) 2 (C 6 H 5 ))(N-2,6-diisopropylphenyl)(OC(CH 3 )(CF 3 )) 2 ). In other aspects, the molybdenum carbene-based metathesis catalyst system can comprise Mo(=CH-C(CH 3 )) 3 )(N-2,6-diisopropylphenyl)(OC(CH 3 )) 3 ); alternatively, Mo(=CH-C(CH 3 )) 2 (C 6 H 5 ))(N-2,6-diisopropylphenyl)(OC(CH 3 )) 3 ); alternatively, Mo(=CH-C(CH 3 )) 3 )(N-2,6-diisopropylphenyl)(OC(CH 3 )(CF 3 )) 2 ); or alternatively, Mo(=CH-C(CH 3 )) 2 (C 6 H 5 ))(N-2,6-diisopropylphenyl)(OC(CH 3 )(CF 3 )) 2 ).

[0089] Optionally, the metathesis catalyst system based on metal carbenes may further comprise a support. Exemplary supports may include solid oxide materials such as alumina, silica, silica-alumina, and aluminum phosphate. Additionally, the support may comprise a polymer, and the metal carbene metathesis catalyst compound may be tethered to the support via any ligand that does not contain a metal-carbon double bond.

[0090] Catalytic isomerization catalyst system

[0091] In step c), in the presence of photochemical irradiation, all or a portion of a linear internal olefin (such as 5-decene) is contacted with the catalytic isomerization catalyst system to form a second composition comprising 1-decene. Any suitable catalytic isomerization catalyst system may be used as long as it can efficiently walk the double bond to the terminal position. In one aspect, the catalytic isomerization catalyst system may include a photocatalyst, a hydrogen atom transfer agent, a metal ion, and a proton donor. First referring to the photocatalyst, the photocatalyst may include transition metal complexes, organic dyes (e.g., 3,6-di-tert-butyl-9-mesityl-10-phenylacridinium tetrafluoroborate), 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, or semiconductors (e.g., TiO 10 ). Exemplary examples of transition metal complexes include iridium-based photocatalysts (e.g., [Ir(dF(CF 2 ))ppy) 3 (5,5'-d(CF 2 ))bpy)]PF 3 )), ruthenium-based photocatalysts, etc. While not limited thereto, suitable photocatalysts generally may have a redox potential in the range of 0.7 V to 2.0 V compared to Fc+ / Fc in MeCN, and in some cases, the range of the redox potential may be 1.3 V to 1.8 V. 6 )

[0092] The hydrogen atom transfer agent may be a Bronsted base, which in some aspects may include an organic base, and in other aspects may include a pyridine base (e.g., 4,4'-di-tert-butyl-2,2'-bipyridine), or a pyridyl ligand of a metal ion (e.g., 4,4'-di-tert-butyl-2,2'-bipyridine). Other exemplary and non-limiting examples of the transfer agent may include cytochrome p450, iron porphyrin, iron cyclam, chromyl chloride, MnO 4 , iron zeolite, etc., and any combination thereof.

[0093] The metal ion component of the catalytic isomerization catalyst system may include chromium ions (e.g., chromium(II) ions, chromium(III) ions), and, for example, the metal ions may include metal salts (e.g., chromium(II) dihalides, chromium(III) trihalides). The proton donor may include alcohols (e.g., primary alcohols, secondary alcohols, aliphatic alcohols, primary aliphatic alcohols, fluorinated alcohols), carboxylic acids, water, etc., and combinations thereof. Thus, the proton donor generally may include C 1 -C 8 Primary aliphatic alcohols, examples of which include methanol, ethanol, n-propanol, isopropanol, and the like.

[0094] There is no particular limitation on the relative amounts of the photocatalyst, hydrogen atom transfer agent, metal ions, and proton donor in the catalytic isomerization catalyst system. However, the molar ratio of the Bronsted base (or other transfer agent) to the photocatalyst generally ranges from 5:1 to 1:1 (e.g., 3:1), and additionally or alternatively, the molar ratio of the metal ions to the photocatalyst generally ranges from 3:1 to 1:1 (e.g., 2:1), and additionally or alternatively, the molar ratio of the proton donor to the photocatalyst generally ranges from 3:1 to 1:1 (e.g., 1:1).

[0095] The amount of the photocatalyst in the catalytic isomerization catalyst system relative to C 10 The amount of the linear internal olefin is not particularly limited. For example, the amount of the photocatalyst based on the linear internal olefin may range from 0.1 mol% to 10 mol% in one aspect, from 0.5 mol% to 8 mol% in another aspect, and from 1 mol% to 5 mol% in yet another aspect. 10 Using this catalyst system, step c) may optionally contact the catalyst system with C

[0096] linear internal olefins in the presence of a solvent. Although not limited thereto, organic solvents such as acetonitrile, dioxane, trifluorobenzene, etc., and mixtures thereof may be utilized. Step c) can be carried out at any suitable temperature. In some non-limiting aspects, the temperature range may be 0°C to 100°C; alternatively, 0°C to 60°C; alternatively, 0°C to 40°C; alternatively, 15°C to 75°C; alternatively, 15°C to 50°C; alternatively, 15°C to 40°C; alternatively, 20°C to 40°C; or alternatively, 30°C to 40°C. These temperature ranges are also intended to cover the cases where step c) is carried out at a series of different temperatures falling within the corresponding temperature ranges rather than at a single fixed temperature. 10 Similarly, step c) can use any suitable photochemical irradiation. The photochemical irradiation may include light of any suitable wavelength, such as blue light (e.g., light from a blue light source), and the photochemical irradiation may include wavelengths in the range of 450 to 495 nm, such as at 456 nm or near 456 nm.

[0097] ​

[0098] In another aspect, the catalytic isomerization catalyst system can include a photocatalyst, a metal-containing cocatalyst, and optionally a disulfide compound. In this regard, the photocatalyst can include decatungstate, such as sodium decatungstate or tetrabutylammonium decatungstate, but is not limited thereto. The metal-containing cocatalyst can include, for example, a cobalt-based cocatalyst, an example of which is cobalt oxime - Co(dmgH(dmgH 2 )Br 2 . When present, any suitable disulfide can be utilized, and a representative example is 2,4,6-triisopropylbenzene disulfide.

[0099] The relative amounts of the photocatalyst, the metal-containing cocatalyst, and the disulfide compound (if present) are not particularly limited. However, the molar ratio of the photocatalyst to the cocatalyst generally ranges from 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, or 1.3:1 to 1:1.3, etc.

[0100] Using this catalyst system, step c) can optionally contact the catalyst system with C 10 linear internal olefins in the presence of a solvent. Although not limited thereto, organic solvents such as acetonitrile, acetone, etc., and mixtures thereof can be utilized. Step c) can be carried out using this catalytic system at any suitable temperature. In some non-limiting aspects, the temperature range can be from 0 °C to 100 °C; alternatively, 0 °C to 60 °C; alternatively, 0 °C to 40 °C; alternatively, 15 °C to 75 °C; alternatively, 15 °C to 50 °C; alternatively, 15 °C to 40 °C; alternatively, 20 °C to 40 °C; or alternatively, 20 °C to 30 °C. These temperature ranges are also intended to cover the case where step c) is carried out at a series of different temperatures falling within the corresponding temperature range rather than at a single fixed temperature.

[0101] As described above, step c) can use suitable photochemical irradiation with this catalytic system. The photochemical irradiation can include light of any suitable wavelength, generally in the range of 300 to 500 nm or in the range of 350 to 450 nm, such as at 390 nm or around 390 nm.

[0102] Manufacturing system

[0103] The first (1-octene and 1-decene) manufacturing system provided herein can include 1) an ethylene oligomerization system, which is configured to oligomerize ethylene in the presence of a catalyst system or catalyst system components to form a composition containing an oligomer product, the oligomer product containing 15 to 80 mol% C 6 olefins, 20 to 80 mol% C 8 olefins, and 5 to 20 mol% C 10+ olefins, 2) a fractionation system configured to separate a composition comprising an oligomer product into i) a first oligomer composition comprising 1-hexene, ii) a second oligomer composition comprising 1-octene, and iii) a heavy stream comprising C 10 + olefins, 3) a metathesis system configured to contact all or a portion of the first oligomer composition with a metathesis catalyst system to form a first composition comprising C 10 linear internal olefins, 4) a catalytic isomerization system configured to contact all or a portion of the C 10 linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a second composition comprising 1-decene, and 5) a purification system configured to separate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0104] The second (1-hexene and 1-decene) production system provided herein may include 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, the oligomer product comprising at least 85 mole % C 6 olefins and at least 5 mole % C 8 + olefins, 2) a fractionation system configured to separate the composition comprising the oligomer product into a first oligomer composition comprising 1-hexene and a heavy stream comprising C 8 + olefins, 3) a metathesis system configured to contact all or a portion of the first oligomer composition with a metathesis catalyst system to form a first composition comprising C 10 linear internal olefins, 4) a catalytic isomerization system configured to contact all or a portion of the C 10 linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a second composition comprising 1-decene, and 5) a purification system configured to separate a third composition comprising at least 90 mole % 1-decene from the second composition.

[0105] Generally, the first production system and the second production system are characterized by the same features as those generally described herein for the corresponding first method and second method. Accordingly, any feature of the first method and the second method may be applied to the corresponding first production system and second production system.

[0106] Optionally, the first production system (or the second production system) may further include a metathesis purification system configured to separate a composition comprising C 10 linear internal olefins from the first composition prior to the catalytic isomerization system. The purification system may include, for example, extraction, filtration, evaporation, distillation, etc., and any combination thereof.

[0107] Now referring toFigure 1 , which illustrates a 1-octene / 1-decene production system 100 consistent with aspects of the present disclosure. The 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 Figure 1 , an ethylene feed stream 105 enters the ethylene oligomerization system 110. Figure 1 , other feed streams to the 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. Those skilled in the art will understand that the ethylene oligomerization system can have many different inputs, and the present disclosure is not limited to the options described with reference to Figure 1 or those otherwise disclosed herein. In the ethylene oligomerization system 110, the ethylene introduced via the ethylene feed stream 105 oligomerizes in the presence of a catalyst system (or catalyst system components) to form a composition 115 containing an oligomer product, which is discharged from the ethylene oligomerization system 110. Generally, the oligomer product contains 15 to 80 mol% C 6 olefins, 20 to 80 mol% C 8 olefins, and 5 to 20 mol% C 10 + olefins.

[0108] This composition 115 containing the oligomer product enters the fractionation system 120, which separates the composition 115 into a heavy stream 122 containing C 10 + 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 can be separated into a 1-hexene product stream 126 and a 1-hexene feed stream 128. Thus, all or a portion of the first oligomer composition 125 can be fed to the metathesis system 130 and contacted with a suitable metathesis catalyst system to form a first composition 135 containing C 10 linear internal olefins, which exits the metathesis system 130.

[0109] In Figure 1 , the composition 135 containing C 10 linear internal olefins enters the catalytic isomerization system 150 and is contacted with a catalytic isomerization catalyst system in the presence of photochemical irradiation in the catalytic isomerization system 150 to form a second composition 155 containing 1-decene. If desired, Figure 1 the system 100 may include a purification system 160. The second composition 155 containing 1-decene exits the catalytic isomerization system 150 and enters the purification system 160, where a third composition 165 containing at least 90 mol% 1-decene is produced and the third composition is discharged from the purification system 160.

[0110] Now referring toFigure 2 , which illustrates another 1-octene / 1-decene manufacturing system 200 consistent with aspects of the present disclosure. System 200 may include 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 an oligomer product, a heavy stream 222 comprising C 10 + olefins (and optionally spent catalyst), a second oligomer composition 224 comprising 1-octene, a first oligomer composition 225 comprising 1-hexene (which may be separated 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 is generally the same as described for the similarly numbered components in Figure 1 .

[0111] In Figure 2 , a composition 235 comprising linear internal olefins leaves the metathesis system 230 and enters a metathesis purification system 240, which is configured to separate a composition 245 comprising linear internal olefins, which leaves the metathesis purification system 240 and enters the catalytic isomerization system 250. A by-product stream 242 containing C 10 olefins is discharged from the metathesis purification system 240 and combined with the 1-hexene product stream 226. 10 6

[0112] Now referring to Figure 3 , which illustrates a 1-hexene / 1-decene manufacturing system 300 consistent with aspects of the present disclosure. System 300 may include a metathesis system 330, a catalytic isomerization system 350, a purification system 360, an ethylene feed stream 305, a first composition 335 comprising linear internal olefins, a second composition 355 comprising 1-decene, and a third composition 365 comprising at least 90 mole% 1-decene, which is generally the same as described for the similarly numbered components in 10 . Figure 1

[0113] In Figure 3 , the ethylene feed stream 305 enters an ethylene oligomerization system 310. Figure 3 Other feed streams to the 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 Figure 3the options described or otherwise disclosed herein. In the ethylene oligomerization system 310, ethylene introduced via the ethylene feed stream 305 oligomerizes in the presence of a catalyst system (or catalyst system components) to form a composition 315 comprising an oligomer product, which is discharged from the ethylene oligomerization system 310. Generally, and in contrast to Figure 1 - Figure 2 different, Figure 3 the oligomer product in 6 contains at least 85 mole % C 8 olefins and at least 5 mole % C

[0114] This composition 315 comprising the oligomer product enters a fractionation system 320, which separates the composition 315 into a heavy stream 322 comprising C 8 + olefins (and optionally spent catalyst) and a first oligomer composition 325 comprising 1-hexene. The first oligomer composition 325 comprising 1-hexene can be split into a 1-hexene product stream 326 and a 1-hexene feed stream 328. Thus, all or a portion of the first oligomer composition 325 can be fed to a metathesis system 330 and contacted with a suitable metathesis catalyst system to form a first composition 335 comprising C 10 linear internal olefins, which exits the metathesis system 330.

[0115] Normal alpha-olefin synthesis

[0116] Aspects of the present invention also relate to methods for producing normal alpha-olefins. For example, the third method described herein can include the steps (or consist essentially of the steps, or consist of the steps) of: (i) contacting a first normal alpha-olefin having the structure CH 3 (CH 2 ) n HC═CH 2 with a metathesis catalyst system to form a linear internal olefin having the structure CH 3 (CH 2 ) n HC═CH(CH 2 ) n CH 3 , and (ii) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a compound having the structure CH 3 (CH 2 ) 2n+1 HC═CH 2The second normal alpha-olefin. In the third method, n is an integer and can range from 0 to 15. Generally, the characteristics of the method (such as the characteristics of the first normal alpha-olefin, the metathesis catalyst, the linear internal olefin, the catalytic isomerization catalyst system, the second normal alpha-olefin, and the conditions for performing each step, etc.) are described independently herein, and these characteristics can be combined in any combination to further describe the disclosed normal alpha-olefin synthesis method. In addition, unless otherwise specified, additional method steps can be performed before, during, and / or after any step of any method disclosed herein.

[0117] As described herein, n can be an integer and can range from 0 to 15. In aspects consistent with the present invention, n can be an integer from 0 to 10, and in another aspect, n can be an integer from 0 to 7. In yet another aspect, n can be an integer from 1 to 7, and in still another aspect, n can be an integer from 1 to 5. For example, n can be equal to 1, equal to 2, equal to 3, equal to 4, and so on.

[0118] In some aspects 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 aspects, the first normal alpha-olefin can 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.

[0119] In one aspect of the present invention, the first normal alpha-olefin may comprise 1-butene (or consist essentially of or consist of the same), and the second normal alpha-olefin may comprise 1-hexene (or consist essentially of or consist of the same). In another aspect of the present invention, the first normal alpha-olefin may comprise 1-pentene (or consist essentially of or consist of the same), and the second normal alpha-olefin may comprise 1-octene (or consist essentially of or consist of the same). In yet another aspect of the present invention, the first normal alpha-olefin may comprise 1-hexene (or consist essentially of or consist of the same), and the second normal alpha-olefin may comprise 1-decene (or consist essentially of or consist of the same). In still another aspect of the present invention, the first normal alpha-olefin may comprise 1-octene (or consist essentially of or consist of the same), and the second normal alpha-olefin may comprise 1-tetradecene (or consist essentially of or consist of the same).

[0120] An integer n, a first normal alpha-olefin, and a second normal alpha-olefin are described herein, and their characteristics can be used without limitation to further describe the normal alpha-olefin synthesis methods disclosed herein. Other suitable values of the integer n and the selection of the first normal alpha-olefin and the second normal alpha-olefin are readily apparent from the present disclosure.

[0121] Step (i) of the third method is generally referred to as the metathesis step, and in this step, a first normal alpha-olefin having the structure CH 3 (CH 2 ) n HC=CH 2 is contacted with a metathesis catalyst system to form a linear internal olefin having the structure CH 3 (CH 2 ) n HC=CH(CH 2 ) n CH 3 . Any suitable metathesis catalyst system or any metathesis catalyst system disclosed herein can be used in the metathesis step of the third method, such as the metathesis steps described herein with respect to the first method and the second method.

[0122] Step (ii) of the third method is generally referred to as the catalytic isomerization step, and in this step, in the presence of photochemical irradiation, the linear internal olefin is contacted with a catalytic isomerization catalyst system to form a second normal alpha-olefin having the structure CH 3 (CH 2 ) 2n+1 HC=CH 2 . Any suitable catalytic isomerization catalyst system or any catalytic isomerization catalyst system disclosed herein can be used in the catalytic isomerization step of the third method, such as the catalytic isomerization steps described herein with respect to the first method and the second method.

[0123] In addition, the features of steps (i) and (ii) of the third method can be any of the features of the corresponding metathesis and catalytic isomerization steps described herein for the first and second methods. Accordingly, any feature of the first and second methods can be applied to the third method.

[0124] A fourth method is provided herein, and this method also relates to the production of normal alpha olefins. The fourth method can include the following steps (or consist essentially of the following steps, or consist of the following steps): (a) contacting a first normal alpha olefin having the structure CH 3 (CH 2 ) p HC═CH 2 and a second normal alpha olefin having the structure CH 3 (CH 2 ) q HC═CH 2 with a metathesis catalyst system to form a linear internal olefin having the structure CH 3 (CH 2 ) p HC═CH(CH 2 ) q CH 3 , and (b) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of a photochemical irradiation to form a third normal alpha olefin having the structure CH 3 (CH 2 ) p+q+1 HC═CH 2 . In the fourth method, p and q are independently integers in the range of 0 to 15. Generally, the features of the method (such as the features of 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 alpha olefin, and the conditions for carrying out each step, etc.) are described independently herein, and these features can be combined in any combination to further describe the disclosed normal alpha olefin synthesis method. In addition, unless otherwise stated, additional method steps can be performed before, during, and / or after any step of any method disclosed herein.

[0125] In this normal alpha olefin synthesis method, p and q can be independently integers in the range of 0 to 15. In aspects consistent with the present invention, p and q can be independently integers in the range of 0 to 10, while in another aspect, p and q can be independently integers in the range of 1 to 10. In yet another aspect, p and q can be independently integers in the range of 1 to 7, and in still another aspect, p and q can be independently integers in the range of 1 to 5. For example, p and q can independently be equal to 1, equal to 2, equal to 3, or equal to 4. Although not required, generally p and q are different integers.

[0126] The third normal α-olefin having the structure CH 3 (CH 2 ) p+q+1 HC=CH 2 produced by the present method is not particularly limited. However, in one aspect of the present invention, the third normal α-olefin may comprise, consist essentially 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 aspect, the third normal α-olefin may comprise, consist essentially 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 aspect, the third normal α-olefin may comprise, consist essentially of, or consist of: 1-hexene, 1-octene, 1-decene, or any combination thereof.

[0127] In one aspect of the present invention, the first normal α-olefin may comprise 1-butene, the second normal α-olefin may comprise 1-octene, and the third normal α-olefin may comprise 1-decene. In another aspect of the present invention, the first normal α-olefin may comprise 1-butene, the second normal α-olefin may comprise 1-hexene, and the third normal α-olefin may comprise 1-octene. In yet another aspect of the present invention, the first normal α-olefin may comprise propylene, the second normal α-olefin may comprise pentene, and the third normal α-olefin may comprise 1-hexene.

[0128] Integers p and q, the first normal α-olefin, the second normal α-olefin, and the third normal α-olefin are described herein, and their characteristics can be used without limitation to further describe the method for synthesizing normal α-olefins disclosed herein. Other suitable values of integers p and q and the selection of the first normal α-olefin, the second normal α-olefin, and the third normal α-olefin are readily apparent from the present disclosure.

[0129] Steps (a) and (b) of the fourth method may also have any features and properties (such as catalyst systems, reaction conditions, etc.) as described herein for steps (i) and (ii) of the third method, respectively, and any features or properties as described in the similar steps of the first method and the second method.

[0130] Examples

[0131] 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 aspects, modifications, and their equivalents will occur to those of ordinary skill in the art without departing from the spirit of the invention or the scope of the appended claims.

[0132] Constructive Example A

[0133] Constructive Example A demonstrates the conversion of 1 - hexene to 1 - decene via metathesis (homogeneous) and retro - isomerization pathways, as shown in the following synthetic scheme (where n = 3).

[0134]

[0135] The reaction scheme for the homogeneous metathesis step is shown below.

[0136]

[0137] The metathesis step can be carried out as follows. In an oven under N 2 atmosphere, a 500 mL round - bottom flask equipped with a magnetic stir bar was charged with 1 - hexene (250 mL, 168 g, approximately 2 moles). The flask was placed in an aluminum block on a temperature - controlled heating plate at about 50 °C and allowed to reach temperature equilibrium. To this stirred solution was added Grubbs 2nd generation catalyst (dichloro[1,3 - bis(2,4,6 - trimethylphenyl)-2 - imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), 4.2 mg, 4.9 μmol) to initiate the reaction. The reaction progress can be monitored by taking aliquots and analyzing their reaction equilibrium by GC - FID, which typically takes 4 - 8 hours. Any ethylene produced was bubbled out of the flask as the flask was not capped in a glove box. After the reaction was complete, the solution was cooled, filtered, and the reaction contents were distilled to isolate 5 - decene. By fractional distillation, the reaction yield was approximately 40 - 50% 5 - decene.

[0138] The reaction scheme for the photochemically induced isomerization step is shown below.

[0139]

[0140] The retro - isomerization step can be carried out as follows. Under nitrogen, a continuously stirred autoclave was charged with 1 mole of 5 - decene. To this vessel was added Ir(dF(CF 3 )ppy) 2 (5,5’ - d(CF 3 )bpy)]PF 6 (40 mmol, 4.0 mol %), 4,4′ - di - tert - butyl - 2,2′ - bipyridine (150 mmol, 15.0 mol %), and CrCl2 (100 mmol, 10 mol %). Then, PhCF was charged via the addition port 3 A solution of (6 L), MeCN (24 L), and MeOH (12 L) was added. The autoclave contained a photoelectric element for irradiating at about 450 nm for 18 hours. The autoclave may have a temperature-controlled cooling kit connected to a process cooler that maintained the reaction temperature at 35 °C. After the reaction was complete, the light source was turned off and the contents of the reactor were discharged through a silica filter plug to remove any residual solids and polar compounds. The mixture was analyzed by GC-FID, revealing a conversion to 1-decene > 90 mol %. The material could be purified by fractional distillation, monitoring the atmospheric distillation temperature of 172 °C using a BR instrument automated distillation system.

[0141] Constructive Example B

[0142] Constructive Example B is similar to Constructive Example A, except that a different retroisomerization pathway was used. The reaction scheme for the photochemically induced isomerization step is shown below.

[0143]

[0144] The retroisomerization step can be carried out as follows. Under nitrogen, 1 mol of 5-decene was charged into a continuously stirred autoclave. Co(dmgh)(dmgH 2 )(Br 2 )(50 mmol, 5.0 mol %) and a decatungstate catalyst (40 mmol, 4.0 mol %) were added to the vessel. Then, a solution of MeCN (10 L) was charged via the addition port. The autoclave contained a photoelectric element for irradiating at about 390 nm for 18 hours. The autoclave may have a temperature-controlled cooling kit connected to a process cooler that maintained the reaction temperature at room temperature (18 - 22 °C). After the reaction was complete, the light source was turned off and the contents of the reactor were discharged through a silica filter plug to remove any residual solids and polar compounds. The mixture was analyzed by GC-FID, revealing a conversion to 1-decene > 90 mol %. The material could be purified by fractional distillation, monitoring the atmospheric distillation temperature of 172 °C using a BR instrument automated distillation system.

[0145] The present invention has been described with reference to many aspects and specific embodiments. Many variations will occur to those skilled in the art in light of the detailed description. All such obvious variations are within the full scope of the appended claims. Other aspects of the present invention may include, but are not limited to, the following aspects (the aspects are described as "comprising", but alternatively may "consist essentially of" or "consist of"):

[0146] Aspect 1. A method (e.g., for manufacturing 1-octene / 1-decene), the method comprising a) separating a composition comprising an oligomer product, the 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, separating the composition into i) a first oligomer composition comprising C 6 alkanes and at least 85 mol% C 6 olefins, the C 6 olefins comprising at least 80 mol% 1-hexene, ii) a second oligomer composition comprising at least 20 mol% C 8 olefins, the C 8 olefins comprising at least 85 mol% 1-octene, and iii) a heavy material stream comprising C 10 + olefins; b) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to form a first composition comprising C 10 linear internal olefins; c) contacting all or a portion of the C 10 linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a second composition comprising 1-decene; and d) purifying the second composition to separate a third composition comprising at least 90 mol% 1-decene.

[0147] Aspect 2. The method as defined in Aspect 1, wherein the oligomer product comprises 30 to 70 mol% or 35 to 65 mol% C 6 olefins (or any other minimum, maximum, or range described herein).

[0148] Aspect 3. The method as defined in Aspect 1 or 2, wherein the oligomer product comprises 30 to 70 mol% or 35 to 65 mol% C 8 olefins (or any other minimum, maximum, or range described herein).

[0149] Aspect 4. The method as defined in any one of Aspects 1 to 3, wherein the oligomer product comprises 5 to 18 mol% or 7 to 20 mol% C 10 + olefins (or any other minimum, maximum, or range described herein).

[0150] Aspect 5. The method as defined in any one of Aspects 1 to 4, wherein the first oligomer composition comprises at least 90 mol%, at least 93 mol%, or at least 95 mol% C 6 olefins (or any other minimum, maximum, or range described herein).

[0151] Aspect 6. The method as defined in any one of Aspects 1 to 5, wherein the first oligomer composition comprises 0.5 to 12 mol%, 1 to 10 mol%, 1.5 to 8 mol% or 2 to 6 mol% C 6 alkanes (or any other minimum, maximum or range described herein).

[0152] Aspect 7. The method as defined in any one of Aspects 1 to 6, wherein the C 6 olefin comprises 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).

[0153] Aspect 8. The method as defined in any one of Aspects 1 to 7, wherein the C 6 olefin comprises 0.1 to 10 mol%, 0.5 to 8 mol% or 1 to 6 mol% internal and cyclic C 6 olefins (or any other minimum, maximum or range described herein).

[0154] Aspect 9. The method as defined in any one of Aspects 1 to 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 8 olefins (or any other minimum, maximum or range described herein).

[0155] Aspect 10. The method as defined in any one of Aspects 1 to 9, wherein the C 8 olefin comprises at least 90 mol%, at least 95 mol% or at least 97 mol% 1-octene (or any other minimum, maximum or range described herein).

[0156] Aspect 11. The method as defined in any one of Aspects 1 to 10, the method further comprising, prior to step c), separating from the first composition a composition comprising at least 90 mol%, at least 93 mol% or at least 96 mol% C 10 linear internal olefins by any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation or any combination thereof.

[0157] Aspect 12. The method as defined in any one of Aspects 1 to 11, the method further comprising contacting all or a portion of the second oligomer composition comprising C 8 olefins with the metathesis catalyst system to form a C 14 olefin composition.

[0158] Aspect 13. The method as defined in any one of Aspects 1 to 12, the method further comprising contacting the metathesis catalyst with a light oligomer composition comprising C 6 and C 8 olefins to form a composition comprising C 10 -C 14 linear internal olefins.

[0159] Aspect 14. A method (e.g., for making 1-hexene / 1-decene), the method comprising a) separating a composition comprising an oligomer product, the oligomer product comprising at least 85 mol% C 6 olefins and at least 5 mol% C 8 + olefins, separating the composition into i) a first oligomer composition comprising C 6 alkanes and at least 90 mol% C 6 olefins, the C 6 olefins comprising at least 90 mol% 1-hexene, and ii) a heavy feed stream comprising C 8 + olefins; b) contacting a metathesis catalyst system with all or a portion of the first oligomer composition to form a first composition comprising C 10 linear internal olefins; c) contacting all or a portion of the C 10 linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a second composition comprising 1-decene; and d) purifying the second composition to separate a third composition comprising at least 90 mol% 1-decene.

[0160] Aspect 15. The method as defined in Aspect 14, wherein the oligomer product comprises at least 85 mol%, at least 87 mol%, at least 90 mol%, at least 91 mol% or at least 93 mol% C 6 olefins (or any other minimum, maximum or range described herein).

[0161] Aspect 16. The method as defined in Aspect 14 or 15, wherein the oligomer product comprises 5 to 15 mol% or 5 to 12 mol% C 8 + olefins (or any other minimum, maximum or range described herein).

[0162] Aspect 17. The method as defined in any one of Aspects 14 to 16, wherein the first oligomer composition comprises at least 94 mol%, at least 96 mol% or at least 98 mol% C 6 olefins (or any other minimum, maximum or range described herein).

[0163] Aspect 18. The method as defined in any one of Aspects 14 to 17, wherein the first oligomer composition comprises 0.1 mol% to 1.5 mol%, 0.15 mol% to 1 mol%, or 0.2 mol% to 0.75 mol% C 6 alkanes (or any other minimum, maximum, or range described herein).

[0164] Aspect 19. The method as defined in any one of Aspects 14 to 18, wherein the C 6 olefin comprises at least 94 mol%, at least 96 mol%, or at least 98 mol% 1-hexene (or any other minimum, maximum, or range described herein).

[0165] Aspect 20. The method as defined in any one of Aspects 14 to 19, wherein the C 6 olefin comprises 0.1 mol% to 3 mol%, 0.2 mol% to 2 mol%, or 0.25 mol% to 1 mol% internal and cyclic C 6 olefins (or any other minimum, maximum, or range described herein).

[0166] Aspect 21. The method as defined in any one of Aspects 14 to 20, the method further comprising, prior to step c), separating from the first composition a composition comprising at least 90 mol%, at least 93 mol%, or at least 96 mol% C 10 linear internal olefins by any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation, or any combination thereof.

[0167] Aspect 22. The method as defined in any one of Aspects 1 to 21, wherein the third composition comprises at least 95 mol% or at least 98 mol% 1-decene (or any other minimum, maximum, or range described herein).

[0168] Aspect 23. The method as defined in any one of Aspects 1 to 22, wherein the purification in step d) comprises any suitable technique or any technique disclosed herein, such as extraction, filtration, evaporation, distillation, or any combination thereof.

[0169] Aspect 24. The method as defined in any one of Aspects 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.

[0170] Aspect 25. The method as defined in Aspect 24, wherein the metal oxide-based metathesis catalyst system comprises cobalt oxide, molybdenum oxide, tungsten oxide, rhenium oxide, or any combination thereof.

[0171] Aspect 26. The method as defined in aspect 25, wherein the metathesis catalyst system based on metal oxides further comprises a support and / or a metal alkyl activator.

[0172] Aspect 27. The method as defined in aspect 24, wherein the metathesis catalyst system based on metal halides comprises a halide of tungsten, a halide of molybdenum, or any combination thereof.

[0173] Aspect 28. The method as defined in aspect 27, wherein the metathesis catalyst system based on metal halides further comprises a metal alkyl activator and / or oxygen or alcohol.

[0174] Aspect 29. The method as defined in aspect 24, wherein the metathesis catalyst system based on metal carbenes comprises tungsten, tantalum, osmium, molybdenum, ruthenium, or any combination thereof.

[0175] Aspect 30. The method as defined in aspect 29, wherein the metathesis catalyst system based on metal carbenes further comprises a support.

[0176] Aspect 31. The method as defined in any one of aspects 1 to 30, wherein the catalytic isomerization catalyst system comprises a photocatalyst, a hydrogen atom transfer agent, a metal ion, and a proton donor.

[0177] Aspect 32. The method as defined in aspect 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., TiO 2 )).

[0178] Aspect 33. The method as defined in aspect 32, wherein the transition metal complex comprises an iridium-based photocatalyst (e.g., [Ir(dF(CF 3 ppy) 2 (5,5'-d(CF 3 )bpy)]PF 6 )) or a ruthenium-based photocatalyst.

[0179] Aspect 34. The method as defined in any one of aspects 31 to 33, wherein the photocatalyst has a redox potential in the range of 0.7 V to 2.0 V or 1.3 V to 1.8 V compared to Fc+ / Fc in MeCN.

[0180] Aspect 35. The method as defined in any one of aspects 31 to 34, wherein the transfer agent is a Bronsted base comprising an organic base.

[0181] Aspect 36. The method as defined in any one of Aspects 31 to 35, wherein the transfer agent is a Bronsted base comprising a pyridine base (e.g., 4,4'-di-tert-butyl-2,2'-bipyridine), or a pyridyl ligand of the metal ion (e.g., 4,4'-di-tert-butyl-2,2'-bipyridine).

[0182] Aspect 37. The method as defined in any one of Aspects 31 to 34, wherein the transfer agent comprises cytochrome p450, iron porphyrin, iron cyclam, chromyl chloride, MnO 4 , iron zeolite or any combination thereof.

[0183] Aspect 38. The method as defined in any one of Aspects 31 to 37, wherein the metal ion comprises chromium ions (e.g., chromium(II) ions, chromium(III) ions) or the metal ion comprises a metal salt (e.g., chromium(II) dihalide, chromium(III) trihalide).

[0184] Aspect 39. The method as defined in any one of Aspects 31 to 38, wherein the proton donor comprises an alcohol (e.g., primary alcohol, secondary alcohol, aliphatic alcohol, primary aliphatic alcohol, fluorinated alcohol), a carboxylic acid or water.

[0185] Aspect 40. The method as defined in any one of Aspects 31 to 38, wherein the proton donor comprises C 1 -C 8 primary aliphatic alcohol (e.g., methanol, ethanol, n-propanol, isopropanol).

[0186] Aspect 41. The method as defined in any one of Aspects 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).

[0187] Aspect 42. The method as defined in any one of Aspects 31 to 41, wherein step c) is carried out at a temperature in the range of 0 to 40 °C (e.g., about 35 °C, or any other minimum temperature, maximum temperature or temperature range disclosed herein).

[0188] Aspect 43. The method as defined in any one of Aspects 31 to 42, wherein the molar ratio of the Bronsted base to the photocatalyst ranges from 5:1 to 1:1 (e.g., 3:1), and / or the molar ratio of the metal ion to the photocatalyst ranges from 3:1 to 1:1 (e.g., 2:1), and / or the molar ratio of the proton donor to the photocatalyst ranges from 3:1 to 1:1 (e.g., 1:1), and any other minimum ratio, maximum ratio or ratio range disclosed herein.

[0189] Aspect 44. The method as defined in any one of Aspects 31 to 43, wherein based on the C 10Linear internal olefins, wherein the amount of the photocatalyst in the catalyst system ranges from 0.1 mol% to 10 mol% or 1 mol% to 5 mol% (or any other minimum amount, maximum amount or range of amounts disclosed herein).

[0190] Aspect 45. The method as defined in any one of aspects 31 to 44, wherein the photochemical irradiation comprises light of any suitable wavelength or any wavelength disclosed herein, for example, blue light, such as 450 to 495 nm, or at about 456 nm.

[0191] Aspect 46. The method as defined in any one of aspects 1 to 30, wherein the catalytic isomerization catalyst system comprises a photocatalyst, a metal-containing cocatalyst, and an optional disulfide compound.

[0192] Aspect 47. The method as defined in aspect 46, wherein the photocatalyst comprises a decatungstate (e.g., sodium decatungstate, tetrabutylammonium decatungstate).

[0193] Aspect 48. The method as defined in aspect 46 or 47, wherein the cocatalyst comprises a cobalt-based cocatalyst (e.g., cobalt oxime).

[0194] Aspect 49. The method as defined in aspect 46 or 47, wherein the cocatalyst comprises cobalt oxime (e.g., Co(dmgH(dmgH 2 )Br 2 )

[0195] Aspect 50. The method as defined in any one of aspects 46 to 49, wherein the disulfide compound comprises 2,4,6-triisopropylbenzene disulfide.

[0196] Aspect 51. The method as defined in any one of aspects 46 to 50, wherein the catalyst system further comprises a solvent (e.g., an organic solvent, such as acetonitrile, acetone, or a mixture thereof).

[0197] Aspect 52. The method as defined in any one of aspects 46 to 51, wherein step c) is carried out at a temperature in the range of 0 to 40 °C (e.g., about 25 °C, or any other minimum temperature, maximum temperature or temperature range disclosed herein).

[0198] Aspect 53. The method as defined in any one of aspects 46 to 52, wherein the molar ratio of the photocatalyst to the cocatalyst ranges from 2:1 to 1:2 (or any other minimum ratio, maximum ratio or ratio range disclosed herein).

[0199] Aspect 54. The method as defined in any one of aspects 46 to 53, wherein the photochemical irradiation comprises light of any suitable wavelength or any wavelength disclosed herein, for example, 300 to 500 nm, 350 to 450 nm or about 390 nm.

[0200] Aspect 55. A (1-octene / 1-decene) production system, the 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, the 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; 2) a fractionation system configured to separate the composition comprising the oligomer product into i) a first oligomer composition comprising 1-hexene, ii) a second oligomer composition comprising 1-octene, and iii) a heavy stream comprising C 10 + olefins; 3) a metathesis system configured to contact all or a portion of the first oligomer composition with a metathesis catalyst system to form a first composition comprising C 10 linear internal olefins; 4) a catalytic isomerization system configured to contact all or a portion of the C 10 linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a second composition comprising 1-decene; and 5) a purification system configured to separate a third composition comprising at least 90 mol% 1-decene from the second composition.

[0201] Aspect 56. A (1-hexene / 1-decene) production system, the 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, the oligomer product comprising at least 85 mol% C 6 olefins and at least 5 mol% C 8 + olefins; 2) a fractionation system configured to separate the composition comprising the oligomer product into a first oligomer composition comprising 1-hexene and a heavy stream comprising C 8 + olefins; 3) a metathesis system configured to contact all or a portion of the first oligomer composition with a metathesis catalyst system to form a first composition comprising C 10 linear internal olefins; 4) a catalytic isomerization system configured to contact all or a portion of the C 10All or a portion of the linear internal olefins is contacted with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and 5) a purification system configured to separate from the second composition a third composition comprising at least 90 mole % 1-decene.

[0202] Aspect 57. The manufacturing system as defined in aspect 55 or 56, the manufacturing system further comprising a metathesis purification system configured to separate from the first composition, prior to the catalytic isomerization system, a composition comprising C 10 A composition of linear internal olefins, wherein the purification system comprises extraction, filtration, evaporation, distillation, or any combination thereof.

[0203] Aspect 58. The manufacturing system as defined in any one of aspects 55 to 57, wherein the catalyst system or catalyst system components comprise a heteroatom ligand chromium compound complex and an alkylaluminum compound, or a heteroatom ligand, a chromium compound, and an alkylaluminum compound.

[0204] Aspect 59. The manufacturing system as defined in any one of aspects 55 to 58, wherein the metathesis catalyst system is as defined in any one of aspects 24 to 30.

[0205] Aspect 60. The manufacturing system as defined in any one of aspects 55 to 59, wherein the catalytic isomerization catalyst system is as defined in any one of aspects 31 to 54.

[0206] Aspect 61. A method comprising: (i) contacting a first normal alpha olefin having the structure CH 3 (CH 2 ) n HC=CH 2 with a metathesis catalyst system to form a linear internal olefin having the structure CH 3 (CH 2 ) n HC=CH(CH 2 ) n CH 3 , and (ii) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of a photochemical irradiation to form a second normal alpha olefin having the structure CH 3 (CH 2 ) 2n+1 HC=CH 2 ; where n is an integer from 0 to 15.

[0207] Aspect 62. The method as defined in aspect 61, wherein n is an integer from 1 to 10.

[0208] Aspect 63. The method as defined in aspect 61, wherein n is an integer from 1 to 7.

[0209] Aspect 64. The method as defined in 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.

[0210] Aspect 65. The method as defined in aspect 61, wherein the first normal alpha-olefin comprises 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or any combination thereof.

[0211] Aspect 66. The method as defined in aspect 61, wherein the first normal alpha-olefin comprises 1-butene and the second normal alpha-olefin comprises 1-hexene.

[0212] Aspect 67. The method as defined in aspect 61, wherein the first normal alpha-olefin comprises 1-pentene and the second normal alpha-olefin comprises 1-octene.

[0213] Aspect 68. The method as defined in aspect 61, wherein the first normal alpha-olefin comprises 1-hexene and the second normal alpha-olefin comprises 1-decene.

[0214] Aspect 69. The method as defined in aspect 61, wherein the first normal alpha-olefin comprises 1-octene and the second normal alpha-olefin comprises 1-tetradecene.

[0215] Aspect 70. A method comprising: (a) contacting a first normal alpha-olefin having the structure CH 3 (CH 2 ) p HC=CH 2 and a second normal alpha-olefin having the structure CH 3 (CH 2 ) q HC=CH 2 with a metathesis catalyst system to form a linear internal olefin having the structure CH 3 (CH 2 ) p HC=CH(CH 2 ) q CH 3 , and (b) contacting the linear internal olefin with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a third normal alpha-olefin having the structure CH 3 (CH 2 ) p+q+1 HC=CH 2 ; wherein p and q are independently integers from 0 to 15.

[0216] Aspect 71. The method as defined in Aspect 70, wherein p and q are independently integers from 1 to 10.

[0217] Aspect 72. The method as defined in Aspect 70, wherein p and q are independently integers from 1 to 7.

[0218] Aspect 73. The method as defined in Aspect 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.

[0219] Aspect 74. The method as defined in Aspect 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.

[0220] Aspect 75. The method as defined in 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.

[0221] Aspect 76. The method as defined in 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.

[0222] Aspect 77. The method as defined in any one of Aspects 61 to 76, wherein the metathesis catalyst system is as defined in any one of Aspects 24 to 30.

[0223] Aspect 78. The method as defined in any one of Aspects 61 to 77, wherein the catalytic isomerization catalyst system is as defined in any one of Aspects 31 to 54.

Claims

1. A method, the method comprises: a) Separating a composition containing an oligomer product, the 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, separating the composition into i) comprising C 6 alkanes and at least 85 mol% C 6 olefin of a first oligomer composition, said C 6 olefins comprising at least 80 mol% 1-hexene, ii) containing at least 20 mol% C 8 a second oligomer composition of an olefin, said C 8 olefin containing at least 85 mol% 1-octene, and iii) comprising C 10 + a heavy feed stream of olefins; b) Contacting the metathesis catalyst system with all or a portion of the first oligomer composition to form a first composition comprising C 10 linear internal olefins; c) In the presence of photochemical irradiation, contacting all or a portion of said C 10 linear internal olefin with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying the second composition to separate a third composition comprising at least 90 mol% 1-decene.

2. The method according to claim 1, wherein the oligomer product comprises: 30 to 70 mol% or 35 to 65 mol% C 6 olefins; 30 to 70 mol% or 35 to 65 mol% C 8 olefins; and 5 to 18 mol% or 7 to 20 mol% C 10 + olefins.

3. The method according to claim 1 or 2, wherein: the first oligomer composition comprises: At least 90 mol%, at least 93 mol% or at least 95 mol% C 6 olefins; and 0.5 to 12 mol%, 1 to 10 mol%, 1.5 to 8 mol% or 2 to 6 mol% C 6 alkanes; and The said C 6 olefins include: 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; and 0.1 to 10 mol%, 0.5 to 8 mol% or 1 to 6 mol% of internal and cyclic C 6 olefins.

4. The method according to any one of claims 1 to 3, 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 8 olefins; and Said C 8 The olefin contains at least 90 mol%, at least 95 mol% or at least 97 mol% 1-octene.

5. The method according to any one of claims 1 to 4, the method further comprising separating from the first composition an internal olefin composition comprising at least 90 mol%, at least 93 mol% or at least 96 mol% C 10 linear internal olefins prior to step c).

6. A method, the method comprises: a) Separating a composition comprising an oligomer product, said oligomer product comprising at least 85 mol% C 6 olefins and at least 5 mol% C 8 + olefins, and separating said composition into i) comprising C 6 alkanes and at least 90 mol% C 6 of a first oligomer composition of olefins, said C 6 olefins comprising at least 90 mol% 1-hexene, and ii) a heavy feed stream containing C 8 + olefins; b) Contacting the metathesis catalyst system with all or a portion of the first oligomer composition to form a first composition comprising C 10 linear internal olefins; c) In the presence of photochemical irradiation, contacting all or a portion of said C 10 linear internal olefins with a catalytic isomerization catalyst system to form a second composition comprising 1-decene; and d) purifying the second composition to separate a third composition comprising at least 90 mol% 1-decene.

7. The method according to claim 6, wherein the oligomer product comprises: At least 85 mol%, at least 87 mol%, at least 90 mol%, at least 91 mol% or at least 93 mol% C 6 olefins; and 5 to 15 mol% or 5 to 12 mol% C 8 + olefins.

8. The method according to claim 6 or 7, wherein: the first oligomer composition comprises: At least 94 mol%, at least 96 mol% or at least 98 mol% C 6 olefin; and 0.1 mol% to 1.5 mol%, 0.15 mol% to 1 mol% or 0.2 mol% to 0.75 mol% C 6 alkanes; and The said C 6 olefins include: at least 94 mol%, at least 96 mol% or at least 98 mol% 1-hexene; and 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 olefins.

9. The method according to any one of claims 6 to 8, the method further comprising separating, before step c), an internal olefin composition comprising at least 90 mol%, at least 93 mol% or at least 96 mol% C 10 linear internal olefins from the first composition.

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

11. A 1-octene / 1-decene production system, the 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 an oligomer product, the oligomer product comprising 15 to 80 mole % C 6 olefins, 20 to 80 mole % C 8 olefins and 5 to 20 mole % C 10 + olefins; 2) A fractionation system configured to separate the composition comprising the oligomer product into i) a first oligomer composition comprising 1-hexene, ii) a second oligomer composition comprising 1-octene, and iii) a heavy feed stream comprising C 10 + olefins; 3) A metathesis system configured to contact all or a portion of the metathesis catalyst system with the first oligomer composition to form a first composition comprising C 10 linear internal olefins; 4) A catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a second composition comprising 1-decene; and 10 ​ 5) a purification system configured to separate from the second composition a third composition comprising at least 90 mol% 1-decene.

12. A 1-hexene / 1-decene production system, the 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 an oligomer product, the oligomer product comprising at least 85 mole % C 6 olefins and at least 5 mole % C 8 + olefins; 2) A fractionation system configured to separate the composition comprising the oligomer product into a first oligomer composition comprising 1-hexene and a heavy feed stream comprising C 8 + olefins; 3) A metathesis system configured to contact all or a portion of the metathesis catalyst system with the first oligomer composition to form a first composition comprising C 10 linear internal olefins; 4) A catalytic isomerization system configured to contact all or a portion of the linear internal olefins with a catalytic isomerization catalyst system in the presence of photochemical irradiation to form a second composition comprising 1-decene; and 10 ​ 5) a purification system configured to separate from the second composition a third composition comprising at least 90 mol% 1-decene.

13. The system according to claim 11 or 12, wherein the system further comprises a metathesis purification system configured to separate from the first composition a composition comprising C 10 linear internal olefins prior to the catalytic isomerization system.

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

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

16. A method, the method comprises: (i) contacting a first normal alpha-olefin having the structure CH 3 (CH 2 ) n HC=CH 2 with a metathesis catalyst system to form a linear internal olefin having the structure CH 3 (CH 2 ) n HC=CH(CH 2 ) n CH 3 ; and (ii) In the presence of photochemical irradiation, contacting the linear internal olefin with a catalytic isomerization catalyst system to form a second normal alpha-olefin having the structure CH 3 (CH 2 ) 2n+1 HC=CH 2 ; where n is an integer from 0 to 15; or (a) To make it have the structure CH 3 (CH 2 ) p HC=CH 2 of the first normal α-olefin and having the structure CH 3 (CH 2 ) q HC=CH 2 of the second normal α-olefin are contacted with a metathesis catalyst system to form a linear internal olefin having the structure CH 3 (CH 2 ) p HC=CH(CH 2 ) q CH 3 ; and (b) In the presence of photochemical irradiation, contacting the linear internal olefin with a catalytic isomerization catalyst system to form a third normal alpha-olefin having the structure CH 3 (CH 2 ) p+q+1 HC=CH 2 ; where p and q are independently integers from 0 to 15.

17. The method according to claim 16, wherein the method comprises step (i) and step (ii).

18. The method according to claim 17, wherein: 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 the first normal alpha-olefin comprises 1-octene and the second normal alpha-olefin comprises 1-tetradecene.

19. The method according to claim 16, wherein the method comprises step (a) and step (b).

20. The method according to claim 19, 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; or The first normal alpha-olefin includes 1-butene, the second normal alpha-olefin includes 1-hexene, and the third normal alpha-olefin includes 1-octene; or The first normal alpha-olefin includes propylene, the second normal alpha-olefin includes pentene, and the third normal alpha-olefin includes 1-hexene.

21. The method or system according to 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. The method or system according to any one of claims 1 to 21, wherein the catalytic isomerization catalyst system includes a photocatalyst, a hydrogen atom transfer agent, metal ions, and a proton donor.

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

24. The method or system according to claim 22 or 23, wherein the photochemical irradiation includes light having a wavelength range of 450 to 495 nm.

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

26. The method or system according to claim 25, wherein the molar ratio of the photocatalyst to the cocatalyst ranges from 2:1 to 1:

2.

27. The method or system according to claim 25 or 26, wherein the photochemical irradiation includes light having a wavelength range of 300 to 500 nm.

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